TREA

FUNGICIDAL HALOMETHYL KETONES AND HYDRATES AND THEIR MIXTURES

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Information

  • Patent Application
  • 20240122180
  • Publication Number
    20240122180
  • Date Filed
    March 11, 2021
    3 years ago
  • Date Published
    April 18, 2024
    18 days ago
Information
Abstract
Disclosed is a fungicidal composition comprising (a) at least one compound selected from the compounds of Formula 1, including all geometric and stereoisomers, tautomers, A-oxides, and salts thereof, wherein E, L, J, A and T are as defined in the disclosure; and (b) at least one additional fungicidal compound. Also disclosed is a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula 1, an A-oxide, or salt thereof (e.g., as a component in the aforesaid composition). Also disclosed is a composition comprising: (a) at least one compound selected from the compounds of Formula 1 described above, A-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.
Description
FIELD OF THE INVENTION

This invention relates to certain halomethyl ketone and hydrate derivatives, their N-oxides and salts, and to mixtures and compositions comprising such halomethyl ketone and hydrate derivatives and methods for using such derivatives and their mixtures and compositions as fungicides.


BACKGROUND OF THE INVENTION

The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. In addition to often being highly destructive, plant diseases can be difficult to control and may develop resistance to commercial fungicides. Many products are commercially available for these purposes, but the need continues for new fungicidal compounds which are more effective, less costly, less toxic, environmentally safer or have different sites of action.


Besides introduction of new fungicides, combinations of fungicides are often used to facilitate disease control, to broaden spectrum of control and to retard resistance development.


Furthermore, certain rare combinations of fungicides demonstrate a greater-than-additive (i.e. synergistic) effect to provide commercially important levels of plant disease control. The advantages of particular fungicide combinations are recognized in the art to vary, depending on such factors as the particular plant species and plant disease to be treated, and whether the plants are treated before or after infection with the fungal plant pathogen. Accordingly new advantageous combinations are needed to provide a variety of options to best satisfy particular plant disease control needs. Such combinations have now been discovered.


SUMMARY OF THE INVENTION

This invention relates to a fungicidal composition (i.e. combination, mixture) comprising

    • (a) at least one compound selected from the compounds of Formula 1 (including all stereoisomers), tautomers, N-oxides, and salts thereof,




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wherein

    • T is selected from the group consisting of:




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    • wherein the bond extending to the left is attached to A;

    • R1 is CF3, CHF2, CCl3, CHCl2, CF2Cl, CFCl2 or CHFCl;

    • W is O, S or NR3;

    • R3 is H, cyano, nitro, C(═O)OH, benzyl, C1-C4 alkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, OR3a or NR3bR3c;

    • R3a is H, benzyl, C1-C4 alkyl, C2-C4 alkylcarbonyl or C2-C4 haloalkylcarbonyl;

    • R3b is H, C1-C4 alkyl, C2-C4 alkylcarbonyl or C2-C4 haloalkylcarbonyl;

    • R3c is H or C1-C4 alkyl; or

    • R3b and R3c are taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups;

    • X is O, S or NR5a;

    • Y is O, S or NR5b;

    • R5a and R5b are each independently H, hydroxy or C1-C4 alkyl;

    • R2a and R2b are each independently H, C1-C4 alkyl, C2-C4 alkenyl, C3-C15 trialkylsilyl, C3-C15 halotrialkylsilyl, (CR4aR4b)p—OH, (CR4aR4b)p—SH, (CR4aR4b)p—Cl or (CR4aR4b)p—Br; or

    • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5- to 7-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members;

    • R2c is C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl or trifluoromethylsulfonyl, each optionally substituted with up 2 substituents independently selected from cyano, hydroxy, SC≡N and C1-C2 alkoxy;

    • R2d is H, cyano, halogen or C1-C4 alkyl;

    • each R4a and R4b is independently H or C1-C4 alkyl;

    • p is 2 or 3;

    • when T is T-1 or T-2, then A is A1-A2-CR6aR6b, wherein A1 is connected to J, and CR6aR6b is connected to T;

    • when T is T-3, then A is A1-A2, wherein A1 is connected to J, and A2 is connected to T;

    • A1 is CR6cR6d, N(R7a), O or S;

    • A2 is a direct bond, CR6eR6f, N(R7b), O or S;

    • R6a, R6b, R6c, R6d, R6e and R6f are each independently H, cyano, hydroxy, halogen, C(═O)OCH3 or C1-C4 alkyl;

    • R7a and R7b are each independently H, C(═O)H, cyano, C1-C4 alkyl or C2-C4 alkylcarbonyl;

    • J is selected from the group consisting of:







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    • wherein the bond extending to the left is attached to L, and the bond extending to the right is attached to A;

    • each R8 is independently F, Cl, I, Br, cyano, methyl, trifluoromethyl or methoxy;

    • q is 0, 1, 2, 3 or 4;

    • L is (CR9aR9b)n;

    • each R9a and R9b is independently H, halogen, cyano, hydroxy, nitro, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy;

    • n is 0, 1, 2 or 3;

    • E is C1-C6 alkyl or C1-C6 haloalkyl; or

    • E is E1 or E2;

    • E1 is amino, cyano, hydroxy, nitro, CH(═O), C(═O)OH, C(═O)NH2, C(═S)NH2, OC(═O)NH2, OC(═S)NH2, NHC(═O)NH2, NHC(═S)NH2, SC≡N, —CH═NNHC(═O)OC1-C6 alkyl or —N(OCH3)C(═O)C1-C6 alkyl; or

    • E1 is C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylthio, C2-C6 alkenylthio, C2-C6 alkynylthio, C1-C6 alkylsulfinyl, C2-C6 alkenylsulfinyl, C2-C6 alkynylsulfinyl, C1-C6 alkylsulfonyl, C2-C6 alkenylsulfonyl, C2-C6 alkynylsulfonyl, C1-C6 alkylsulfonylamino, C2-C6 alkenylsulfonylamino, C2-C6 alkynylsulfonylamino, C1-C6 alkylaminosulfonyl, C2-C6 dialkylaminosulfonyl, C2-C6 alkenylaminosulfonyl, C2-C6 alkynylaminosulfonyl, C1-C6 alkylaminosulfonylamino, C2-C6 alkenylaminosulfonylamino, C2-C6 alkynylaminosulfonylamino, C2-C6 alkylcarbonyl, C3-C6 alkenylcarbonyl, C3-C6 alkynylcarbonyl, C2-C6 alkylaminocarbonyl, C3-C6 alkenylaminocarbonyl, C3-C6 alkynylaminocarbonyl, C2-C6 alkylcarbonylamino, C3-C6 alkenylcarbonylamino, C3-C6 alkynylcarbonylamino, C2-C6 alkylaminocarbonylamino, C3-C6 alkenylaminocarbonylamino, C3-C6 alkynylaminocarbonylamino, C2-C6 alkylcarbonyloxy, C3-C6 alkenylcarbonyloxy, C3-C6 alkynylcarbonyloxy, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C2-C6 alkylaminocarbonyloxy, C3-C6 alkenylaminocarbonyloxy, C3-C6 alkynylaminocarbonyloxy, C2-C6 alkoxycarbonylamino, C3-C6 alkenyloxycarbonylamino, C3-C6 alkynyloxycarbonylamino, C2-C6 alkylamino(thiocarbonyl)oxy, C3-C6 alkenylamino(thiocarbonyl)oxy, C3-C6 alkynylamino(thiocarbonyl)oxy, C2-C6 alkoxy(thiocarbonyl)amino, C3-C6 alkenyloxy(thiocarbonyl)amino, C3-C6 alkynyloxy(thiocarbonyl)amino, C2-C6 alkyl(thiocarbonyl), C2-C6 (alkylthio)carbonyl, C3-C6 alkenyl(thiocarbonyl), C3-C6 (alkenylthio)carbonyl, C3-C6 alkynyl(thiocarbonyl), C3-C6 (alkynylthio)carbonyl, C2-C6 alkylamino(thiocarbonyl), C3-C6 alkenylamino(thiocarbonyl), C3-C6 alkynylamino(thiocarbonyl), C2-C6 alkyl(thiocarbonyl)amino, C2-C6 (alkylthio)carbonylamino, C3-C6 alkenyl(thiocarbonyl)amino, C3-C6 (alkenylthio)carbonylamino, C3-C6 alkynyl(thiocarbonyl)amino, C3-C6 (alkynylthio)carbonylamino, C2-C6 alkylamino(thiocarbonyl)amino, C3-C6 alkenylamino(thiocarbonyl)amino or C3-C6 alkynylamino(thiocarbonyl)amino, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b;

    • R10a is phenyl optionally substituted with up to 3 substituents independently selected from R11a; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 3 carbon atom ring members are independently selected from C(═O) and C(═S), and sulfur atom ring members are independently S(═O)u(═NR12)v, each ring optionally substituted with up to 3 substituents independently selected from R11a on carbon atom ring members and R11b on nitrogen atom ring members;

    • each R10b is independently amino, cyano, halogen, hydroxy, nitro, SC≡N, —SH, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C4 dialkylamino, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C2-C5 haloalkoxycarbonyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl;

    • each R11a is independently halogen, hydroxy, cyano, amino, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 hydroxyalkyl, C3-C6 cycloalkyl, C4-C7 cycloalkylalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 alkoxyalkyl, C2-C6 alkylcarbonyloxy, C1-C4 alkylthio, C1-C4 haloalkylthio, C2-C6 alkylcarbonylthio, C1-C4 alkylsulfinyl, C1-C4 haloalkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfonyloxy, C1-C4 alkylamino, C2-C8 dialkylamino, C3-C6 cycloalkylamino, C2-C4 alkylcarbonyl, C3-C5 alkenylcarbonyl, C3-C5 alkynylcarbonyl, C4-C7 cycloalkylcarbonyl, C5-C8 cycloalkylalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7 alkenyloxycarbonyl, C3-C7 alkynyloxycarbonyl, C4-C7 cycloalkoxylcarbonyl, C5-C8 cycloalkylalkoxylcarbonyl, C2-C6 alkylaminocarbonyl, C3-C6 alkenylaminocarbonyl, C3-C6 alkynylaminocarbonyl, C4-C7 cycloalkylaminocarbonyl, C5-C8 cycloalkylalkylaminocarbonyl, C3-C8 dialkylaminocarbonyl or C3-C6 trialkylsilyl;

    • each R11b is independently C(═O)H, C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl;

    • each R12 is independently H, cyano, C1-C3 alkyl or C1-C3 haloalkyl;

    • each u and v are independently 0, 1 or 2, provided that the sum of u and v are 0, 1 or 2;

    • E2 is G-Z, wherein Z is attached to L;

    • G is phenyl optionally substituted with up to 3 substituents independently selected from R13; or

    • G is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R13; or

    • G is a 3- to 7-membered nonaromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(═O), C(═S), S(═O) and S(═O)2, each ring or ring system optionally substituted with up to 3 substituents independently selected from R13;

    • each R13 is independently cyano, halogen, hydroxy, nitro, —SH, SF5, CH(═O), C(═O)OH, NR14aR14b, C(═O)NR14aR14b, C(═O)C(═O)NR14aR14b, C(═S)NR14aR14b, C(R15)═NR16, N═CR17NR18aR18b or —U—V-Q; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C3-C7 cycloalkenyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C3-C7 cycloalkoxy, C1-C6 alkylthio, C1-C6 alkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 alkylaminosulfinyl, C2-C6 dialkylaminosulfinyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C3-C6 alkoxycarbonylcarbonyl, C2-C6 alkylcarbonyloxy, C4-C7 cycloalkylcarbonyloxy, C2-C6 alkoxycarbonyloxy, C4-C7 cycloalkoxycarbonyloxy, C2-C6 alkylaminocarbonyloxy, C4-C7 cycloalkylaminocarbonyloxy, C2-C6 alkylcarbonylamino, C4-C7 cycloalkylcarbonylamino, C2-C6 alkoxycarbonylamino, C4-C7 cycloalkoxycarbonylamino, C2-C6 alkylaminocarbonylamino, C4-C7 cycloalkylaminocarbonylamino or C2-C6 dialkoxyphosphinyl, each optionally substituted with up to 3 substituents independently selected from R19;

    • each R14a is independently H, cyano, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C1-C5 alkoxy, C2-C4 alkoxyalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylthioalkyl, C2-C4 alkylsulfinylalkyl, C2-C4 alkylsulfonylalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl;

    • each R14b is independently H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 hydroxyalkyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C6-C14 cycloalkylcycloalkyl, C5-C10 alkylcycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C8 alkoxyalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfinylalkyl, C2-C6 alkylsulfonylalkyl, C2-C6 alkylaminoalkyl, C2-C6 haloalkylaminoalkyl, C3-C8 dialkylaminoalkyl or C4-C10 cycloalkylaminoalkyl, each optionally substituted with up to 1 substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C3-C15 trialkylsilyl, C3-C15 halotrialkylsilyl and pyrimidinyl; or

    • R14a and R14b are taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 3 substituents independently selected from halogen and C1-C3 alkyl;

    • each R15 is independently H, cyano, halogen, methyl, methoxy, methylthio or methoxycarbonyl;

    • each R16 is independently hydroxy or NR20aR20b; or C1-C4 alkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 alkylcarbonyloxy, C2-C5 alkoxycarbonyloxy, C2-C5 alkylaminocarbonyloxy or C3-C5 dialkylaminocarbonyloxy, each optionally substituted with up to 1 substituent selected from cyano, halogen, hydroxy and C(═O)OH;

    • each R17 is independently H, methyl, methoxy or methylthio;

    • each R18a and R18b is independently H or C1-C4 alkyl; or

    • R18a and R18b are taken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups;

    • each R19 is independently amino, cyano, halogen, hydroxy, nitro, —SH, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxyalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C5 alkoxycarbonyl, C1-C6 alkylamino, C2-C6 dialkylamino, C2-C5 alkylaminocarbonyl, C3-C5 dialkylaminocarbonyl, C3-C5 alkylthioalkylcarbonyl, C3-C15 trialkylsily, C3-C15 halotrialkylsilyl, C(R21)═NOR22 or C(R23)═NR24;

    • each U is independently a direct bond, C(═O)O, C(═O)N(R25) or C(═S)N(R26), wherein the atom to the left is connected to G, and the atom to the right is connected to V;

    • each V is independently a direct bond; or C1-C6 alkylene, C2-C6 alkenylene, C3-C6 alkynylene, C3-C6 cycloalkylene or C3-C6 cycloalkenylene, wherein up to 1 carbon atom is C(═O), each optionally substituted with up to 3 substituents independently selected from halogen, cyano, nitro, hydroxy, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy;

    • each Q is independently phenyl or phenoxy, each optionally substituted with up to 2 substituents independently selected from R27; or

    • each Q is independently a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R27; or

    • each Q is independently a 3- to 7-membered nonaromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(═O), C(═S), S(═O) and S(═O)2, each ring optionally substituted with up to 2 substituents independently selected from R27;

    • each R20a is independently H, C1-C4 alkyl or C2-C4 alkylcarbonyl;

    • each R20b is independently H, cyano, C1-C5 alkyl, C2-C5 alkylcarbonyl, C2-C5 haloalkylcarbonyl, C4-C7 cycloalkylcarbonyl, C2-C5 alkoxycarbonyl, C3-C5 alkoxycarbonylalkyl, C2-C5 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl; or

    • R20a and R20b are taken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups;

    • each R21 and R23 is independently H, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl or C1-C3 alkoxy; or phenyl optionally substituted with up to 2 substituents independently selected from halogen and C1-C3 alkyl;

    • each R22 is independently H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C2-C5 haloalkenyl, C2-C5 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C5 alkylcarbonyl or C2-C5 alkoxycarbonyl; or

    • each R22 is phenyl optionally substituted with up to 2 substituents independently selected halogen and C1-C3 alkyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and C1-C3 alkyl;

    • each R24 is independently H, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

    • each R25 and R26 is independently H, cyano, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkylcarbonyl, C2-C4 haloalkylcarbonyl, C2-C4 alkoxycarbonyl or C2-C4 haloalkoxycarbonyl;

    • each R27 is independently halogen, cyano, hydroxy, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C1-C4 alkoxy, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

    • Z is a direct bond, O, S(═O)m, N(R28), C(═O), C(═O)O, C(═O)N(R28), NR28C(═O), N(R28)C(═O)N(R28), N(R28)C(═S)N(R28), OC(═O)N(R28), N(R28)C(═O)O, S(O)2N(R28), N(R28)S(═O)2 or N(R28)S(O)2N(R28), wherein the atom to the right is connected to L;

    • each R28 is independently H, C1-C3 alkyl, C1-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; and

    • m is 0, 1 or 2; and

    • (b) at least one additional fungicidal compound;


      provided that:

    • (a) when A1 is N(R7a), O or S, then A2 is a direct bond or CR6eR6f; and

    • (b) when A2 is N(R7b), O or S; then A1 is CR6cR6d.





This invention also relates to a composition comprising: (a) at least one compound selected from the compounds of Formula 1 described above, N-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.


This invention also relates to a composition comprising one of the aforesaid compositions comprising component (a) and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.


This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of one of the aforesaid compositions.


The aforedescribed method can also be described as a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of one of the aforesaid compositions to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed).


This invention also relates to a compound of Formula 1 described above, a tautomer, an N-oxide or salt thereof.







DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.


The transitional phrase “consisting of” excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.


The transitional phrase “consisting essentially of” is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.


Where applicants have defined an invention or a portion thereof with an open-ended term such as “comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of” or “consisting of.”


Further, unless expressly stated to the contrary, “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).


Also, the indefinite articles “a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore “a” or “an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.


The term “agronomic” refers to the production of field crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).


The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.


The term “crop vigor” refers to rate of growth or biomass accumulation of a crop plant. An “increase in vigor” refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant. The term “crop yield” refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant. An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.


The term “biologically effective amount” refers to the amount of a biologically active compound (e.g., a compound of Formula 1 or a mixture with at least one other fungicidal compound) sufficient to produce the desired biological effect when applied to (i.e. contacted with) a fungus to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the fungal disease or for other desired effect (e.g., increasing plant vigor).


As referred to in the present disclosure and claims, “plant” includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds). Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.


As referred to herein, the term “seedling”, used either alone or in a combination of words means a young plant developing from the embryo of a seed.


As referred to herein, the term “broadleaf” used either alone or in words such as “broadleaf crop” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.


As referred to in this disclosure, the terms “fungal pathogen” and “fungal plant pathogen” include pathogens in the Ascomycota, Basidiomycota and Zygomycota phyla, and the fungal-like Oomycota class that are the causal agents of a broad spectrum of plant diseases of economic importance, affecting ornamental, turf, vegetable, field, cereal and fruit crops. In the context of this disclosure, “protecting a plant from disease” or “control of a plant disease” includes preventative action (interruption of the fungal cycle of infection, colonization, symptom development and spore production) and/or curative action (inhibition of colonization of plant host tissues).


As used herein, the term “mode of action” (MOA) is as define by the Fungicide Resistance Action Committee (FRAC), and is used to distinguish fungicides according to their biochemical mode of action in the biosynthetic pathways of plant pathogens, and their resistance risk. FRAC-defined modes of actions include (A) nucleic acids metabolism, (B) cytoskeleton and motor protein, (C) respiration, (D) amino acids and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell wall, (P) host plant defense induction, (U) unknown mode of action, (M) chemicals with multi-site activity and (BM) biologicals with multiple modes of action. Each mode of action (i.e. letters A through BM) contain one or more subgroups (e.g., A includes subgroups A1, A2, A3 and A4) based either on individual validated target sites of action, or in cases where the precise target site is unknown, based on cross resistance profiles within a group or in relation to other groups. Each of these subgroups (e.g., A1, A2, A3 and A4) is assigned a FRAC code which is a number and/or letter. For example, the FRAC code for subgroup A1 is 4. Additional information on target sites and FRAC codes can be obtained from publicly available databases maintained, for example, by FRAC.


As used herein, the term “cross resistance” refers to the phenomenon that occurs when a pathogen develops resistance to one fungicide and simultaneously becomes resistant to one or more other fungicides. These other fungicides are typically, but not always, in the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.


In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain and branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, and the different butyl, pentyl and hexyl isomers. “Alkenyl” includes straight-chain and branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. “Alkynyl” includes straight-chain and branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. “Alkylene” denotes a straight-chain or branched alkanediyl. Examples of “alkylene” include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and the different butylene isomers. “Alkenylene” denotes a straight-chain or branched alkenediyl containing one olefinic bond. Examples of “alkenylene” include CH═CH, CH2CH═CH, CH═C(CH3) and the different butenylene isomers. “Alkynylene” denotes a straight-chain or branched alkynediyl containing one triple bond. Examples of “alkynylene” include CH2C≡C, C≡CCH2, and the different butynylene, pentynylene or hexynylene isomers. The term “cycloalkylene” denotes a cycloalkanediyl ring. Examples of “cycloalkylene” include cyclobutanediyl, cyclopentanediyl and cyclohexanediyl. The term “cycloalkenylene” denotes a cycloalkenediyl ring containing one olefinic bond. Examples of “cycloalkenylene” include cyclopropenediyl and cyclopentenediyl.


“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy, i-propyloxy, and the different butoxy, pentoxy and hexyloxy isomers. “Alkenyloxy” includes straight-chain and branched alkenyl attached to and linked through an oxygen atom. Examples of “alkenyloxy” include H2C═CHCH2O and CH3CH═CHCH2O. “Alkynyloxy” includes straight-chain and branched alkynyl attached to and linked through an oxygen atom. Examples of “alkynyloxy” include HC≡CCH2O and CH3C≡CCH2O.


The term “alkylthio” includes straight-chain and branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers. “Alkylsulfinyl” includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH3S(═O), CH3CH2S(═O), CH3CH2CH2S(═O), (CH3)2CHS(═O), and the different butylsulfinyl isomers. Examples of “alkylsulfonyl” include CH3S(═O)2, CH3CH2S(═O)2, CH3CH2CH2S(═O)2, (CH3)2CHS(═O)2, and the different butylsulfonyl isomers. “Alkenylthio” includes straight-chain and branched alkenyl attached to and linked through a sulfur atom. Examples of “alkenylthio” include H2C═CHCH2S and CH3CH═CHCH2S. “Alkenylsulfinyl” includes both enantiomers of an alkenylsulfinyl group. Examples of “alkenylsulfinyl” include H2C═CHCH2S(═O), CH3CH═CHCH2S(═O), (CH3)2C═CHCH2S(═O). Examples of “alkenylsulfonyl” include CH3CH═CHS(═O)2, (CH3)2C═CHCH2S(═O)2. “Alkynylthio” includes straight-chain and branched alkynyl attached to and linked through a sulfur atom. Examples of “alkynylthio” include HC≡CCH2S and CH3C≡CCH2S. “Alkynylsulfinyl” includes both enantiomers of an alkynylsulfinyl group. Examples of “alkynylsulfinyl” include HC≡CCH2S(═O), CH3C≡CCH2S(═O). Examples of “alkynylsulfonyl” include CH3C≡CS(═O)2, CH3C≡CCH2S(═O)2.


“Alkylthioalkyl” denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2SCH2 and CH3CH2SCH2CH2; “alkylsulfinylalkyl” and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively.


“(Alkylthio)carbonyl” denotes a straight-chain or branched alkylthio group bonded to a C(═O) moiety. Examples of “(alkylthio)carbonyl” include CH3SC(═O), CH3CH2CH2SC(═O) and (CH3)2CHSC(═O). The terms “(alkenylthio)carbonyl” and “(alkynylthio)carbonyl” are likewise defined. Examples of “(alkenylthio)carbonyl” include H2C═CHCH2SC(═O) and CH3CH2CH═CHSC(═O). Examples of “(alkynylthio)carbonyl” include HC≡CCH2SC(═O) and CH3C≡CCH2SC(═O).


“Alkyl(thiocarbonyl)” denotes a straight-chain or branched alkyl group bonded to a C(═S) moiety. Examples of “alkyl(thiocarbonyl)” include CH3CH2C(═S), CH3CH2CH2C(═S) and (CH3)2CHCH2C(═S). The terms “alkenyl(thiocarbonyl)” and “alkynyl(thiocarbonyl)” are likewise defined. Examples of “alkenyl(thiocarbonyl)” include H2C═CHCH2CH2C(═S) and CH3CH2CH═CHC(═S). Examples of “alkynyl(thiocarbonyl)” include HC≡CCH2CH2C(═S) and CH3C≡CCH2C(═S).


“Alkylamino(thiocarbonyl)” denotes a straight-chain or branched alkylamino group bonded to a C(═S) moiety. Examples of “alkylamino(thiocarbonyl)” include CH3NHC(═S), CH3CH2CH2NHC(═S) and (CH3)2CHNHC(═S). The terms “alkenylamino(thiocarbonyl)” and “alkynylamino(thiocarbonyl)” are likewise defined. Examples of “alkenylamino(thiocarbonyl)” include H2C═CHCH2CH2NHC(═S) and CH3CH2CH═CHNHC(═S). Examples of “alkynylamino(thiocarbonyl)” include HC≡CCH2CH2NHC(═S) and CH3C≡CCH2NHC(═S).


“(Alkylthio)carbonylamino” denotes a straight-chain or branched alkylthio group bonded to a C(═O)NH moiety. Examples of “(alkylthio)carbonylamino” include CH3CH2SC(═O)NH, CH3CH2CH2SC(═O)NH and (CH3)2CHSC(═O)NH. The terms “(alkenylthio)carbonylamino” and “(alkynylthio)carbonylamino” are likewise defined. Examples of “(alkenylthio)carbonylamino include H2C═CHCH2SC(═O)NH and CH3CH═CHSC(═O)NH. Examples of “(alkynylthio)carbonylamino” include HC≡CCH2CH2SC(═O)NH and CH3C≡CCH2CH2SC(═O)NH.


“Alkylamino” includes an NH radical substituted with a straight-chain or branched alkyl group. Examples of “alkylamino” include CH3CH2NH, CH3CH2CH2NH, and (CH3)2CHCH2NH. Examples of “dialkylamino” include (CH3)2N, (CH3CH2CH2)2N and CH3CH2(CH3)N. “Alkylaminoalkyl” denotes alkylamino substitution on alkyl. Examples of “alkylaminoalkyl” include CH3NHCH2, CH3NHCH2CH2, CH3CH2NHCH2, CH3CH2CH2CH2NHCH2 and CH3CH2NHCH2CH2.


“Alkylcarbonyl” denotes a straight-chain or branched alkyl group bonded to a C(═O) moiety. Examples of “alkylcarbonyl” include CH3C(═O), CH3CH2CH2C(═O) and (CH3)2CHC(═O). The terms “alkenylcarbonyl” and “alkynylcarbonyl” are likewise defined. Examples of “alkenylcarbonyl” include H2C═CHCH2C(═O) and CH3CH2CH═CHC(═O). Examples of “alkynylcarbonyl” include HC≡CCH2C(═O) and CH3C≡CCH2C(═O). “Alkoxycarbonyl” includes a C(═O) moiety substituted with a straight-chain or branched alkoxy group. Examples of “alkoxycarbonyl” include CH3OC(═O), CH3CH2OC(═O), CH3CH2CH2OC(═O), (CH3)2CHOC(═O). The terms “alkenyloxycarbonyl” and “alkynyloxycarbonyl” are likewise defined. Examples of “alkenyloxycarbonyl” include H2C═CHCH2OC(═O) and CH3CH2CH═CHOC(═O). Examples of “alkynyloxycarbonyl” include HC≡CCH2OC(═O) and CH3C≡CCH2OC(═O).


“Alkylaminocarbonyl” denotes a straight-chain or branched alkyl group bonded to a NHC(═O) moiety. Examples of “alkylaminocarbonyl” include CH3NHC(═O), CH3CH2NHC(═O), CH3CH2CH2NHC(═O), (CH3)2CHNHC(═O). The terms “alkenylaminocarbonyl” and “alkynylaminocarbonyl” are likewise defined. Examples of “alkenylaminocarbonyl” include H2C═CHCH2NHC(═O) and (CH3)2C═CHCH2NHC(═O). Examples of “alkynylaminocarbonyl” include CH3C≡CNHC(═O) and CH3C≡CCH2NHC(═O). Examples of “dialkylaminocarbonyl” include (CH3)2N(═O), (CH3CH2)2NC(═O), CH3CH2(CH3)NC(═O), (CH3)2CH(CH3)NC(═O) and CH3CH2CH2(CH3)NC(═O).


The term “alkylcarbonylamino” denotes a straight-chain or branched alkyl group bonded to a C(═O)NH moiety. Examples of “alkylcarbonylamino” include CH3CH2C(═O)NH and CH3CH2CH2C(═O)NH. The terms “alkenylcarbonylamino” and “alkynylcarbonylamino” are likewise defined. Examples of “alkenylcarbonylamino” include H2C═CHCH2C(═O)NH and (CH3)2C═CHCH2C(═O)NH. Examples of “alkynylcarbonylamino” include CH3C≡CCH(CH3)C(═O)NH and HC≡CCH2CH2C(═O)NH. The term “alkoxycarbonylamino” denotes alkoxy bonded to a C(═O)NH moiety. Examples of “alkoxycarbonylamino” include CH3OC(═O)NH and CH3CH2OC(═O)NH.


The term “alkylaminocarbonylamino” denotes a straight-chain or branched alkyl group bonded to a NHC(═O)NH moiety. Examples of “alkylaminocarbonylamino” include CH3CH2NHC(═O)NH and (CH3CH2)2CH2NHC(═O)NH. The terms “alkenylaminocarbonylamino” and “alkynylaminocarbonylamino” are likewise defined. Examples of “alkenylaminocarbonylamino” include H2C═CHCH2NHC(═O)NH and (CH3)2C═CHCH2NHC(═O)NH. Examples of “alkynylaminocarbonylamino” include CH3C≡CCH(CH3)NHC(═O)NH and HC≡CCH2CH2NHC(═O)NH.


“Alkylsulfonylamino” denotes an NH radical substituted with alkylsulfonyl. Examples of “alkylsulfonylamino” include CH3CH2S(═O)2NH and (CH3)2CHS(═O)2NH. The terms “alkenylsulfonylamino” and “alkynylsulfonylamino” are likewise defined. Examples of “alkenylsulfonylamino” include H2C═CHCH2CH2S(═O)2NH and (CH3)2C═CHCH2S(═O)2NH. Examples of “alkynylsulfonylamino” include CH3C≡CCH(CH3)S(═O)2NH and HC≡CCH2CH2S(═O)2NH. The term “alkylsulfonyloxy” denotes an alkylsulfonyl group bonded to an oxygen atom. Examples of “alkylsulfonyloxy” include CH3S(═O)2O, CH3CH2S(═O)2O, CH3CH2CH2S(═O)2O, (CH3)2CHS(═O)2O, and the different butylsulfonyloxy, pentylsulfonyloxy and hexylsulfonyloxy isomers.


“Alkylaminosulfonyl” denotes a straight-chain or branched alkyl group bonded to a NHS(═O)2 moiety. Examples of “alkylaminosulfonyl” include CH3CH2NHS(═O)2 and (CH3)2CHNHS(═O)2. The terms “alkenylaminosulfonyl” and “alkynylaminosulfonyl” are likewise defined. Examples of “alkenylaminosulfonyl” include H2C═CHCH2CH2NHS(═O)2 and (CH3)2C═CHCH2NHS(═O)2. Examples of “alkynylaminosulfonyl” include CH3C≡CCH(CH3)NHS(═O)2 and HC≡CCH2CH2NHS(═O)2.


“Alkylaminosulfonylamino” denotes a straight-chain or branched alkyl group bonded to a NHS(═O)2NH moiety. Examples of “alkylaminosulfonylamino” include CH3CH2NHS(═O)2NH and (CH3)2CHNHS(═O)2NH. The terms “alkenylaminosulfonylamino” and “alkynylaminosulfonylamino” are likewise defined. Examples of “alkenylaminosulfonylamino” include H2C═CHCH2CH2NHS(═O)2NH and (CH3)2C═CHCH2NHS(═O)2NH. Examples of “alkynylaminosulfonylamino” include CH3C≡CCH(CH3)NHS(═O)2NH and HC≡CCH2CH2NHS(═O)2NH.


“Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2 and CH3CH2OCH2CH2. “Alkoxyalkoxy” denotes alkoxy substitution on another alkoxy moiety. “Alkoxyalkoxyalkyl” denotes alkoxyalkoxy substitution on alkyl. Examples of “alkoxyalkoxyalkyl” include CH3OCH2OCH2, CH3OCH2OCH2CH2 and CH3CH2OCH2OCH2.


The term “alkylcarbonyloxy” denotes a straight-chain or branched alkyl bonded to a C(═O)O moiety. Examples of “alkylcarbonyloxy” include CH3CH2C(═O)O and (CH3)2CHC(═O)O. The terms “alkenylcarbonyloxy” and “alkynylcarbonyloxy” are likewise defined. Examples of “alkenylcarbonyloxy” include H2C═CHCH2CH2C(═O)O and (CH3)2C═CHCH2C(═O)O. Examples of “alkynylcarbonyloxy” include CH3C≡CCH(CH3)C(═O)O and HC≡CCH2CH2C(═O)O. The term “alkoxycarbonyloxy” denotes a straight-chain or branched alkoxy bonded to a C(═O)O moiety. Examples of “alkoxycarbonyloxy” include CH3CH2CH2OC(═O)O and (CH3)2CHOC(═O)O. The term “alkoxycarbonylalkyl” denotes alkoxycarbonyl substitution on alkyl. Examples of “alkoxycarbonylalkyl” include CH3CH2OC(═O)CH2, (CH3)2CHOC(═O)CH2 and CH3OC(═O)CH2CH2. The term “alkylaminocarbonyloxy” denotes a straight-chain or branched alkylaminocarbonyl attached to and linked through an oxygen atom. Examples of “alkylaminocarbonyloxy” include (CH3)2CHCH2NHC(═O)O and CH3CH2NHC(═O)O. The terms “alkenylaminocarbonyloxy” and “alkynylaminocarbonyloxy” are likewise defined.


The term “alkylcarbonylthio” denotes a straight-chain or branched alkyl group bonded to a C(═O)S moiety. Examples of “alkylcarbonylthio” include CH3CH2C(═O)S and CH3CH2CH2C(═O)S. “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.


The term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to a straight-chain or branched alkyl group. The term “alkylcycloalkyl” denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl. “Alkylcycloalkylalkyl” denotes alkylcycloalkyl substitution on alkyl. Examples of “alkylcycloalkylalkyl” include methylcyclohexylmethyl and ethylcycloproylmethyl. “Cycloalkenyl” includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- or 1,4-cyclohexadienyl. The term “cycloalkylcycloalkyl” denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members. Examples of cycloalkylcycloalkyl include cyclopropylcyclopropyl (such as 1,1′-bicyclopropyl-1-yl, 1,1′-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as 1,1′-bicyclohexyl-1-yl), and the different cis- and trans-cycloalkylcycloalkyl isomers, (such as (1R,2S)-1,1′-bicyclopropyl-2-yl and (1R,2R)-1,1′-bicyclopropyl-2-yl).


The term “cycloalkoxy” denotes cycloalkyl attached to and linked through an oxygen atom including, for example, cyclopentyloxy and cyclohexyloxy. The term “cycloalkoxyalkyl” denotes cycloalkoxy substitution on an alkyl moiety. Examples of “cycloalkoxyalkyl” include cyclopropyloxymethyl, cyclopentyloxyethyl, and other cycloalkoxy groups bonded to a straight-chain or branched alkyl moiety.


The term “cycloalkylaminoalkyl” denotes cycloalkylamino substitution on an alkyl group. Examples of “cycloalkylaminoalkyl” include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to a straight-chain or branched alkyl group.


“Cycloalkylcarbonyl” denotes cycloalkyl bonded to a C(═O) group including, for example, cyclopropylcarbonyl and cyclopentylcarbonyl. “Cycloalkylcarbonyloxy” denotes cycloalkylcarbonyl attached to and linked through an oxygen atom. Examples of “cycloalkylcarbonyloxy” include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy. The term “cycloalkoxycarbonyl” means cycloalkoxy bonded to a C(═O) group, for example, cyclopropyloxycarbonyl and cyclopentyloxycarbonyl. “Cycloalkylaminocarbonylamino” denotes cycloalkylamino bonded to a C(═O)NH group, for example, cyclopentylaminocarbonylamino and cyclohexylaminocarbonylamino.


The term “halogen”, either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include CF3, ClCH2, CF3CH2 and CF3CCl2. The terms “haloalkenyl”, “haloalkynyl” “haloalkoxy”, “haloalkylsulfonyl”, “halocycloalkyl”, and the like, are defined analogously to the term “haloalkyl”. Examples of “haloalkenyl” include Cl2C═CHCH2 and CF3CH2CH═CHCH2. Examples of “haloalkynyl” include HC≡CCHCl, CF3C≡C, CCl3C≡C and FCH2C≡CCH2. Examples of “haloalkoxy” include CF3O, CCl3CH2O, F2CHCH2CH2O and CF3CH2O. Examples of “haloalkylsulfonyl” include CF3S(═O)2, CCl3S(═O)2, CF3CH2S(═O)2 and CF3CF2S(═O)2. Examples of “halocycloalkyl” include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chorocyclohexyl.


“Cyanoalkyl” denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. “Hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyalkyl” include HOCH2CH2, CH3CH2(OH)CH and HOCH2CH2CH2CH2.


“Trialkylsilyl” includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl. The term “halotrialkylsilyl” is likewise defined. Examples of “halotrialkylsilyl” include trifluormethylsilyl and trichloromethylsilyl.


The total number of carbon atoms in a substituent group is indicated by the “Ci-Cj” prefix where i and j are numbers from 1 to 15. For example, C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2.


Generally when a molecular fragment (i.e. radical) is denoted by a series of atom symbols (e.g., C, H, N, O and S) the implicit point or points of attachment will be easily recognized by those skilled in the art. In some instances herein, particularly when alternative points of attachment are possible, the point or points of attachment may be explicitly indicated by a hyphen (“-”).


The term “unsubstituted” in connection with a group such as a ring or ring system means the group does not have any substituents other than its one or more attachments to the remainder of Formula 1. The term “optionally substituted” means that the number of substituents can be zero. Unless otherwise indicated, optionally substituted groups may be substituted with as many optional substituents as can be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom. Commonly, the number of optional substituents (when present) ranges from 1 to 3. As used herein, the term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.”


The number of optional substituents may be restricted by an expressed limitation. For example, the phrase “optionally substituted with up to 3 substituents independently selected from R13” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows). When a range specified for the number of substituents (e.g., x being an integer from 0 to 3 in Exhibit A) exceeds the number of positions available for substituents on a ring (e.g., 1 position available for (R13)x on G-7 in Exhibit A), the actual higher end of the range is recognized to be the number of available positions.


When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can vary (e.g., (R13)x in Exhibit A wherein x is 1 to 3), then said substituents are independently selected from the group of defined substituents, unless otherwise indicated. When a variable group is shown to be optionally attached to a position, for example (R13)x in Exhibit A wherein x may be 0, then hydrogen may be at the position even if not recited in the definition of the variable group.


The dotted line in rings depicted in the present description (e.g., the rings G-44, G-45, G-48 and G-49 shown in Exhibit A) represents that the bond indicated can be a single bond or double bond.


Naming of substituents in the present disclosure uses recognized terminology providing conciseness in precisely conveying to those skilled in the art the chemical structure. For sake of conciseness, locant descriptors may be omitted.


Unless otherwise indicated, a “ring” or “ring system” as a component of Formula 1 (e.g., G) is carbocyclic or heterocyclic. The term “ring system” denotes two or more connected rings. The term “spirocyclic ring system” denotes a ring system consisting of two rings connected at a single atom (so the rings have a single atom in common). The term “bicyclic ring system” denotes a ring system consisting of two rings sharing two or more common atoms. In a “fused bicyclic ring system” the common atoms are adjacent, and therefore the rings share two adjacent atoms and a bond connecting them.


The term “ring member” refers to an atom (e.g., C, O, N or S) or other moiety (e.g., C(═O), C(═S), S(═O) and S(═O)2) forming the backbone of a ring or ring system. The term “aromatic” indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n+2) π electrons, where n is a positive integer, are associated with the ring to comply with Hückel's rule


The term “carbocyclic ring” denotes a ring wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies Hückel's rule, then said ring is also called an “aromatic ring”. “Saturated carbocyclic” refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.


As used herein, the term “partially unsaturated ring” or “partially unsaturated heterocycle” refers to a ring which contains unsaturated ring atoms and one or more double bonds but is not aromatic.


The terms “heterocyclic ring” or “heterocycle” denotes a ring wherein at least one of the atoms forming the ring backbone is other than carbon. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hückel's rule, then said ring is also called a “heteroaromatic ring” or aromatic heterocyclic ring. “Saturated heterocyclic ring” refers to a heterocyclic ring containing only single bonds between ring members.


Unless otherwise indicated, heterocyclic rings and ring systems are attached to the remainder of Formula 1 through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom.


Compounds of this invention can exist as one or more stereoisomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis- and trans-isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.


Compounds of this invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. For example, when T is T-3, then Formula 1 compounds contain at least one double bond and the configuration of substituents about that double bond can be (Z) or (E) (cis or trans), or a mixture thereof. In the context of the present disclosure and claims, a wavy bond (e.g., as shown in the T-3 moiety in the Summary of the Invention) indicates a single bond which is linked to an adjacent double bond wherein the geometry about the adjacent double bond is either (Z)-configuration (syn-isomer or cis-isomer) or (E)-configuration (anti-isomer or trans-isomer), or a mixture thereof. That is, a wavy bond represents an unspecified (Z)- or (E)- (cis- or trans-) isomer, or mixture thereof. In addition, the compounds of the present invention can contain one or more chiral centers and therefore exist in enantiomeric and diastereomeric forms. Unless the structural formula or the language of this application specifically designate a particular cis- or trans-isomer, or a configuration of a chiral center, the scope of the present invention is intended to cover all such isomers per se, as well as mixtures of cis- and trans-isomers, mixtures of diastereomers and racemic mixtures of enantiomers (optical isomers) as well.


This invention also includes compounds of Formula 1 wherein one stereoisomer is enriched relative to the other stereoisomer(s). Of note are compounds of Formula 1 wherein T is T-3 and the substituents attached to the double bond in the T-3 moiety are in a predominately (Z)-configuration, or predominately an (E)-configuration. The ratio of the (Z)- to (E)-isomers in any compounds of Formula 1, whether produced stereoselectivity or non-stereoselectivity, may take on a broad range of values. For example, compounds of Formula 1 may comprise from about 10 to 90 percent by weight of the (Z)-isomer to about 90 to 10 percent by weight of the (E)-isomer. In other embodiments, Formula 1 compounds may contain from about 15 to 85 percent by weight of the (Z)-isomer and about 85 to 15 percent by weight of the (E)-isomer; in another embodiment, the mixture contains about 25 to 75 percent by weight of the (Z)-isomer and about 75 to 25 percent by weight of the (E)-isomer; in another embodiment, the mixture contains about 35 to 65 percent by weight of the (Z)-isomer and about 65 to 35 percent by weight of the (E)-isomer; in another embodiment, the mixture contains about 45 to 55 percent by weight of the (Z)-isomer and about 55 to 45 percent by weight of the (E)-isomer. These percentages by weight are based on the total weight of the composition, and it will be understood that the sum of the weight percent of the (Z)-isomer and the (E)-isomer is 100 weight percent. In other words, compounds of Formula 1 might contain 65 percent by weight of the (Z)-isomer and 35 percent by weight of the (E)-isomer, or vice versa.


In addition, this invention includes compounds that are enriched compared to the racemic mixture in an enantiomer of Formula 1. Also included are the essentially pure enantiomers of compounds of Formula 1. When enantiomerically enriched, one enantiomer is present in greater amounts than the other, and the extent of enrichment can be defined by an expression of enantiomeric excess (“ee”), which is defined as (2x−1)·100%, where x is the mole fraction of the dominant enantiomer in the mixture (e.g., an ee of 20% corresponds to a 60:40 ratio of enantiomers).


Preferably the compositions of this invention have at least a 50% enantiomeric excess; more preferably at least a 75% enantiomeric excess; still more preferably at least a 90% enantiomeric excess; and the most preferably at least a 94% enantiomeric excess of the more active isomer. Of particular note are enantiomerically pure embodiments of the more active isomer.


Compounds of this invention can exist as one or more conformational isomers due to restricted rotation about an amide bond (e.g., C(═O)—N) in Formula 1. This invention comprises mixtures of conformational isomers. In addition, this invention includes compounds that are enriched in one conformer relative to others.


This invention comprises all stereoisomers, conformational isomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.


One skilled in the art will appreciate that not all nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.


One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of the compounds of Formula 1 are useful for control of plant diseases caused by fungal plant pathogens (i.e. are agriculturally suitable). The salts of the compounds of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides, and agriculturally suitable salts, and solvates thereof.


Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides, and salts thereof, typically exist in more than one form, and Formula 1 thus includes all crystalline and non-crystalline forms of the compounds that Formula 1 represents. Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts. Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types). The term “polymorph” refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1. Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.


One skilled in the art recognizes that compounds of Formula 1 can exist as mixtures of ketonic and solvated forms (e.g., hemiketals, ketals and hydrates) and each are independently interconvertible and agriculturally active. For example, ketones of Formula 11 (i.e. compounds of Formula 1 wherein T is T-1) may exist in equilibrium with their corresponding hydrates of Formula 12 (i.e. compounds of Formula 1 wherein T is T-2, and R2aX and R2bY are both OH). In cases where the ketone group is in close proximity to an electron-withdrawing group, such as when R1 is a trifluoromethyl group, the equilibrium typically favors the hydrate form.




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This invention comprises all ketonic and solvated forms of Formula 1 compounds, and mixtures thereof in all proportions. Unless otherwise indicated, reference to a compound by one tautomer description is to be considered to include all tautomers.


Additionally, some of the unsaturated rings and ring systems depicted in Exhibit A can have an arrangement of single and double bonds between ring members different from that depicted. Such differing arrangements of bonds for a particular arrangement of ring atoms correspond to different tautomers. For these unsaturated rings and ring systems, the particular tautomer depicted is to be considered representative of all the tautomers possible for the arrangement of ring atoms shown.


As described in the Summary of the Invention, an aspect of the present invention is directed at a composition comprising (a) at least one compound selected from Formula 1, N-oxides, and salts thereof, with (b) at least one additional fungicidal compound. More particularly, Component (b) is selected from the group consisting of

    • (b1) methyl benzimidazole carbamate (MBC) fungicides;
    • (b2) dicarboximide fungicides;
    • (b3) demethylation inhibitor (DMI) fungicides;
    • (b4) phenylamide (PA) fungicides;
    • (b5) amine/morpholine fungicides;
    • (b6) phospholipid biosynthesis inhibitor fungicides;
    • (b7) succinate dehydrogenase inhibitor (SDHI) fungicides;
    • (b8) hydroxy(2-amino-)pyrimidine fungicides;
    • (b9) anilinopyrimidine (AP) fungicides;
    • (b10) N-phenyl carbamate fungicides;
    • (b11) quinone outside inhibitor (QoI) fungicides;
    • (b12) phenylpyrrole (PP) fungicides;
    • (b13) azanaphthalene fungicides;
    • (b14) cell peroxidation inhibitor fungicides;
    • (b15) melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;
    • (b16a) melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides;
    • (b16b) melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides;
    • (b17) keto reductase inhibitor (KRI) fungicides;
    • (b18) squalene-epoxidase inhibitor fungicides;
    • (b19) polyoxin fungicides;
    • (b20) phenylurea fungicides;
    • (b21) quinone inside inhibitor (QiI) fungicides;
    • (b22) benzamide and thiazole carboxamide fungicides;
    • (b23) enopyranuronic acid antibiotic fungicides;
    • (b24) hexopyranosyl antibiotic fungicides;
    • (b25) glucopyranosyl antibiotic: protein synthesis fungicides;
    • (b26) glucopyranosyl antibiotic fungicides;
    • (b27) cyanoacetamideoxime fungicides;
    • (b28) carbamate fungicides;
    • (b29) oxidative phosphorylation uncoupling fungicides;
    • (b30) organo tin fungicides;
    • (b31) carboxylic acid fungicides;
    • (b32) heteroaromatic fungicides;
    • (b33) phosphonate fungicides;
    • (b34) phthalamic acid fungicides;
    • (b35) benzotriazine fungicides;
    • (b36) benzene-sulfonamide fungicides;
    • (b37) pyridazinone fungicides;
    • (b38) thiophene-carboxamide fungicides;
    • (b39) complex I NADH oxido-reductase inhibitor fungicides;
    • (b40) carboxylic acid amide (CAA) fungicides;
    • (b41) tetracycline antibiotic fungicides;
    • (b42) thiocarbamate fungicides;
    • (b43) benzamide fungicides;
    • (b44) microbial fungicides;
    • (b45) quinone outside inhibitor, stigmatellin binding (QoSI) fungicides;
    • (b46) plant extract fungicides;
    • (b47) cyanoacrylate fungicides;
    • (b48) polyene fungicides;
    • (b49) oxysterol binding protein inhibitor (OSBPI) fungicides;
    • (b50) aryl-phenyl-ketone fungicides;
    • (b51) host plant defense induction fungicides;
    • (b52) multi-site activity fungicides;
    • (b53) biologicals with multiple modes of action;
    • (b54) fungicides other than fungicides of component (a) and components (b1) through (b53); and
    • salts of compounds of (b1) through (b54).


Of note are embodiments wherein component (b) comprises at least one fungicidal compound from each of two different groups selected from (b1) through (b54).


“Methyl benzimidazole carbamate (MBC) fungicides (b1)” (FRAC code 1) inhibit mitosis by binding to β-tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Methyl benzimidazole carbamate fungicides include benzimidazole and thiophanate fungicides. The benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole. The thiophanates include thiophanate and thiophanate-methyl.


“Dicarboximide fungicides (b2)” (FRAC code 2) inhibit a mitogen-activated protein (MAP)/histidine kinase in osmotic signal transduction. Examples include chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.


“Demethylation inhibitor (DMI) fungicides (b3)” (FRAC code 3) (Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, which plays a role in sterol production. Sterols, such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. DMI fungicides are divided between several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles and triazolinthiones. The piperazines include triforine. The pyridines include buthiobate, pyrifenox, pyrisoxazole and (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol. The pyrimidines include fenarimol, nuarimol and triarimol. The imidazoles include econazole, imazalil, oxpoconazole, pefurazoate, prochloraz and triflumizole. The triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole. The triazolinthiones include prothioconazole. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides—Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.


“Phenylamide (PA) fungicides (b4)” (FRAC code 4) are specific inhibitors of RNA polymerase in Oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced capacity to incorporate uridine into rRNA. Growth and development in sensitive fungi is prevented by exposure to this class of fungicide. Phenylamide fungicides include acylalanine, oxazolidinone and butyrolactone fungicides. The acylalanines include benalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyl and metalaxyl-M (also known as mefenoxam). The oxazolidinones include oxadixyl. The butyrolactones include ofurace.


“Amine/morpholine fungicides (b5)” (FRAC code 5) (SBJ: Class II) inhibit two target sites within the sterol biosynthetic pathway, Δ8→Δ7 isomerase and Δ14 reductase. Sterols, such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Amine/morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) include morpholine, piperidine and spiroketal-amine fungicides. The morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide. The piperidines include fenpropidin and piperalin. The spiroketal-amines include spiroxamine.


“Phospholipid biosynthesis inhibitor fungicides (b6)” (FRAC code 6) inhibit growth of fungi by affecting phospholipid biosynthesis. Phospholipid biosynthesis fungicides include phophorothiolate and dithiolane fungicides. The phosphorothiolates include edifenphos, iprobenfos and pyrazophos. The dithiolanes include isoprothiolane.


“Succinate dehydrogenase inhibitor (SDHI) fungicides (b7)” (FRAC code 7) inhibit complex II fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibiting respiration prevents the fungus from making ATP, and thus inhibits growth and reproduction. SDHI fungicides include phenylbenzamide, phenyloxoethylthiophene amide, pyridinylethylbenzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole-4-carboxamide, N-cyclopropyl-N-benzyl-pyrazole carboxamide, N-methoxy-(phenyl-ethyl)-pyrazole carboxamide, pyridine carboxamide and pyrazine carboxamide fungicides. The phenylbenzamides include benodanil, flutolanil and mepronil. The phenyloxoethylthiophene amides include isofetamid. The pyridinylethylbenzamides include fluopyram. The furan carboxamides include fenfuram. The oxathiin carboxamides include carboxin and oxycarboxin. The thiazole carboxamides include thifluzamide. The pyrazole-4-carboxamides include benzovindiflupyr, bixafen, flubeneteram (provisional common name, Registry Number 1676101-39-5), fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne (provisional common name, Registry Number 1803108-03-3), sedaxane and N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide. The N-cyclopropyl-N-benzyl-pyrazole carboxamides include isoflucypram. The N-methoxy-(phenyl-ethyl)-pyrazole carboxamides include pydiflumetofen. The pyridine carboxamides include boscalid. The pyrazine carboxamides include pyraziflumid.


“Hydroxy-(2-amino-)pyrimidine fungicides (b8)” (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.


“Anilinopyrimidine (AP) fungicides (b9)” (FRAC code 9) are proposed to inhibit biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.


“N-Phenyl carbamate fungicides (b10)” (FRAC code 10) inhibit mitosis by binding to (3-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include diethofencarb.


“Quinone outside inhibitor (QoI) fungicides (b11)” (FRAC code 11) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the “quinone outside” (Qo) site of the cytochrome bc1 complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone outside inhibitor fungicides include methoxyacrylate, methoxyacetamide, methoxycarbamate, oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides (collectively also known as strobilurin fungicides), and oxazolidinedione, imidazolinone and benzylcarbamate fungicides. The methoxyacrylates include azoxystrobin, coumoxystrobin, enoxastrobin (also known as enestroburin), flufenoxystrobin, picoxystrobin and pyraoxystrobin. The methoxyacetamides include mandestrobin. The methoxy-carbamates include pyraclostrobin, pyrametostrobin and triclopyricarb. The oximinoacetates include kresoxim-methyl and trifloxystrobin. The oximinoacetamides include dimoxystrobin, fenaminstrobin, metominostrobin and orysastrobin. The dihydrodioxazines include fluoxastrobin. The oxazolidinediones include famoxadone. The imidazolinones include fenamidone. The benzylcarbamates include pyribencarb.


“Phenylpyrrole (PP) fungicides (b12)” (FRAC code 12) inhibit a MAP/histidine kinase associated with osmotic signal transduction in fungi. Fenpiclonil and fludioxonil are examples of this fungicide class.


“Azanaphthalene fungicides (b13)” (FRAC code 13) are proposed to inhibit signal transduction by a mechanism which is as yet unknown. They have been shown to interfere with germination and/or appressorium formation in fungi that cause powdery mildew diseases. Azanaphthalene fungicides include aryloxyquinolines and quinazolinones. The aryloxyquinolines include quinoxyfen. The quinazolinones include proquinazid.


“Cell peroxidation inhibitor fungicides (b14)” (FRAC code 14) are proposed to inhibit lipid peroxidation which affects membrane synthesis in fungi. Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis. Cell peroxidation fungicides include aromatic hydrocarbon and 1,2,4-thiadiazole fungicides. The aromatic hydrocarboncarbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl. The 1,2,4-thiadiazoles include etridiazole.


“Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides (b15)” (FRAC code 16.1) inhibit the naphthal reduction step in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fungicides. The isobenzofuranones include fthalide. The pyrroloquinolinones include pyroquilon. The triazolobenzothiazoles include tricyclazole.


“Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides (b16a)” (FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides. The cyclopropanecarboxamides include carpropamid. The carboxamides include diclocymet. The propionamides include fenoxanil.


“Melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides (b16b)” (FRAC code 16.3) inhibit polyketide synthase in melanin biosynthesis. Melanin is required for host plant infection by some fungi. Melanin biosynthesis inhibitor-polyketide synthase fungicides include trifluoroethylcarbamate fungicides. The trifluoroethylcarbamates include tolprocarb.


“Keto reductase inhibitor (KRI) fungicides (b17)” (FRAC code 17) inhibit 3-keto reductase during C4-demethylation in sterol production. Keto reductase inhibitor fungicides (also known as Sterol Biosynthesis Inhibitors (SBI): Class III) include hydroxyanilides and amino-pyrazolinones. Hydroxyanilides include fenhexamid. Amino-pyrazolinones include fenpyrazamine. Quinofumelin (provisional common name, Registry Number 861647-84-9) and ipflufenoquin (provisional common name, Registry Number 1314008-27-9) are also believed to be keto reductase inhibitor fungicides.


“Squalene-epoxidase inhibitor fungicides (b18)” (FRAC code 18) (SBJ: Class IV) inhibit squalene-epoxidase in the sterol biosynthesis pathway. Sterols such as ergosterol are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi. Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides. The thiocarbamates include pyributicarb. The allylamines include naftifine and terbinafine.


“Polyoxin fungicides (b19)” (FRAC code 19) inhibit chitin synthase. Examples include polyoxin.


“Phenylurea fungicides (b20)” (FRAC code 20) are proposed to affect cell division. Examples include pencycuron.


“Quinone inside inhibitor (QiI) fungicides (b21)” (FRAC code 21) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Reduction of ubiquinone is blocked at the “quinone inside” (Qi) site of the cytochrome bc1 complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development. Quinone inside inhibitor fungicides include cyanoimidazole, sulfamoyltriazole and picolinamide fungicides. The cyanoimidazoles include cyazofamid. The sulfamoyltriazoles include amisulbrom. The picolinamides include fenpicoxamid (Registry Number 517875-34-2).


“Benzamide and thiazole carboxamide fungicides (b22)” (FRAC code 22) inhibit mitosis by binding to β-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. The benzamides include toluamides such as zoxamide. The thiazole carboxamides include ethylaminothiazole carboxamides such as ethaboxam.


“Enopyranuronic acid antibiotic fungicides (b23)” (FRAC code 23) inhibit growth of fungi by affecting protein biosynthesis. Examples include blasticidin-S.


“Hexopyranosyl antibiotic fungicides (b24)” (FRAC code 24) inhibit growth of fungi by affecting protein biosynthesis. Examples include kasugamycin.


“Glucopyranosyl antibiotic: protein synthesis fungicides (b25)” (FRAC code 25) inhibit growth of fungi by affecting protein biosynthesis. Examples include streptomycin.


“Glucopyranosyl antibiotic fungicides (b26)” (FRAC code U18, previously FRAC code 26 reclassified to U18) are proposed to inhibit trehalase and inositol biosynthesis. Examples include validamycin.


“Cyanoacetamideoxime fungicides (b27)” (FRAC code 27) include cymoxanil.


“Carbamate fungicides (b28)” (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in cell membranes, which then disrupts cell membrane permeability. Iodocarb, propamacarb and prothiocarb are examples of this fungicide class.


“Oxidative phosphorylation uncoupling fungicides (b29)” (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development. This class includes dinitrophenyl crotonates such as binapacryl, meptyldinocap and dinocap, and 2,6-dinitroanilines such as fluazinam.


“Organo tin fungicides (b30)” (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in oxidative phosphorylation pathway. Examples include fentin acetate, fentin chloride and fentin hydroxide.


“Carboxylic acid fungicides (b31)” (FRAC code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.


“Heteroaromatic fungicides (b32)” (FRAC code 32) are proposed to affect DNA/ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. The isoxazoles include hymexazole and the isothiazolones include octhilinone.


“Phosphonate fungicides (b33)” (FRAC code P07, previously FRAC code 33 reclassified to P07) include phosphorous acid and its various salts, including fosetyl-aluminum.


“Phthalamic acid fungicides (b34)” (FRAC code 34) include teclofthalam.


“Benzotriazine fungicides (b35)” (FRAC code 35) include triazoxide.


“Benzene-sulfonamide fungicides (b36)” (FRAC code 36) include flusulfamide.


“Pyridazinone fungicides (b37)” (FRAC code 37) include diclomezine.


“Thiophene-carboxamide fungicides (b38)” (FRAC code 38) are proposed to affect ATP production. Examples include silthiofam.


“Complex I NADH oxidoreductase inhibitor fungicides (b39)” (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidinamines such as diflumetorim, pyrazole-5-carboxamides such as tolfenpyrad, and quinazoline such as fenazaquin.


“Carboxylic acid amide (CAA) fungicides (b40)” (FRAC code 40) inhibit cellulose synthase which prevents growth and leads to death of the target fungus. Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate and mandelic acid amide fungicides. The cinnamic acid amides include dimethomorph, flumorph and pyrimorph. The valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb and valifenalate (also known as valiphenal). The mandelic acid amides include mandipropamid, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide and N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.


“Tetracycline antibiotic fungicides (b41)” (FRAC code 41) inhibit growth of fungi by affecting protein synthesis. Examples include oxytetracycline.


“Thiocarbamate fungicides (b42)” (FRAC code M12, previously FRAC code 42 reclassified to M12) include methasulfocarb.


“Benzamide fungicides (b43)” (FRAC code 43) inhibit growth of fungi by delocalization of spectrin-like proteins. Examples include pyridinylmethyl benzamides such as fluopicolide and fluopimomide.


“Microbial fungicides (b44)” (FRAC code BM02, previously FRAC code 44 reclassified to BM02) disrupt fungal pathogen cell membranes. Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB1600, D747, TJ100 (also called strain 1 BE; known from EP2962568), and the fungicidal lipopeptides which they produce.


“Quinone outside inhibitor, stigmatellin binding (QoSI) fungicides (b45)” (FRAC code 45) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase at the “quinone outside” (Qo) site, stigmatellin binding sub-site, of the cytochrome bc1 complex. Inhibiting mitochondrial respiration prevents normal fungal growth and development. QoSI fungicides include triazolopyrimidylamines such as ametoctradin.


“Plant extract fungicides (b46)” (FRAC code 46) cause cell membrane disruption. Plant extract fungicides include terpene hydrocarbons, terpene alcohols and terpen phenols such as the extract from Melaleuca alternifolia (tea tree) and plant oils (mixtures) such as eugenol, geraniol and thymol.


“Cyanoacrylate fungicides (b47)” (FRAC code 47) bind to the myosin motor domain and effect motor activity and actin assembly. Cyanoacrylates include fungicides such as phenamacril.


“Polyene fungicides (b48)” (FRAC code 48) cause disruption of the fungal cell membrane by binding to ergosterol, the main sterol in the membrane. Examples include natamycin (pimaricin).


“Oxysterol binding protein inhibitor (OSBPI) Fungicides (b49)” (FRAC code 49) bind to the oxysterol-binding protein in oomycetes causing inhibition of zoospore release, zoospore motility and sporangia germination. Oxysterol binding fungicides include piperdinylthiazoleisoxazolines such as oxathiapiprolin and fluoxapiprolin.


“Aryl-phenyl-ketone fungicides (b50)” (FRAC code 50, previously FRAC code U8 reclassified to 50) inhibit the growth of mycelium in fungi. Aryl-phenyl ketone fungicides include benzophenones such as metrafenone, and benzoylpyridines such as pyriofenone.


“Host plant defense induction fungicides (b51)” induce host plant defense mechanisms. Host plant defense induction fungicides include benzothiadiazole (FRAC code P01), benzisothiazole (FRAC code P02), thiadiazole carboxamide (FRAC code P03), polysaccharide (FRAC code P04), plant extract (FRAC code P05), microbial (FRAC code P06) and phosphonate fungicides (FRAC code P07, see (b33) above). The benzothiadiazoles include acibenzolar-S-methyl. The benzisothiazoles include probenazole. The thiadiazole carboxamides include tiadinil and isotianil. The polysaccharides include laminarin. The plant extracts include extract from Reynoutria sachalinensis (giant knotweed). The microbials include Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS117.


“Multi-site activity fungicides (b52)” inhibit fungal growth through multiple sites of action and have contact/preventive activity. Multi-site activity fungicides include copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfamide fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code M11) and thiocarbamate (FRAC code M12, see (b42) above) fungicides. Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide (e.g., including compositions such as Bordeaux mixture (tribasic copper sulfate). Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur. Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb and ziram. Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol. Chloronitrile fungicides contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil. Sulfamide fungicides include dichlofluanid and tolyfluanid. Multi-site contact guanidine fungicides include, guazatine, iminoctadine albesilate and iminoctadine triacetate. Triazine fungicides include anilazine. Quinone fungicides include dithianon. Quinoxaline fungicides include quinomethionate (also known as chinomethionate). Maleimide fungicides include fluoroimide.


“Biologicals with multiple modes of action (b53)” include agents from biological origins showing multiple mechanisms of action without evidence of a dominating mode of action. This class of fungicides includes polypeptide (lectin), phenol, sesquiterpene, tritepenoid and coumarin fungicides (FRAC code BM01) such as extract from the cotyledons of lupine plantlets. This class also includes momicrobial fungicides (FRAC code BMO2, see (b44) above).


“Fungicides other than fungicides of component (a) and components (b1) through (b53); (b54)”; include certain fungicides whose mode of action may be unknown. These include: (b54.1) “phenyl-acetamide fungicides” (FRAC code U06), (b54.2) “guanidine fungicides” (FRAC code U12), (b54.3) “thiazolidine fungicides” (FRAC code U13), (b54.4) “pyrimidinone-hydrazone fungicides” (FRAC code U14), (b54.5) “4-quinolylacetate fungicides” (FRAC code U16), (54.6) “tetrazolyloxime fungicides” (FRAC code U17) and “glucopyranosyl antibiotic fungicides” (FRAC code U18, see (b26) above). The phenyl-acetamides include cyflufenamid. The guanidines include dodine. The thiazolidines include flutianil. The pyrimidinonehydrazones include ferimzone. The 4-quinolylacetates include tebufloquin. The tetrazolyloximes include picarbutrazox.


The (b54) class also includes bethoxazin, dichlobentiazox (provisional common name, Registry Number 957144-77-3), dipymetitrone (provisional common name, Registry Number 16114-35-5), flometoquin, neo-asozin (ferric methanearsonate), pyrrolnitrin, tolnifanide (Registry Number 304911-98-6), N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate.


Additional “Fungicides other than fungicides of classes (1) through (54)” whose mode of action may be unknown, or may not yet be classified include a fungicidal compound selected from components (b54.7) through (b54.13), as described below.


Component (54.7) relates to (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name florylpicoxamid, Registry Number 1961312-55-9) which is believed to be a Quinone inside inhibitor (QiI) fungicide (FRAC code 21) inhibiting the Complex III mitochondrial respiration in fungi.


Component (54.8) relates to 1-[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]-3-methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazol-5-one (provisional common name metyltetraprole, Registry Number 1472649-01-6), which is believed to be a quinone outside inhibitor (QoI) fungicide (FRAC code 45) inhibiting the Complex III mitochondrial respiration in fungi, and is effective against QoI resistant strains.


Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional common name pyridachlometyl, Registry Number 1358061-55-8), which is believed to be promoter tubulin polymerization, resulting antifungal activity against fungal species belonging to the phyla Ascomycota and Basidiomycota.


Component (54.10) relates to (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (provisional common name aminopyrifen, Registry Number 1531626-08-0) which is believed to inhibit GWT-1 protein in glycosylphosphatidylinositol-anchor biosynthesis in Neurospora crassa.


Component (b54.11) relates a compound of Formula b54.11




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    • wherein
      • Rb1 and Rb3 are each independently halogen; and
      • Rb2 is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl.


        Examples of compounds of Formula b54.11 include (b54.11a) methyl N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl] methyl]carbamate, (b54.11b) methyl N-[[5-[1-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11c) methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]-methyl]carbamate, (b54.11d) methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11e) methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate and (b54.11f) methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate. Compounds of Formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT Patent Publications WO 2008/124092, WO 2014/066120 and WO 2020/097012.





Component (b54.12) relates a compound of Formula b54.12




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wherein

    • Rb4 is




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    • Rb6 is C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;

    • L is CH2 or CH2O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12; and

    • Rb5 is







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Examples of compounds of Formula b54.12 include (b54.12a) N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide and (b54.12b) ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate. Compounds of Formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT Patent Publication WO 2020/056090.


Component (b54.13) relates a compound of Formula b54.13




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    • wherein
      • Rb7, Rb8 and Rb9 are each independently H, halogen or cyano; and
      • Rb10 and Rb11 are each independently H, halogen, C1-C3 alkyl or C1-C3 methoxy.


        Examples of compounds of Formula b54.13 include (b54.13a) 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (b54.13b) 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (b54.13c) 3,5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile and (b54.13d) N-(2-chloro-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine. Compounds of Formula b54.11, their use as fungicides and methods of preparation are generally known; see, for example, PCT Patent Publication WO 2020051402.





Embodiments of the present invention as described in the Summary of the Invention include those described below. In the following Embodiments, Formula 1 includes stereoisomers, N-oxides, and salts thereof, and reference to “a compound of Formula 1” includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.

    • Embodiment 1. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-1.
    • Embodiment 2. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-2.
    • Embodiment 3. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-3.
    • Embodiment 3a. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-2 or T-3.
    • Embodiment 4. The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, R1 is CF3.
    • Embodiment 5. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 4 wherein in Formula 1, W is O or S.
    • Embodiment 6. The composition of Embodiment 5 wherein W is O.
    • Embodiment 7. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 4 wherein in Formula 1, W is NR3.
    • Embodiment 8. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 7 wherein in Formula 1, R3 is H, cyano, C(═O)OH, C1-C2 alkyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, OR3a or NR3bR3c.
    • Embodiment 9. The composition of Embodiment 8 wherein R3 is H, cyano, C1-C2 alkyl or OR3a.
    • Embodiment 10. The composition of Embodiment 9 wherein R3 is H, cyano or OR3a.
    • Embodiment 11. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 10 wherein in Formula 1, R3a is H, C1-C2 alkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl.
    • Embodiment 12. The composition of Embodiment 11 wherein R3a is H.
    • Embodiment 13. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 12 wherein in Formula 1, when R3b is separate (i.e. not taken together with R3c to form a ring), then R3b is H, C1-C3 alkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl.
    • Embodiment 14. The composition of Embodiment 13 wherein R3b is H or methyl.
    • Embodiment 15. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 14 wherein in Formula 1, when R3c is separate (i.e. not taken together with R3b to form a ring), then R3c is H or C1-C2 alkyl.
    • Embodiment 16. The composition of Embodiment 15 wherein R3c is H or methyl.
    • Embodiment 17. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 16 wherein in Formula 1, X is O or NR5a.
    • Embodiment 18. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 16 wherein in Formula 1, X is O, S, NH or NOH.
    • Embodiment 19. The composition of Embodiment 18 wherein X is O or NOH.
    • Embodiment 20. The composition of Embodiment 20 wherein X is O.
    • Embodiment 21. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 20 wherein in Formula 1, Y is O or NR5b.
    • Embodiment 22. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 20 wherein in Formula 1, Y is O, S, NH or NOH.
    • Embodiment 23. The composition of Embodiment 22 wherein Y is O or NOH.
    • Embodiment 24. The composition of Embodiment 23 wherein Y is O.
    • Embodiment 25. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 24 wherein in Formula 1, R5a and R5b are each independently H, hydroxy or C1-C2 alkyl.
    • Embodiment 26. The composition of Embodiment 25 wherein R5a and R5b are each independently H, hydroxy or methyl.
    • Embodiment 27. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 26 wherein in Formula 1, when R2a and R2b are separate (i.e. not taken together to form a ring), then R2a and R2b are each independently H, C1-C3 alkyl, C2-C3 alkenyl, (CR4aR4b)p—OH, (CR4aR4b)p—Cl or (CR4aR4b)p—Br.
    • Embodiment 27a. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 26 wherein in Formula 1, when R2a and R2b are separate (i.e. not taken together to form a ring), then R2a and R2b are each independently H, C1-C3 alkyl, C3-C15 trialkylsilyl or C3-C15 halotrialkylsilyl.
    • Embodiment 27b. The composition of Embodiment 27a wherein R2a and R2b are each independently H, methyl, trimethylsilyl or halotrimethylsilyl.
    • Embodiment 27c. The composition of Embodiment 27b wherein R2a and R2b are each independently H, methyl, trimethylsilyl or trifluoromethylsilyl Embodiment 27d. The composition of Embodiment 27c wherein R2a and R2b are each independently H, methy or trimethylsilyl.
    • Embodiment 27e. The composition of Embodiment 27d wherein R2a is H and R2b is trimethylsilyl.
    • Embodiment 27f. The composition of Embodiment 27d wherein R2a is methyl and R2b is trimethylsilyl.
    • Embodiment 28. The composition of Embodiment 27 wherein R2a and R2b are each independently H, C1-C3 alkyl, (CR4aR4b)p—Cl or (CR4aR4b)p—Br.
    • Embodiment 29. The composition of Embodiment 28 wherein R2a and R2b are each independently H, methyl, (CR4aR4b)p—Cl or (CR4aR4b)p—Br.
    • Embodiment 30. The composition of Embodiment 28 wherein R2a and R2b are each independently H or C1-C3 alkyl.
    • Embodiment 31. The composition of Embodiment 30 wherein R2a and R2b are each independently H or C1-C2 alkyl.
    • Embodiment 32. The composition of Embodiment 31 wherein R2a and R2b are each independently H or methyl.
    • Embodiment 33. The composition of Embodiment 32 wherein R2a and R2b are each H.
    • Embodiment 34. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 33 wherein in Formula 1, when R2a and R2b are separate (i.e. not taken together to form a ring), then one of R2a and R2b is (CR4aR4b)p—OH, (CR4aR4b)p—SH, (CR4aR4b)p—Cl or (CR4aR4b)p—Br, and the other is H.
    • Embodiment 35. The composition of Embodiment 34 wherein one of R2a and R2b is (CR4aR4b)p—Cl or (CR4aR4b)p—Br, and the other is H.
    • Embodiment 36. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 35 wherein in Formula 1, R2a and R2b are each independently H, methyl, (CR4aR4b)p—OH, (CR4aR4b)p—Cl or (CR4aR4b)p—Br; or R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 2 carbon atom ring members are independently selected from C(═O) and C(═S), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy on carbon atom ring members.
    • Embodiment 37. The composition of Embodiment 36 wherein R2a and R2b are each independently H or methyl; or R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(═O), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members.
    • Embodiment 38. The composition of Embodiment 37 wherein R2a and R2b are each independently H or methyl; or R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, cyano and methyl on carbon atom ring members.
    • Embodiment 39. The composition of Embodiment 38 wherein R2a and R2b are each H; or
    • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected methyl on a carbon atom ring member.
    • Embodiment 40. The composition of Embodiment 39 wherein R2a and R2b are each H; or
    • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
    • Embodiment 41. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 40 wherein in Formula 1, when R2a and R2b are taken together to form a ring (i.e. not separate), then R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(═O), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members.
    • Embodiment 42. The composition of Embodiment 41 wherein R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl and methoxy on carbon atom ring members.
    • Embodiment 43. The composition of Embodiment 42 wherein R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member.
    • Embodiment 44. The composition of Embodiment 43 wherein R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
    • Embodiment 45. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 44 wherein in Formula 1, R2e is C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl or C2-C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano, hydroxy, SC≡N and C1-C2 alkoxy.
    • Embodiment 46. The composition of Embodiment 45 wherein R2c is C1-C2 alkyl, C1-C2 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl, C2-C3 alkynyl or C2-C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano and methoxy.
    • Embodiment 46a. The composition of Embodiment 46 wherein R2c is C1-C2 alkyl, C1-C2 haloalkyl, C2-C3 alkenyl, C2-C3 haloalkenyl or C2-C3 alkynyl.
    • Embodiment 47. The composition of Embodiment 46a wherein R2c is C1-C2 alkyl, C2-C3 alkenyl or C2-C3 alkynyl.
    • Embodiment 48. The composition of Embodiment 47 wherein R2c is methyl or ethyl.
    • Embodiment 48a. The composition of Embodiment 48 wherein R2c is ethyl.
    • Embodiment 49. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 48a wherein in Formula 1, R2d is H, cyano, halogen or C1-C2 alkyl.
    • Embodiment 49a. The composition of Embodiment 49 wherein R2d is H, cyano, Cl, F or methyl.
    • Embodiment 50. The composition of Embodiment 49a wherein R2d is H or methyl.
    • Embodiment 51. The composition of Embodiment 50 wherein R2d is H.
    • Embodiment 52. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 51 wherein in Formula 1, each R4a and R4b is independently H or C1-C2 alkyl.
    • Embodiment 53. The composition of Embodiment 52 wherein each R4a and R4b is independently H or methyl.
    • Embodiment 54. The composition of Embodiment 53 wherein each R4a and R4b is H.
    • Embodiment 55. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 54 wherein in Formula 1, p is 2.
    • Embodiment 56. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 54 wherein in Formula 1, p is 3.
    • Embodiment 57. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 56 wherein in Formula 1, wherein A1 is CR6cR6d, O or S.
    • Embodiment 58. The composition of Embodiment 57 wherein A1 is CR6cR6d or O.
    • Embodiment 59. The composition of Embodiment 58 wherein A1 is CR6cR6d.
    • Embodiment 60. The composition of Embodiment 58 wherein A1 is O.
    • Embodiment 61. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 60 wherein in Formula 1, A1 is CH2, NH, O or S.
    • Embodiment 62. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 61 wherein in Formula 1, A1 is N(R7a).
    • Embodiment 63. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 63 wherein in Formula 1, A2 is a direct bond, CR6eR6f, O or S.
    • Embodiment 64. The composition of Embodiment 63 wherein A2 is a direct bond, CR6eR6f or O.
    • Embodiment 65. The composition of Embodiment 64 wherein A2 is a direct bond or O.
    • Embodiment 66. The composition of Embodiment 65 wherein A2 is a direct bond.
    • Embodiment 67. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 62 wherein in Formula 1, A2 is a direct bond, CH2, NH, O or S.
    • Embodiment 67a. The composition of Embodiment 67 wherein A2 is a direct bond, CH2 or 0.
    • Embodiment 68. The composition of Embodiment 67a wherein A2 is a direct bond or O.
    • Embodiment 69. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 62 wherein in Formula 1, A2 is N(R7b).
    • Embodiment 70. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 69 wherein in Formula 1, when A is A1-A2-CR6aR6b, then A1-A2-CR6aR6b is selected from OCH2, OCH(Me), CH(OH)CH2, CH2CH2, SCH2, OCF2 and CH2OCH2.
    • Embodiment 71. The composition of Embodiment 70 wherein A1-A2-CR6aR6b is selected from OCH2, OCH(Me) and CH2CH2.
    • Embodiment 72. The composition of Embodiment 71 wherein A1-A2-CR6aR6b is selected from OCH2 and CH2CH2.
    • Embodiment 73. The composition of Embodiment 72 wherein A1-A2-CR6aR6b is OCH2.
    • Embodiment 74. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 74 wherein in Formula 1, when A is A1-A2, then A1-A2 is selected from O, CH2, OCH2 and CH2O.
    • Embodiment 75. The composition of Embodiment 74 wherein A1-A2 is selected from O, CH2 and CH2O.
    • Embodiment 76. The composition of Embodiment 75 wherein A1-A2 is selected from O and CH2.
    • Embodiment 77. The composition of Embodiment 76 wherein A1-A2 is O.
    • Embodiment 78. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 77 wherein in Formula 1, R6a, R6b, R6c, R6d, R6e and R6f are each independently H, cyano, hydroxy, Br, Cl, F or methyl.
    • Embodiment 79. The composition of Embodiment 78 wherein R6a, R6b, R6c, R6d, R6e and R6f are each independently H, cyano hydroxy or methyl.
    • Embodiment 80. The composition of Embodiment 79 wherein R6a, R6b, R6c, R6d, R6e and R6f are each independently H or methyl.
    • Embodiment 81. The composition of Embodiment 80 wherein R6a, R6b, R6c, R6d, R6e and R6f are each H.
    • Embodiment 82. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 81 wherein in Formula 1, R7a and R7b are each independently H, C1-C2 alkyl or C2-C3 alkylcarbonyl.
    • Embodiment 83. The composition of Embodiment 82 wherein R7a and R7b are each independently H or C1-C2 alkyl.
    • Embodiment 84. The composition of Embodiment 83 wherein R7a and R7b are each H.
    • Embodiment 85. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 84 wherein in Formula 1, when T is T-1 or T-2, then A is A1-A2-CH2.
    • Embodiment 86. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 85 wherein in Formula 1, when T is T-1 or T-2, then A is OCH2, SCH2, NHCH2, CH2CH2, OCH2CH2, SCH2CH2, NHCH2CH2, CH2OCH2, CH2SCH2 or CH2NHCH2.
    • Embodiment 87. The composition of Embodiment 86 wherein when T is T-1 or T-2, then A is OCH2, SCH2, CH2CH2, OCH2CH2, SCH2CH2, CH2OCH2 or CH2SCH2.
    • Embodiment 88. The composition of Embodiment 87 wherein when T is T-1 or T-2, then A is OCH2 or CH2CH2.
    • Embodiment 89. The composition of Embodiment 88 wherein when T is T-1 or T-2, then A is OCH2.
    • Embodiment 90. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 89 wherein in Formula 1, when T is T-3, then A is O, OCH2, SCH2, NHCH2, CH2, CH2CH2, CH2O, CH2S or CH2NH.
    • Embodiment 91. The composition of Embodiment 82 wherein when T is T-3, then A is O, CH2 or OCH2.
    • Embodiment 92. The composition of Embodiment 91 wherein when T is T-3, then A is O or CH2.
    • Embodiment 93. The composition of Embodiment 92 wherein when T is T-3, then A is O.
    • Embodiment 94. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 93 wherein in Formula 1, J is J-1 through J-3, J-6 through J-10 or J-14.
    • Embodiment 95. The composition of Embodiment 94 wherein J is J-1, J-2, J-3, J-6 or J-14.
    • Embodiment 96. The composition of Embodiment 95 wherein J is J-1, J-6 or J-14.
    • Embodiment 97. The composition of Embodiment 96 wherein J is J-1 or J-6.
    • Embodiment 97a. The composition of Embodiment 96 wherein J is J-14.
    • Embodiment 98. The composition of Embodiment 97 wherein J is J-1.
    • Embodiment 99. The composition of Embodiment 97 wherein J is J-6.
    • Embodiment 100. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 99 wherein in Formula 1, each R8 is independently F, Cl or methyl.
    • Embodiment 100a. The composition of Embodiment 100 wherein each R8 is independently F or C1.
    • Embodiment 101. The composition of Embodiment 100 wherein each R8 is independently F or methyl.
    • Embodiment 101a. The composition of Embodiment 101 wherein each R8 is F.
    • Embodiment 102. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 101a wherein in Formula 1, q is 0 or 1.
    • Embodiment 102a. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 101a wherein in Formula 1, q is 3 or 4.
    • Embodiment 102b. The composition of Embodiment 102a wherein in Formula 1, q is 4.
    • Embodiment 103. The composition of Embodiment 102 wherein q is 0.
    • Embodiment 103a. The composition of Embodiment 102 wherein q is 1.
    • Embodiment 104. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 103a wherein in Formula 1, each R9a and R9b is independently H, halogen, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy.
    • Embodiment 105. The composition of Embodiment 104 wherein each R9a and R9b is independently H, halogen, C1-C2 alkyl or C1-C2 haloalkyl.
    • Embodiment 106. The composition of Embodiment 105 wherein each R9a and R9b is independently H, halogen or methyl.
    • Embodiment 107. The composition of Embodiment 106 wherein each R9a and R9b is independently H or methyl.
    • Embodiment 108. The composition of Embodiment 107 wherein each R9a and R9b is H.
    • Embodiment 109. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 108 wherein in Formula 1, n is 0, 1 or 2.
    • Embodiment 109a. The composition of Embodiment 109 wherein n is 1 or 2.
    • Embodiment 110. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 109a wherein in Formula 1, n is 0 or 1.
    • Embodiment 111. The composition of Embodiments 109, 109a or 110 wherein n is 1.
    • Embodiment 112. The composition of Embodiments 109 or 110 wherein n is 0.
    • Embodiment 113. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 112 wherein in Formula 1, L is a direct bond, CH2, CH(Me) or CH2CH2.
    • Embodiment 113a. The composition of Embodiment 113 wherein L is a direct bond, CH2 or CH2CH2.
    • Embodiment 114. The composition of Embodiment 113a wherein L is a direct bond or CH2.
    • Embodiment 115. The composition of Embodiment 114 wherein L is CH2.
    • Embodiment 115a. The composition of Embodiment 114 wherein L is a direct bond.
    • Embodiment 116. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 115a wherein in Formula 1, E is E1.
    • Embodiment 116a. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 116 wherein in Formula 1, when L is a direct bond, then E is E1.
    • Embodiment 117. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 116a wherein in Formula 1, E1 is cyano, nitro, C(═O)H, C(═O)OH or SC≡N; or C1-C6 alkoxy, C2-C6 alkenyloxy, C1-C6 alkylsulfonyl, C2-C6 alkenylsulfonyl, C2-C6 alkynylsulfonyl, C1-C6 alkylsulfonylamino, C2-C6 alkenylsulfonylamino, C2-C6 alkynylsulfonylamino, C1-C6 alkylaminosulfonyl, C2-C6 dialkylaminosulfonyl, C2-C6 alkenylaminosulfonyl, C2-C6 alkylcarbonyl, C2-C6 alkylaminocarbonyl, C3-C6 alkenylaminocarbonyl, C3-C6 alkynylaminocarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C2-C6 alkoxycarbonylamino, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b.
    • Embodiment 118. The composition of Embodiment 117 wherein E1 is cyano, nitro, C(═O)H, C(═O)OH or SC≡N; or C1-C6 alkoxy, C2-C6 alkenyloxy, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonylamino, C2-C6 alkenylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl or C3-C6 alkynyloxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b.
    • Embodiment 119. The composition of Embodiment 118 wherein E1 is C1-C6 alkoxy, C1-C6 alkylsulfonyl, C2-C6 alkylcarbonyl or C2-C6 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b.
    • Embodiment 120. The composition of Embodiment 119 wherein E1 is C1-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b.
    • Embodiment 120a. The composition of Embodiment 120 wherein E1 is C1-C3 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a.
    • Embodiment 121. The composition of Embodiment 120 wherein E1 is C1-C2 alkoxy, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b.
    • Embodiment 121a. The composition of Embodiment 120 wherein E1 is C1-C2 alkoxy, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a.
    • Embodiment 121b. The composition of Embodiment 121a wherein E1 is methoxy optionally substituted with up to 1 substituent selected from R10a.
    • Embodiment 121c. The composition of Embodiment 121a wherein E1 is methoxy substituted with 1 substituent selected from R10a.
    • Embodiment 122. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 121c wherein in Formula 1, R10a is phenyl optionally substituted with up to 3 substituents independently selected from R11a; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R11a on carbon atom ring members and R11b on nitrogen atom ring members.
    • Embodiment 123. The composition of Embodiment 122 wherein R10a is phenyl optionally substituted with up to 2 substituents independently selected from R11a; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members and R11b on nitrogen atom ring members.
    • Embodiment 123a. The composition of Embodiment 123 wherein R10a is a 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O and up to 3 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members.
    • Embodiment 123b. The composition of Embodiment 123a wherein R10a is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members.
    • Embodiment 123c. The composition of Embodiment 123b wherein R10a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members.
    • Embodiment 123d. The composition of Embodiment 123c wherein R10a is pyrazolyl optionally substituted with up to 1 substituent selected from R11a on a carbon atom ring member.
    • Embodiment 124. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 123c wherein in Formula 1, each R10b is independently cyano, halogen, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C3-C6 cycloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-C4 dialkylamino, C2-C4 alkylcarbonyl or C2-C5 alkoxycarbonyl.
    • Embodiment 125. The composition of Embodiment 124 wherein each R10b is independently halogen, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, C2-C4 alkylcarbonyl or C2-C5 alkoxycarbonyl.
    • Embodiment 125a. The composition of Embodiment 125 wherein each R10b is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C4 alkoxycarbonyl.
    • Embodiment 126. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 125a wherein in Formula 1, each R11a is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkynyloxy, C2-C4 alkoxyalkyl, C2-C6 alkylcarbonyloxy, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfonyloxy, C2-C4 alkylcarbonyl, C3-C5 alkenylcarbonyl, C3-C5 alkynylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7 alkenyloxycarbonyl, C3-C7 alkynyloxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C6 alkenylaminocarbonyl, C3-C6 alkynylaminocarbonyl or C3-C8 dialkylaminocarbonyl.
    • Embodiment 127. The composition of Embodiment 126 wherein each R11a is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkoxyalkyl, C2-C4 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7 alkenyloxycarbonyl or C2-C6 alkylaminocarbonyl.
    • Embodiment 128. The composition of Embodiment 127 wherein each R11a is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkenyloxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl or C3-C5 alkenyloxycarbonyl.
    • Embodiment 128a. The composition of Embodiment 128 wherein each R11a is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C3 alkoxycarbonyl.
    • Embodiment 128b. The composition of Embodiment 128a wherein each R11a is independently methoxycarbonyl or ethoxycarbonyl.
    • Embodiment 128c. The composition of Embodiment 128b wherein each R11a is ethoxycarbonyl.
    • Embodiment 129. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 128c wherein in Formula 1, each R11b is independently C1-C2 alkyl, C1-C2 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl.
    • Embodiment 130. The composition of Embodiment 129 wherein each R11b is independently methyl, methoxy, methylcarbonyl or methoxycarbonyl.
    • Embodiment 131. The composition of Embodiment 130 wherein each R11b is independently methyl or methoxy.
    • Embodiment 132. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 131 wherein in Formula 1, E is E2.
    • Embodiment 133. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 132 wherein in Formula 1, G is phenyl optionally substituted with up to 3 substituents independently selected from R13; or a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R13; or a 3- to 7-membered nonaromatic ring or an 8- to 11-membered bicyclic ring system, each ring or ring system containing ring members selected from carbon atoms and optionally up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(═O), S(═O) and S(═O)2, each ring or ring system optionally substituted with up to 3 substituents independently selected from R13.
    • Embodiment 134. The composition of Embodiment 133 wherein G is selected from G-1 through G-118 as shown in Exhibit A.


Exhibit A



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    • wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3.

    • Embodiment 135. The composition of Embodiment 134 wherein G is G-1 through G-16, G-20, G-22 through G-30, G-36 through G-42, G-54 through G-60, G-85, G-86, G-108, G-110 or G-111.

    • Embodiment 136. The composition of Embodiment 135 wherein G is G-1 through G-16, G-22, G-24, G-25, G-26, G-28, G-29, G-30, G-36, G-37, G-38, G-41, G-42, G-54, G-57, G-58, G-59, G-60, G-85, G-86, G-108, G-110 or G-111.

    • Embodiment 137. The composition of Embodiment 136 wherein G is G-1 through G-13, G-22, G-24, G-25, G-26, G-28, G-29, G-41, G-42, G-54, G-57, G-58, G-59 or G-60.

    • Embodiment 138. The composition of Embodiment 137 wherein G is G-1, G-2, G-3, G-7, G-8, G-9, G-10, G-12, G-13, G-22, G-29, G-42, G-54 or G-58.

    • Embodiment 139. The composition of Embodiment 138 wherein G is G-1, G-3, G-12, G-13, G-22 or G-42.

    • Embodiment 140. The composition of Embodiment 139 wherein G is G-1, G-3, G-12, G-13 or G-22.

    • Embodiment 141. The composition of Embodiment 140 wherein G is G-1, G-3, G-12 or G-22.

    • Embodiment 142. The composition of Embodiment 141 wherein G is G-1 or G-12.

    • Embodiment 143. The composition of Embodiment 142 wherein G is G-1.

    • Embodiment 144. The composition of Embodiment 142 wherein G is G-12.

    • Embodiment 145. The composition of Embodiment 140 wherein G is G-3.

    • Embodiment 146. The composition of Embodiment 140 wherein G is G-22.

    • Embodiment 147. The composition of Embodiment 143 wherein the 2-position of G-1 is connected to Z and the 4-position is connected to R13.

    • Embodiment 148. The composition of Embodiment 143 wherein the 2-position of G-1 is connected to Z and the 5-position is connected to R13.

    • Embodiment 149. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 4-position is connected to R13.

    • Embodiment 150. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 3-position is connected to R13.

    • Embodiment 151. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 3- and 5-positions are connected to R13.

    • Embodiment 152. The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 5-position is connected to R13.

    • Embodiment 153. The composition of Embodiment 145 wherein the 1-position of G-3 is connected to Z and the 4-position is connected to R13.

    • Embodiment 154. The composition of Embodiment 146 wherein the 4-position of G-22 is connected to Z and the 2-position is connected to R13.

    • Embodiment 155. The composition of any one of Embodiments 147 through 154 wherein Z is a direct bond.

    • Embodiment 156. The composition of any one of Embodiments 147 through 155 wherein x is 1 and R13 is methoxycarbonyl or ethoxycarbonyl.

    • Embodiment 157. The composition of any one of Embodiments 134 through 155 wherein x is 1 or 2.

    • Embodiment 158. The composition of Embodiment 157 wherein x is 1.

    • Embodiment 159. The composition of Embodiment 157 wherein x is 2.

    • Embodiment 160. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 134 through 155 wherein in Formula 1, x is 0.

    • Embodiment 161. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 159 wherein in Formula 1, each R13 is independently cyano, halogen, NR14aR14b, C(═O)NR14aR14b, C(R15)═NR16, N═CR17NR18aR18b or —U—V-Q; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C7 cycloalkoxycarbonyl, C2-C6 alkylcarbonyloxy, C2-C6 alkoxycarbonyloxy, C4-C7 cycloalkoxycarbonyloxy, C2-C6 alkylaminocarbonyloxy, C2-C6 alkylcarbonylamino, C2-C6 alkoxycarbonylamino or C2-C6 alkylaminocarbonylamino, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 162. The composition of Embodiment 161 wherein each R13 is independently cyano, halogen, C(═O)NR14aR14b or —U—V-Q; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 163. The composition of Embodiment 162 wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C6 cycloalkoxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 163a. The composition of Embodiment 162 wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 163b. The composition of Embodiment 163a wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19.

    • Embodiment 164. The composition of Embodiment 163a wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 164a. The composition of Embodiment 164 wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, or C3-C6 alkynyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 165. The composition of Embodiment 164a wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, or C3-C5 alkynyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 165a. The composition of Embodiment 165 wherein each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl or C3-C5 alkenyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 166. The composition of Embodiment 165 wherein each R13 is independently C2-C5 alkoxycarbonyl or C3-C5 alkenyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 167. The composition of Embodiment 166 wherein each R13 is independently C2-C5 alkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 168. The composition of Embodiment 167 wherein each R13 is independently methoxycarbonyl or ethoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19.

    • Embodiment 169. The composition of Embodiment 168 wherein each R13 is independently methoxycarbonyl or ethoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19.

    • Embodiment 170. The composition of Embodiment 169 wherein each R13 is independently ethoxycarbonyl optionally substituted with up to 1 substituent selected from R19.

    • Embodiment 171. The composition of Embodiment 169 wherein each R13 is independently methoxycarbonyl or ethoxycarbonyl.

    • Embodiment 172. The composition of Embodiment 171 wherein each R13 is ethoxycarbonyl.

    • Embodiment 173. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 172 wherein in Formula 1, when each R14a is separate (i.e. not taken together with R14b to form a ring), then each R14a is independently H, cyano, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C2-C4 alkylcarbonyl, C2-C5 alkoxycarbonyl or C3-C5 dialkylaminocarbonyl.

    • Embodiment 174. The composition of Embodiment 173 wherein each R14a is independently H, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl, C2-C5 alkoxycarbonyl or C3-C5 dialkylaminocarbonyl.

    • Embodiment 175. The composition of Embodiment 174 wherein each R14a is independently H, C1-C2 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

    • Embodiment 176. The composition of Embodiment 175 wherein each R14a is independently H or C1-C2 alkyl.

    • Embodiment 177. The composition of Embodiment 176 wherein each R14a is independently H or methyl.

    • Embodiment 177a. The composition of Embodiment 177 wherein each R14a is H.

    • Embodiment 178. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 177a wherein in Formula 1, when each R14b is separate (i.e. not taken together with R14a to form a ring), then each R14b is independently H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 cyanoalkyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C4-C10 halocycloalkylalkyl, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkylsulfonylalkyl, C2-C6 alkylaminoalkyl or C3-C8 dialkylaminoalkyl, each optionally substituted with up to 1 substituent selected from cyano, hydroxy, nitro, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl.

    • Embodiment 179. The composition of Embodiment 178 wherein each R14b is independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylaminoalkyl or C3-C5 dialkylaminoalkyl.

    • Embodiment 180. The composition of Embodiment 179 wherein each R14b is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl or C2-C4 alkoxyalkyl.

    • Embodiment 181. The composition of Embodiment 180 wherein each R14b is independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl.

    • Embodiment 181a. The composition of Embodiment 181 wherein each R14b is independently H, C1-C2 alkyl, C1-C2 haloalkyl or cyclopropylmethyl.

    • Embodiment 181b. The composition of Embodiment 181a wherein each R14b is independently H, methyl or cyclopropylmethyl.

    • Embodiment 182. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 181b wherein in Formula 1, when R14a and R14b are taken together to form a 4- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.

    • Embodiment 183. The composition of Embodiment 182 wherein R14a and R14b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.

    • Embodiment 184. The composition of Embodiment 183 wherein R14a and R14b are taken together to form an azetidinyl or pyrrolidinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.

    • Embodiment 185. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 184 wherein in Formula 1, each R15 is independently H, cyano, halogen, methyl or methoxy.

    • Embodiment 186. The composition of Embodiment 185 wherein each R15 is independently H or methyl.

    • Embodiment 187. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 186 wherein in Formula 1, each R16 is independently hydroxy, NR20aR20b, C1-C2 alkoxy, C2-C4 alkenyloxy, C2-C4 alkylcarbonyloxy or C2-C4 alkoxycarbonyloxy.

    • Embodiment 188. The composition of Embodiment 187 wherein each R16 is independently hydroxy, NR20aR20b or C1-C4 alkoxy.

    • Embodiment 189. The composition of Embodiment 188 wherein each R16 is independently hydroxy, NR20aR20b or methoxy.

    • Embodiment 190. The composition of Embodiment 189 wherein each R16 is hydroxy.

    • Embodiment 191. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 190 wherein in Formula 1, each R17 is independently H or methyl.

    • Embodiment 192. The composition of Embodiment 191 wherein each R17 is H.

    • Embodiment 193. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 192 wherein in Formula 1, when each R18a and R18b is separate (i.e. not taken together to form a ring), then each R18a and R18b is independently H, methyl or ethyl.

    • Embodiment 194. The composition of Embodiment 193 wherein each R18a and R18b is independently H or methyl.

    • Embodiment 195. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 194 wherein in Formula 1, when R18a and R18b are taken together to form a 5- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 methyl groups.

    • Embodiment 196. The composition of Embodiment 195 wherein R18a and R18b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.

    • Embodiment 197. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 196 wherein in Formula 1, each R19 is independently cyano, halogen, hydroxy, C1-C3 alkyl, C1-C3 haloalkyl, C3-C6 cycloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C2-C3 alkoxyalkoxy, C1-C3 alkylthio, C1-C3 alkylsulfinyl, C1-C3 alkylsulfonyl, C1-C3 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl, C2-C3 alkylaminocarbonyl or C3-C5 dialkylaminocarbonyl.

    • Embodiment 198. The composition of Embodiment 197 wherein each R19 is independently cyano, halogen, hydroxy, C1-C2 alkyl, C1-C2 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio, C1-C2 alkylsulfonyl, C1-C2 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl or C2-C3 alkylaminocarbonyl.

    • Embodiment 199. The composition of Embodiment 197 wherein each R19 is independently cyano, halogen, C1-C2 alkyl, C1-C2 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl or C2-C3 alkoxycarbonyl.

    • Embodiment 200. The composition of Embodiment 199 wherein each R19 is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl.

    • Embodiment 200a. The composition of Embodiment 200 wherein each R19 is independently cyano, halogen, cyclopropyl or methoxy.

    • Embodiment 200b. The composition of Embodiment 200a wherein each R19 is independently cyano, Cl, F, cyclopropyl or methoxy.

    • Embodiment 201. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 200b wherein in Formula 1, each U is independently a direct bond, C(═O)O or C(═O)N(R25).

    • Embodiment 202. The composition of Embodiment 201 wherein each U is independently a direct bond or C(═O)O.

    • Embodiment 203. The composition of Embodiment 202 wherein each U is C(═O)O.

    • Embodiment 204. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 203 wherein in Formula 1, each V is independently a direct bond; or C1-C6 alkylene, C2-C6 alkenylene or C3-C6 alkynylene, each optionally substituted with up to 2 substituents independently selected from halogen, cyano, nitro, hydroxy, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

    • Embodiment 205. The composition of Embodiment 204 wherein each V is independently a direct bond; or C1-C3 alkylene, each optionally substituted with up to 2 substituents independently selected from halogen, hydroxy, C1-C2 alkyl, C1-C2 alkoxy and C1-C2 haloalkoxy.

    • Embodiment 206. The composition of Embodiment 205 wherein each V is independently a direct bond or C1-C3 alkylene.

    • Embodiment 207. The composition of Embodiment 206 wherein each V is independently a direct bond or CH2.

    • Embodiment 208. The composition of Embodiment 207 wherein each V is a direct bond.

    • Embodiment 209. The composition of Embodiment 207 wherein each V is independently C1-C2 alkylene.

    • Embodiment 210. The composition of Embodiment 209 wherein each V is CH2.

    • Embodiment 211. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 210 wherein in Formula 1, each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R27; or a 3- to 6-membered nonaromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are independently selected from C(═O), C(═S), S(═O) and S(═O)2, each ring optionally substituted with up to 2 substituents independently selected from R27.

    • Embodiment 212. The composition of Embodiment 210 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thienyl, isoxazolinyl, piperidinyl, morpholinyl or piperazinyl, each optionally substituted with up to 2 substituents independently selected from R27.

    • Embodiment 213. The composition of Embodiment 212 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each optionally substituted with up to 2 substituents independently selected from R27.

    • Embodiment 214. The composition of Embodiment 213 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl or pyrazolyl, each optionally substituted with up to 2 substituents independently selected from R27.

    • Embodiment 214a. The composition of Embodiment 214 wherein each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27.

    • Embodiment 214b. The composition of Embodiment 214a wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27.

    • Embodiment 215. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 214b wherein in Formula 1, when each R20a is separate (i.e. not taken together with R20b to form a ring), then each R20a is independently H, methyl or methylcarbonyl.

    • Embodiment 216. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 215 wherein in Formula 1, when each R20b is separate (i.e. not taken together with R20a to form a ring), then each R20b is independently H, cyano, methyl, methylcarbonyl, methoxycarbonyl, methoxycarbonylmethyl, methylaminocarbonyl or dimethylaminocarbonyl.

    • Embodiment 217. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 216 wherein in Formula 1, when R20a and R20b are taken together to form a 5- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 methyl groups.

    • Embodiment 218. The composition of Embodiment 217 wherein R20a and R20b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.

    • Embodiment 219. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 218 wherein in Formula 1, each R21 and R23 is independently H, cyano, halogen, methyl or methoxy.

    • Embodiment 220. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 219 wherein in Formula 1, each R22 is independently H, C1-C3 alkyl, C1-C3 haloalkyl, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; or phenyl optionally substituted with up to 2 substituents independently selected halogen and methyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.

    • Embodiment 221. The composition of Embodiment 220 wherein each R22 is independently H or C1-C2 alkyl.

    • Embodiment 222. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 221 wherein in Formula 1, each R24 is independently H, cyano or C1-C2 alkyl.

    • Embodiment 223. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 222 wherein in Formula 1, each R25 and R26 is independently H, cyano, hydroxy, C1-C4 alkyl or C1-C4 haloalkyl.

    • Embodiment 224. The composition of Embodiment 223 wherein each R25 and R26 is independently H, cyano, hydroxy or C1-C2 alkyl.

    • Embodiment 225. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 224 wherein in Formula 1, each R27 is independently halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy.

    • Embodiment 226. The composition of Embodiment 225 wherein each R27 is independently halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C1-C2 alkoxy.

    • Embodiment 227. The composition of Embodiment 226 wherein each R27 is independently halogen, methyl or methoxy.

    • Embodiment 228. The composition of Embodiment 227 wherein each R27 is independently halogen.

    • Embodiment 229. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 228 wherein in Formula 1, Z is a direct bond, 0, NH, C(═O), C(═O)NH, NHC(═O), NHC(═O)NH, OC(═O)NH, NHC(═O)O, S(═O)2NH, NHS(═O)2 or NHS(═O)2NH.

    • Embodiment 230. The composition of Embodiment 229 wherein Z is a direct bond, 0, NH, C(═O), C(═O)NH or NHC(═O).

    • Embodiment 231. The composition of Embodiment 230 wherein Z is a direct bond, 0, NH or C(═O).

    • Embodiment 232. The composition of Embodiment 231 wherein Z is a direct bond.

    • Embodiment 233. The composition of Formula 1 or any one of Embodiments 1 through 232 wherein each R28 is independently H or C1-C3 alkyl.

    • Embodiment 234. The composition of Embodiment 233 wherein each R28 is independently H or methyl.

    • Embodiment 235. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 234 wherein in Formula 1, m is 0 or 2.

    • Embodiment 236. The composition of Embodiment 235 wherein m is 2.

    • Embodiment 237. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 236 wherein component (a) does not comprise an N-oxide of a compound of Formula 1.

    • Embodiment 238. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 236 wherein component (a) comprises a compound selected from the group consisting of



  • ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 1);

  • ethyl 1-[[4-L[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 32);

  • ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 64);

  • ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-3-carboxylate (Compound 231);

  • ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]-3-fluorophenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 262);

  • ethyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 265);

  • ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenoxy]methyl]-1H-pyrazole-4-carboxylate (Compound 364);

  • N-(cyclopropylmethyl)-2-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]-methyl]thiazole-4-carboxamide (Compound 71);

  • 2-methylpropyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 126);

  • cyclopropylmethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 127);

  • ethyl 1-[2-[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]ethyl]-1H-pyrazole-4-carboxylate (Compound 132);

  • 2-methoxyethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 162);

  • 2-butyn-1-yl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 163);

  • 3-cyanopropyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 171);

  • phenylmethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 186);

  • butyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 218);

  • 3-chloropropyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 221);

  • methyl 4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenylcarboxylate (Compound 229);

  • ethyl 1-[[3-fluoro-4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 263);

  • ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenylmethoxy]methyl]-1H-pyrazole-4-carboxylate (Compound 297);

  • methyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 330); and

  • propyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 331).
    • Embodiment 239. The composition of Embodiment 238 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 71, 126, 127, 132, 162, 163, 171, 186, 218, 229, 263, 297, 330 and 331.
    • Embodiment 240. The composition of Embodiment 239 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 71, 126, 127, 132, 162, 163, 171, 218, 229 and 263.
    • Embodiment 241. The composition of Embodiment 240 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 126, 127, 132, 162, 163, 171 and 263.
    • Embodiment 242. The composition of Embodiment 241 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 126, 132, 163 and 263.
    • Embodiment 243. The composition of Embodiment 242 wherein component (a) comprises a compound selected from the group consisting of Compounds 32 and 64.
    • Embodiment 243a. The composition of Embodiment 243 wherein component (a) is Compound 32.
    • Embodiment 243b. The composition of Embodiment 243 wherein component (a) is Compound 64.
    • Embodiment 244. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 245. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 246. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]-3-fluorophenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 247. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 248. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenoxy]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 249. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[2-[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]ethyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 250. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is phenylmethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 251. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is butyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 252. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is 3-chloropropyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 253. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenylmethoxy]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 254. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is methyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 255. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is propyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate, its (E)-isomer or a mixture thereof.
    • Embodiment 256. The composition of Embodiments 238 through 255 wherein wherin component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, metconazole, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, boscalid, fluopyram, luindapyr, fluxapyroxad, isopyrazam, kresoxim-methyl, penthiopyrad, picoxystrobin, proquinazid, pyraclostrobin, quinoxyfen, sedaxane or trifloxystrobin.
    • Embodiment 257. The composition of Embodiments 238 through 256 wherein wherin component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin, or trifloxystrobin.
    • Embodiment 258. The composition of Embodiment 257 wherein (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin or trifloxystrobin.



Embodiments of this invention, including Embodiments 1-258 above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments not only to the compositions comprising compounds of Formula 1 with at least one other fungicidal compound but also to compositions comprising compounds of Formula 1 with at least one invertebrate pest control compound or agent, and also to the compounds of Formula 1 and their compositions, and also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-258 above as well as any other embodiments described herein, and any combination thereof, pertain to the methods of the present invention. Therefore of note as a further embodiment is the composition disclosed above comprising (a) at least one compound selected from the compounds of Formula 1 described above, N-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.


Combinations of Embodiments 1-258 are illustrated by:

    • Embodiment A. The composition comprising components (a) and (b) described Summary of the Invention wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein in Formula 1,
      • R1 is CF3, CCl3 or CF2Cl;
      • W is O;
      • R5a and R5b are each independently H, hydroxy or methyl;
      • R2a and R2b are each independently H or methyl; or
      • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(═O), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members;
      • R2c is C1-C2 alkyl, C2-C3 alkenyl or C2-C3 alkynyl;
      • R2d is H or methyl;
      • A1 is CR6cR6d or O;
      • A2 is a direct bond, CR6eR6f or O;
      • R6a, R6b, R6c, R6d, R6e and R6f are each independently H, cyano, hydroxy, Br, Cl, F or methyl;
      • J is J-1, J-6 or J-14;
      • each R8 is independently F, Cl or methyl;
      • each R9a and R9b is independently H, halogen or methyl;
      • n is 0, 1 or 2;
      • E1 is C1-C6 alkoxy, C1-C6 alkylsulfonyl, C2-C6 alkylcarbonyl or C2-C6 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b;
      • R10a is phenyl optionally substituted with up to 2 substituents independently selected from R11a; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members and R11b on nitrogen atom ring members;
      • each R10b is independently halogen, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, C2-C4 alkylcarbonyl or C2-C5 alkoxycarbonyl;
      • each R11a is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C3 alkoxycarbonyl;
      • each R11b is independently methyl, methoxy, methylcarbonyl or methoxycarbonyl;
      • G is selected from the group consisting of:




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      • wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3;

      • each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C1-C6 alkoxy, C2-C6 alkenyloxy, C2-C6 alkynyloxy, C1-C6 alkylsulfonyl, C1-C6 alkylsulfonyloxy, C1-C6 alkylsulfonylamino, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C6 alkenyloxycarbonyl, C3-C6 alkynyloxycarbonyl, C4-C6 cycloalkoxycarbonyl or C2-C6 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from R19;

      • each R14a is independently H, C1-C2 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkylcarbonyl or C2-C4 alkoxycarbonyl;

      • each R14b is independently H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylaminoalkyl or C3-C5 dialkylaminoalkyl; or

      • R14a and R14b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl;

      • each R19 is independently cyano, halogen, C1-C2 alkyl, C1-C2 haloalkyl, C3-C6 cycloalkyl, C1-C2 alkoxy, C1-C2 haloalkoxy, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl or C2-C3 alkoxycarbonyl;

      • each U is independently a direct bond, C(═O)O or C(═O)N(R25);

      • each V is independently a direct bond; or C1-C3 alkylene, each optionally substituted with up to 2 substituents independently selected from halogen, hydroxy, C1-C2 alkyl, C1-C2 alkoxy and C1-C2haloalkoxy;

      • each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R27; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each optionally substituted with up to 2 substituents independently selected from R27;

      • each R25 is independently H, cyano, hydroxy or C1-C2 alkyl;

      • each R27 is independently halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C1-C2 alkoxy; and

      • Z is a direct bond, O, NH, C(═O), C(═O)NH, NHC(═O), NHC(═O)NH, OC(═O)NH, NHC(═O)O, S(═O)2NH, NHS(═O)2 or NHS(═O)2NH.



    • Embodiment AA. The composition of Embodiment A wherein in Formula 1,
      • R1 is CF3;
      • X is O;
      • Y is O;
      • L is a direct bond or CH2; and
      • Z is a direct bond.

    • Embodiment AAA. The composition of Embodiment A wherein in Formula 1,
      • R1 is CF3;
      • Z is a direct bond.

    • Embodiment B. The composition of Embodiment A wherein in Formula 1,
      • T is T-2 or T-3;
      • R1 is CF3;
      • X is O;
      • Y is O;
      • R2a and R2b are each independently H or methyl; or
      • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member;
      • R2c is methyl or ethyl;
      • R2d is H;
      • A1 is O;
      • A2 is a direct bond or CH2;
      • R6a and R6b are each independently H, cyano hydroxy or methyl;
      • J is J-1 or J-6;
      • q is 0 or 1;
      • each R9a and R9b is independently H or methyl;
      • E1 is C1-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b;
      • R10a is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members;
      • each R10b is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C4 alkoxycarbonyl;
      • G is G-1, G-3, G-12 or G-22;
      • x is 1 or 2;
      • each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19;
      • each R14a is independently H or C1-C2 alkyl;
      • each R14b is independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl;
      • each R19 is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl;
      • each U is independently a direct bond or C(═O)O;
      • each V is independently a direct bond or CH2;
      • each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27;
      • each R27 is independently halogen, methyl or methoxy; and
      • Z is a direct bond, O, NH, C(═O), C(═O)NH or NHC(═O).

    • Embodiment BB. The composition of Embodiment B wherein in Formula 1,
      • L is a direct bond or CH2;
      • G is G-1 or G-12; and
      • Z is a direct bond.

    • Embodiment BBB. The composition of Embodiment B wherein in Formula 1,
      • Z is a direct bond.

    • Embodiment C. The composition of Embodiment B wherein in Formula 1,
      • R2a and R2b are each H; or
      • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms;
      • A2 is a direct bond;
      • R6a and R6b are each H;
      • R8 is F or C1;
      • L is a direct bond, CH2 or CH2CH2;
      • E1 is C1-C2 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a;
      • R10a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members;
      • each R11a is independently methoxycarbonyl or ethoxycarbonyl;
      • G is G-1 and the 2-position of G-1 is connected to Z and the 4-position is connected to R13 or G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13;
      • x is 1;
      • R13 is C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19;
      • R14a is H;
      • R14b is H, methyl or cyclopropylmethyl;
      • R19 is cyano, halogen, cyclopropyl or methoxy;
      • U is C(═O)O;
      • V is CH2;
      • Q is phenyl optionally substituted with up to 2 substituents independently selected from R27; and
      • Z is a direct bond, O, NH or C(═O).

    • Embodiment CC. The composition of Embodiment C wherein in Formula 1,
      • L is a direct bond or CH2; and
      • Z is a direct bond.

    • Embodiment D. The composition of Embodiment C wherein in Formula 1,
      • R8 is F;
      • L is a direct bond or CH2;
      • E1 is methoxy substituted with 1 substituent selected from R10a;
      • R10a is pyrazolyl optionally substituted with up to 1 substituent selected from R11a on a carbon atom ring member;
      • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; and
      • R13 is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from R19;
      • R19 is cyano, Cl, F, cyclopropyl or methoxy; and
      • Z is a direct bond.

    • Embodiment DD. The composition of Embodiment D wherein in Formula 1,
      • L is a direct bond or CH2, provided that when L is a direct bond, then E is E1, and when L is CH2, then E is E2.

    • Embodiment E. The composition of Embodiment D wherein in Formula 1,
      • J is J-1;
      • q is O;
      • L is CH2;
      • E is E2;
      • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; and
      • R13 is methoxycarbonyl or ethoxycarbonyl.

    • Embodiment EE. The composition of Embodiment E wherein in Formula 1,
      • R2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.

    • Embodiment F. The composition of any one of Embodiments A through EE wherein in Formula 1,
      • T is T-2; and
      • R13 is ethoxycarbonyl.

    • Embodiment G. The composition of any one of Embodiments A through E wherein in Formula 1,
      • T is T-3; and
      • R13 is ethoxycarbonyl.

    • Embodiment H. The composition any one of Embodiments A through G wherein component (a) comprises a compound selected from the group consisting of: Compound 1, Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 221, Compound 229, Compound 231, Compound 262, Compound 263, Compound 265, Compound 297, Compound 330, Compound 331 and Compound 364.

    • Embodiment I. The composition of Embodiment H wherein component (a) comprises a compound selected from the group consisting of: Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 229, Compound 263, Compound 297, Compound 330 and Compound 331.

    • Embodiment J. The composition of Embodiment I wherein component (a) comprises a Compound 32.

    • Embodiment K. The composition of Embodiment I wherein component (a) comprises Compound 64.

    • Embodiment B1. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b1) methyl benzimidazole carbamate fungicides such as benomyl, carbendazim, fuberidazole thiabendazole, thiophanate and thiophanate-methyl.

    • Embodiment B2. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b2) dicarboximide fungicides such as chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.

    • Embodiment B3. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b3) demethylation inhibitor fungicides such as triforine, buthiobate, pyrifenox, pyrisoxazole fenarimol, nuarimol, triarimol econazole, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizoleazaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, ipfentrifluconazole, quinconazole, simeconazole, tebuconazole, tetraconazole triadimefon, triadimenol, triticonazole, uniconazole and uniconazole-P.

    • Embodiment B4. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b4) phenylamide fungicides such as metalaxyl, metalaxyl-M, benalaxyl, benalaxyl-M, furalaxyl, ofurace and oxadixyl.

    • Embodiment B5. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b5) amine/morpholine fungicides such as aldimorph, dodemorph, fenpropimorph, tridemorph, trimorphamide, fenpropidin, piperalin and spiroxamine.

    • Embodiment B6. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b6) phospholipid biosynthesis inhibitor fungicides such as edifenphos, iprobenfos, pyrazophos and isoprothiolane.

    • Embodiment B7. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b7) succinate dehydrogenase inhibitor fungicides such as benodanil, flutolanil, mepronil, isofetamid, fluopyram, fenfuram, carboxin, oxycarboxin thifluzamide, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne, sedaxane, flubeneteram, isoflucypram, pydiflumetofen, boscalid and pyraziflumid.

    • Embodiment B8. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b8) hydroxy(2-amino-)pyrimidine fungicides such as bupirimate, dimethirimol and ethirimol.

    • Embodiment B9. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b9) anilinopyrimidine fungicides such as cyprodinil, mepanipyrim and pyrimethanil.

    • Embodiment B10. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b10) N-phenyl carbamate fungicides such as diethofencarb.

    • Embodiment B11. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b11) fungicides quinone outside inhibitor fungicides such as azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, fluoxastrobin, famoxadone, fenamidone and pyribencarb.

    • Embodiment B12. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b12) phenylpyrrole fungicides compound such as fenpiclonil and fludioxonil.

    • Embodiment B13. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b13) azanaphthalene fungicides such as quinoxyfen and proquinazid.

    • Embodiment B14. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b14) cell peroxidation inhibitor fungicides such as biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl and etridiazole.

    • Embodiment B15. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b15) melanin biosynthesis inhibitors-reductase fungicides such as fthalide, pyroquilon and tricyclazole.

    • Embodiment B16a. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b16a) melanin biosynthesis inhibitors-dehydratase fungicides such as carpropamid, diclocymet, and fenoxanil.

    • Embodiment B16b. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b16b) melanin biosynthesis inhibitor-polyketide synthase fungicides such as tolprocarb.

    • Embodiment B17. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b17) keto reductase inhibitor fungicides such as fenhexamid, fenpyrazamine, quinofumelin and ipflufenoquin.

    • Embodiment B18. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b18) squalene-epoxidase inhibitor fungicides such as pyributicarb, naftifine and terbinafine.

    • Embodiment B19. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b19) polyoxin fungicides such as polyoxin.

    • Embodiment B20. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 243 and A through K) wherein component (b) includes at least one compound selected from (b20) phenylurea fungicides such as pencycuron.

    • Embodiment B21. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b21) quinone inside inhibitor fungicides such as cyazofamid, amisulbrom and fenpicoxamid (Registry Number 517875-34-2).

    • Embodiment B22. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b22) benzamide and thiazole carboxamide fungicides such as zoxamide and ethaboxam.

    • Embodiment B23. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b23) enopyranuronic acid antibiotic fungicides such as blasticidin-S.

    • Embodiment B24. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b24) hexopyranosyl antibiotic fungicides such as kasugamycin.

    • Embodiment B25. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b25) glucopyranosyl antibiotic: protein synthesis fungicides such as streptomycin.

    • Embodiment B26. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides such as validamycin.

    • Embodiment B27. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b27) cyanoacetylamideoxime fungicides such as cymoxanil.

    • Embodiment B28. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b28) carbamate fungicides such as propamacarb, prothiocarb and iodocarb.

    • Embodiment B29. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b29) oxidative phosphorylation uncoupling fungicides such as fluazinam, binapacryl, meptyldinocap and dinocap.

    • Embodiment B30. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b30) organo tin fungicides such as fentin acetate, fentin chloride and fentin hydroxide.

    • Embodiment B31. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b31) carboxylic acid fungicides such as oxolinic acid.

    • Embodiment B32. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b32) heteroaromatic fungicides such as hymexazole and octhilinone.

    • Embodiment B33. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b33) phosphonate fungicides such as phosphorous acid and its various salts, including fosetyl-aluminum.

    • Embodiment B34. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b34) phthalamic acid fungicides such as teclofthalam.

    • Embodiment B35. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b35) benzotriazine fungicides such as triazoxide.

    • Embodiment B36. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b36) benzene-sulfonamide fungicides such as flusulfamide.

    • Embodiment B37. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b37) pyridazinone fungicides such as diclomezine.

    • Embodiment B38. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b38) thiophene-carboxamide fungicides such as silthiofam.

    • Embodiment B39. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b39) complex I NADH oxidoreductase inhibitor fungicides such as diflumetorim, tolfenpyrad and fenazaquin.

    • Embodiment B40. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b40) carboxylic acid amide fungicides such as dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalate, mandipropamid, flumorph, dimethomorph, flumorph, pyrimorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb, valifenalate and mandipropamid.

    • Embodiment B41. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b41) tetracycline antibiotic fungicides such as oxytetracycline.

    • Embodiment B42. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b42) thiocarbamate fungicides such as methasulfocarb.

    • Embodiment B43. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b43) benzamide fungicides such as fluopicolide and fluopimomide.

    • Embodiment B44. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b44) microbial fungicides such as Bacillus amyloliquefaciens strains QST713, FZB24, MB1600, D747, F727, TJ100 (also called strain 1 BE; known from EP2962568) and the fungicidal lipopeptides which they produce.

    • Embodiment B45. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b45) quinone outside inhibitor, stigmatellin binding fungicides such as ametoctradin.

    • Embodiment B46. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b46) plant extract fungicides such as Melaleuca alternifolia, eugenol, geraniol and thymol.

    • Embodiment B47. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b47) cyanoacrylate fungicides such as phenamacril.

    • Embodiment B48. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b48) polyene fungicides such as natamycin.

    • Embodiment B49. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b49) oxysterol binding protein inhibitor fungicides such as oxathiapiprolin and fluoxapiprolin.

    • Embodiment B50. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b50) aryl-phenyl-ketone fungicides such as metrafenone and pyriofenone.

    • Embodiment B51. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b51) host plant defense induction fungicides such as acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, extract from Reynoutria sachalinensis and Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS117.

    • Embodiment B52. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b52) multi-site activity fungicides such as copper oxychloride, copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), elemental sulfur, ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb, ziram, folpet, captan, captafol, chlorothalonil, dichlofluanid, tolyfluanid, guazatine, iminoctadine albesilate, iminoctadine triacetate, anilazine, dithianon, quinomethionate and fluoroimide.

    • Embodiment B53. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b53) biological fungicides with multiple modes of action such as extract from the cotyledons of lupine plantlets.

    • Embodiment B54. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54) fungicides other than fungicides of component (a) and components (b1) through (b53), such as cyflufenamid, bethoxazin, neo-asozin, pyrrolnitrin, tebufloquin, dodine, flutianil, ferimzone, picarbutrazox, dichlobentiazox (Registry Number 957144-77-3), dipymetitrone (Registry Number 16114-35-5), flometoquin, tolnifanide (Registry Number 304911-98-6), N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenyl N-[l-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate (XR-539).

    • Embodiment B55. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name florylpicoxamid).

    • Embodiment B56. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes 1-[2-[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]-3-methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazol-5-one (provisional common name metyltetraprole).

    • Embodiment B57. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional common name pyridachlometyl).

    • Embodiment B58. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate (provisional common name aminopyrifen).

    • Embodiment B59. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.11) (i.e Formula b54.11)







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      • wherein
        • Rb10 and Rb11 are each independently halogen; and
        • R6 is H, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl.



    • Embodiment B60. The composition of Embodiment B59 wherein component (b) includes at least one fungicidal compound selected from the group consisting of methyl N-[[5-[1-(2,6-difluoro-4-formylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl] methyl]carbamate, methyl N-[[5-[11-(4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]-carbamate, methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methyl-phenyl]methyl]carbamate, methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl) phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate and methyl N-[[5-[1-[2,6-di fluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate.

    • Embodiment B61. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.12) (i.e Formula b54.12)







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    • wherein
      • Rb4 is







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      • Rb6 is C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;

      • L is CH2 or CH2O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12; and

      • Rb5 is









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    • Embodiment B62. The composition of Embodiment B61 wherein component (b) includes at least one fungicidal compound selected from the group consisting of N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide and ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate.

    • Embodiment B63. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.13) (i.e Formula b54.13)







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    • wherein
      • Rb7, Rb8 and Rb9 are each independently H, halogen or cyano; and
      • Rb10 and Rb11 are each independently H, halogen, C1-C3 alkyl or C1-C3 methoxy

    • Embodiment B64. The composition of Embodiment B63 wherein component (b) includes at least one fungicidal compound selected from the group consisting of 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 3,5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile and N-(2-chloro-4-fluoro-6-nitrophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine.

    • Embodiment B65. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one fungicidal compound (fungicide) selected from the group consisting of azoxystrobin, benzovindiflupyr, boscalid (nicobifen), bixafen, bromuconazole, carbendazim, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenbuconazole, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, hexaconazole, ipconazole kresoxim-methyl, manzate, metconazole, metominostrobin, metrafenone, myclobutanil, penconazole, penthiopyrad, picoxystrobin, prochloraz, propiconazole, proquinazid, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyriofenone quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine and 3,5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile.

    • Embodiment B66. The composition of Embodiment B65 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, kresoxim-methyl, manzate, metconazole, metominostrobin, metrafenone, myclobutanil, penthiopyrad, picoxystrobin, propiconazole, proquinazid, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyriofenone, quinoxyfen, tebuconazole, trifloxystrobin, triticonazole, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1, 2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine and 3, 5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile.

    • Embodiment B67. The composition of Embodiment B66 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, difenoconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, manzate, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole, trifloxystrobin, methyl N-[[5-[1-[2,6-difluoro-4-(1-methylethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, methyl N-[[5-[1-[2,6-difluoro-4-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, N-(2,2,2-trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-4-methyl-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, 4-(2-chloro-4-fluorophenyl)-N-(2-fluoro-6-nitrophenyl)-1,3-dimethyl-1H-pyrazol-5-amine and 3,5-difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]-1,3-dimethyl-1H-pyrazol-4-yl]-benzonitrile.

    • Embodiment B68. The composition of Embodiment B67 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, manzate, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole, trifloxystrobin.





Of note is the composition of any one of the embodiments described herein, including any Embodiments 1 through 258, A through K, and B1 through B68, wherein reference to Formula 1 includes salts thereof but not N-oxides thereof; therefore the phrase “a compound of Formula 1” can be replaced by the phrase “a compound of Formula 1 or a salt thereof”. In this composition of note, component (a) comprises a compound of Formula 1 or a salt thereof.


Also noteworthy as embodiments are fungicidal compositions of the present invention comprising a fungicidally effective amount of a composition of Embodiments 1 through 258, A through K, and B1 through B68, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.


Embodiments of the invention further include methods for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a composition any one of Embodiments 1 through 258, A through K, and B1 through B68 (e.g., as a composition including formulation ingredients as described herein). Embodiments of the invention also include methods for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of a composition of any one of Embodiments 1 through 258, A through K, and B1 through B68 to the plant or plant seed.


Some embodiments of the invention involve control of a plant disease or protection from a plant disease that primarily afflicts plant foliage and/or applying the composition of the invention to plant foliage (i.e. plants instead of seeds). The preferred methods of use include those involving the above preferred compositions; and the diseases controlled with particular effectiveness include plant diseases caused by fungal plant pathogens. Combinations of fungicides used in accordance with this invention can facilitate disease control and retard resistance development.


Method embodiments further include:

    • Embodiment C1. A method for protecting a plant from a disease selected from rust, powdery mildew and Septoria diseases comprising applying to the plant a fungicidally effective amount of the composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 258.
    • Embodiment C2. The method of Embodiment Cl wherein the disease is a rust disease and component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b5) amine/morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b11) quinone outside inhibitor (QoI) fungicides, (b13) methyl benzimidazole carbamate fungicides and (b52) multi-site activity fungicides.
    • Embodiment C3. The method of Embodiment C2 wherein component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides and (b11) quinone outside inhibitor (QoI) fungicides.
    • Embodiment C4. The method of Embodiment C3 wherein component (b) of the composition includes at least one fungicidal compound selected from the group consisting of azoxystrobin, cyproconazole, difenoconazole, epoxiconazole, fluindapyr, flutriafol, fluxapyroxad, picoxystrobin, prothioconazole, pyraclostrobin, tebuconazole and trifloxystrobin.
    • Embodiment C5. The method of Embodiments C2 through C4 wherein the disease is Asian soybean rust caused by Puccinia recondite.
    • Embodiment C6. The method of Embodiments C2 through C4 wherein the disease is wheat leaf rust caused by Phakopsora pachyrhizi.
    • Embodiment C7. The method of Embodiment Cl wherein the disease is a powdery mildew disease and component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b11) quinine outside inhibitor (QoI) fungicides and (b13) azanaphthalene fungicides.
    • Embodiment C8. The method of Embodiment C7 wherein the disease is wheat powdery mildew.
    • Embodiment C9. The method of Embodiment C7 wherein the disease is grape downy mildew.
    • Embodiment C10. The method of Embodiments C7 through C9 wherein component (b) includes at least one fungicidal compound selected from (b3) DMI fungicides.
    • Embodiment C11. The method of Embodiment C10 wherein component (b) includes at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, prothioconazole and tebuconazole.
    • Embodiment C12. The method of Embodiment C11 wherein component (b) includes at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole and prothioconazole.
    • Embodiment C13. The method of Embodiments C8 through C10 wherein component (b) includes at least one fungicidal compound selected from (b11) QoI fungicides.
    • Embodiment C14. The method of Embodiment C12 wherein component (b) includes at least one fungicidal compound selected from the group consisting of azoxystrobin, picoxystrobin and pyraclostrobin.
    • Embodiment C15. The method of Embodiment C1 wherein the disease is a Septoria disease and component (b) of the composition includes at least one fungicidal compound selected from the group consisting of epoxiconazole, metalaxyl (including metalaxyl-M), iprovalicarb and fenpropimorph.
    • Embodiment C16. The method of Embodiment C15 wherein the disease is wheat leaf blotch.
    • Embodiment C17. The method of any one of Embodiments C1 through C16 wherein components (a) and (b) are applied in synergistically effective amounts (and in a synergistic ratio relative to each other).


Of note are embodiments that are counterparts of Embodiments C1 through C17 relating to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, a fungicidally effective amount of a fungicidal composition of the invention.


As noted in the Summary of the Invention, this invention also relates to a compound of Formula 1, or an N-oxide or salt thereof. Also noted is that the embodiments of this invention, including Embodiments 1-258, relate also to compounds of Formula 1. Accordingly, combinations of Embodiments 1-258 are further illustrated by:

    • Embodiment D1. A compound of Formula 1, or an N-oxide or salt thereof, wherein
      • T is T-2;
      • R1 is CF3;
      • X is O;
      • Y is O;
      • R2a is H or methyl;
      • R2b is C3-C15 trialkylsilyl or C3-C15 halotrialkylsilyl;
      • A1 is O;
      • A2 is a direct bond or CH2;
      • R6a and R6b are each independently H, cyano hydroxy or methyl;
      • J is J-1 or J-6;
      • q is 0 or 1;
      • L is a direct bond or CH2;
      • E is E1 or E2;
      • E1 is C1-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b;
      • R10a is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members;
      • each R10b is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C4 alkoxycarbonyl;
      • each R11a is independently methoxycarbonyl or ethoxycarbonyl;
      • G is G-1, G-3, G-12 or G-22;
      • x is 1 or 2;
      • each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19;
      • each R14a is independently H or C1-C2 alkyl;
      • each R14b is independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl;
      • each R19 is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl;
      • each U is independently a direct bond or C(═O)O;
      • each V is independently a direct bond or CH2;
      • each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27;
      • each R27 is independently halogen, methyl or methoxy; and
      • Z is a direct bond, O, NH, C(═O), C(═O)NH or NHC(═O).
    • Embodiment D2. A compound of Embodiment D1 wherein
      • R2a is H or methyl;
      • R2b is trimethylsilyl or halotrimethylsilyl;
      • A2 is a direct bond;
      • R6a and R6b are each H;
      • R8 is F or C1;
      • E1 is C1-C2 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a;
      • R10a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members;
      • each R11a is independently methoxycarbonyl or ethoxycarbonyl;
      • G is G-1 and the 2-position of G-1 is connected to Z and the 4-position is connected to R13 or G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13;
      • x is 1;
      • R13 is C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19;
      • R14a is H;
      • R14b is H, methyl or cyclopropylmethyl;
      • R19 is cyano, halogen, cyclopropyl or methoxy;
      • U is C(═O)O;
      • V is CH2;
      • Q is phenyl optionally substituted with up to 2 substituents independently selected from R27; and
      • Z is a direct bond, O, NH or C(═O).
    • Embodiment D3. A compound of Embodiment D2 wherein
      • R2a is H or methyl;
      • R2b is trimethylsilyl;
      • R8 is F;
      • E1 is methoxy substituted with 1 substituent selected from R10a;
      • R10a is pyrazolyl optionally substituted with up to 1 substituent selected from R11a on a carbon atom ring member;
      • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; and
      • R13 is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from R19;
      • R19 is cyano, Cl, F, cyclopropyl or methoxy; and
      • Z is a direct bond.
    • Embodiment D3. A compound of Embodiment D3 wherein
      • R2a is methyl;
      • J is J-1;
      • q is O;
      • L is CH2;
      • E is E2;
      • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; and
      • R13 is methoxycarbonyl or ethoxycarbonyl.


Additional embodiments include a fungicidal composition comprising: (1) a compound of any one of Embodiments D1 through D3; and (2) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Additional embodiments also include a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of the compound of any one of Embodiments D1 through D3 to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed). Of note are embodiments relating to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, a fungicidally effective amount of a compound of any one of Embodiments D1 through D3.


This invention also provides a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof) (i.e. in a fungicidally effective amount), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Of note as embodiments of such compositions are compositions comprising a compound corresponding to any of the compound embodiments described above.


One or more of the following methods and variations as described in Schemes 1-17 can be used to prepare the compounds of Formula 1. The definitions of E, L, A, A1, A2, J, T, X, Y, R1, R2a. R2b. R2c. R2d. R6a. R6b and R29 in the compounds of Formulae 1-14 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae 1a-1a1, 1b-1b6 and 1c-1c1 are various subsets of Formula 1, and all substituents for Formulae 1a-1a1, 1b-1b6 and 1c-1c1 are as defined above for Formula 1 unless otherwise noted. As the synthetic literature includes many halomethyl ketone and hydrate-forming methods, which can readily be adapted to prepare compounds of the present invention, the following methods in Schemes 1-17 are simply representative examples of a wide variety of procedures useful for the preparation of the compounds of Formula 1. For reviews of ketone and hydrate-forming methods, see, for example, Tetrahedron 1991, 47, 3207-3258 and Chem. Communications 2013, 49(95), 11133-11148, and references cited therein. Also see the methods outlined in U.S. Pat. No. 6,350,892.


As shown in Scheme 1, Compounds of Formula 1a (i.e. Formula 1 wherein T is T-1 and W is O) wherein R1 is CF3 can be prepared by trifluoroacetylation of organometallic compounds of Formula 2. Typically, the ethyl ester of trifluoroacetic acid (i.e. ethyl trifluoroacetate) is used as the source of the trifluoroacetyl group in this method, but trifluoroacetonitrile and various trifluoroacetate salts can also be used. Depending on the reaction conditions, double-addition on the trifluoroacetyl compound can occur. Conducting the reaction at −65° C., or more preferably at −78° C., can reduce the occurrence of double addition adducts to trace amounts, particularly when using organometallic species of Formula 2 wherein M is Li or MgBr. Many other organometallic species yield similar results. For reaction conditions useful in the method of Scheme 1, as well as other well-established routes for the synthesize trifluoromethyl ketones see, for example, Journal of Organic Chemistry 1987, 52(22), 5026-5030; Chemical Communications 2013, 49(95), 11133-11148; and Journal of Fluorine Chemistry 1981, 18, 117-129. Conditions described in these references can easily be modified to prepare compounds of Formula 1a wherein R1 is other than CF3 (e.g., dihalo- or trichloro-moieties).




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Compounds of Formula 1a (i.e. Formula 1 wherein T is T-1 and W is O) wherein R1 is CF3 can also be prepared via alkylation of ethyl 4,4,4-trifluoroacetoacetate (ETFAA) with compounds of Formula 3 wherein La is a leaving group such as halogen (e.g., Cl, Br) or sulfonate (e.g., mesylate). In this method ETFAA is first treated with a base such as sodium hydride in a polar aprotic solvent such tetrahydrofuran (THF), THF/hexamethylphosphoramide (HMPA) or acetone. The ETFAA anion then displaces the leaving group in compounds of Formula 3 to give an intermediate ester which undergoes hydrolysis and decarboxylation in the presence of lithium chloride (LiCl) and N,N-dimethylformamide (DMF) to give the ketone compound of Formula 1a. For reaction conditions see Journal Chemical Society, Chemical Communications 1989, (2), 83-84; Chemical Communications 2013, 49(95), 11133-11148; and Journal of Fluorine Chemistry 1989, 44, 377-394.




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As shown in Scheme 3, compounds of Formula 1a (i.e. Formula 1 wherein T is T-1 and W is O) wherein R1 is CF3 can also be prepared by trifluoromethylation of an ester of Formula 5 with trifluoromethyltrimethylsilane (TMS-CF3). The reaction is run in the present of a fluoride initiator such as tetrabutylammonium fluoride, and in an anhydrous solvent such as toluene or dichloromethane at about −78° C. (for reaction conditions see, for example, Angew. Chem., Int. Ed. 1998, 37(6), 820-821). Cesium fluoride can also be used as an initiator in a solvent such as 1,2-dimethoxyethane (glyme) at room temperature (for reaction conditions see, for example, J. Org. Chem., 1999, 64, 2873). The reaction proceeds through a trimethylsilicate intermediate, which is hydrolyzed with aqueous acid to give the desired trifluoromethyl ketone compound of Formula 1a. Weinreb amides may also be used in place of the starting esters (see, for example, Chem. Commun. 2012, 48, 9610).




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As shown in Scheme 4, compounds of Formula 1a1 (i.e. Formula 1a wherein A is A1-A2-CR6aR6b) wherein R1 is CF3 and at least one R6a or R6b is H can be prepared by reacting acid chlorides of Formula 6 with trifluoroacetic anhydride (TFAA) and pyridine in a solvent such as dichloromethane or toluene at a temperature between about 0 to 80° C. followed by aqueous hydrolysis (for reaction conditions see, for example, Tetrahedron 1995, 51, 2573-2584). Compounds of Formula 6 can be prepared from compounds of Formula 5 by ester hydrolysis to the corresponding carboxylic acid and treatment with oxalyl chloride, as known to one skilled in the art.




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As shown in Scheme 5, compounds of Formula 1b (i.e. Formula 1 wherein T is T-2) wherein R2aX and R2bY are OH can be prepared by oxidation of alcohols of Formula 4 to the corresponding dihydroxy. The oxidation reaction can be performed by a variety of means, such as by treatment of the alcohols of Formula 4 with manganese dioxide, Dess-Martin periodinane, pyridinium chlorochromate or pyridinium dichromate. For typical reaction conditions, see present Example 6, Step F and Example 8, Step F.




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Scheme 6 illustrates a specific example of the general method of Scheme 5 for the preparation of a compound of Formula 1b1 (i.e. Formula 1b wherein L is CH2, J is phenyl (i.e. J-1), A is OCH2 and R1 is CF3). In this method a compound of Formula 4a (i.e. Formula 4 wherein L is CH2, J is phenyl (i.e. J-1), A is OCH2 and R1 is CF3) is reacted with an oxidizing reagent such as Dess-Martin periodinane in a solvent such as dichloromethane at a temperature between about 0 to 80° C. Present Example 1, Step C illustrates the method of Scheme 6.




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As shown in Scheme 7, compounds of Formula 4 can be prepared by reaction of compounds of Formula 2 with R1CHO. For reactions conditions see, Tetrahedron Letters 2007, 48, 6372-6376.




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As shown in Scheme 8, compounds of Formula 4b (i.e. Formula 4 wherein A is OCR6aR6b) can be prepared by reacting a compound of Formula 7 with an epoxide of Formula 8. The reaction is typically carried out in a solvent such as acetonitrile with a catalytic amount of a base such as cesium or potassium carbonate at a temperature between about 20 to 80° C.; or in a solvent such as dichloromethane with a catalytic amount of a Lewis acid such as boron trifluoride etherate at a temperature between about 0 to 40° C. Present Example 8, Step E illustrates the method of Scheme 8. One skilled in the art will recognize that the method of Scheme 8 can also be performed when A is SCR6aR6b or N(R7a)CR6aR6b, thus providing other compounds of Formula 4b.


Compounds of Formulae 7 and 8 are available from commercial sources and can easily be prepared using commercial precursors and known methods. Present Example 1, Step A, Example 6, Step D and Example 8, Step D illustrate the preparation of a compound of Formula 7.




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Scheme 9 illustrates a specific example of the general method of Scheme 8 for the preparation of a compound of Formula 4b1 (i.e. Formula 4b wherein L is CH2, J is phenyl (i.e. J-1), R6a and R6b are H and R1 is CF3) In this method a compound of Formula 7a (i.e. Formula 7 wherein L is CH2 and J is phenyl (i.e. J-1)) is reacted with 2-(trifluoromethyl)oxirane (i.e. Formula 8a) in the presence of cesium carbonate in a solvent such as acetonitrile at a temperature between about 60 to 80° C. Present Example 1, Step B illustrates the method of Scheme 9.




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As illustrated in Scheme 10, ketones of Formula 1a (i.e. Formula 1 wherein T is T-1 and W is O) may exist in equilibrium with their corresponding ketone hydrates (i.e. dihydroxy) of Formula 1b (i.e. Formula 1 wherein T is T-2) wherein R2aX and R2bY are OH. The predominance of Formula 1a or Formula 1b is dependent upon several factors, such as environment and structure. For example, in an aqueous environment ketones of Formula 1a can react with water to give ketone hydrates (also known as 1,1-geminal diols) of Formula 1b. Conversion back to the keto-form can usually be achieved by treatment with a dehydrating agent such as magnesium sulfate or molecular sieves. When the ketone moiety is in close proximity to an electron-withdrawing group, such as when R1 is a trifluoromethyl group, the equilibrium typically favors the dihydrate form. In these cases, conversion back to the keto-form may require a strong dehydrating agent, such as phosphorus pentoxide (P2O5). For reaction conditions see, for example, Eur. J. Org. Chem. 2013, 3658-3661; and Chemical Communications 2013, 49(95), 11133-11148, and references cited therein.




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As shown in Scheme 11, ketones of Formula 1a may also exist in equilibrium with their hemiketals, hemithioketals and hemiaminals of Formula 1b2 (i.e. Formula 1b wherein R2bY is OH and R2a is other than H) along with their ketals, thioketals aminals of Formula 1b wherein R2a and R2b are other than H. Compounds of Formula 1b2 can be prepared by reacting a compound of Formula 1a with a compound of formula R2aX—H (e.g., alcohols for X being O, thiols for X being S or amines for X being NR5a), usually in the presence of an catalysis, such as a Bronsted (i.e. protic) acid or Lewis acid (e.g. BF3), (see, for example, Master Organic Chemistry (Online), On Acetals and Hemiacetals, May 28, 2010, www.masterorganic-chemistry.com/2010/05/28/on-acetals-and-hemiacetals). In a subsequent step, compounds of Formula 1b2 can be treated with a compound of formula R2bY—H (e.g., alcohols for Y being O, thiols for Y being S or amines for Y being NR5b) under dehydrating conditions, or other means of water removal that will drive the equilibrium in the reaction to the right, to provide compounds of Formula 1b wherein R2a and R2b are other than H. Alternatively, ketones of Formula 1a can initially be treated with two equivalents (or an excess amount) of an alcohol, thiol or amine typically in the presence of a catalysis together with a dehydrating agent to provide compounds of Formula 1b directly (see, for example, the preparation of the dimethylketals using methanol and trimethyl orthoformate in U.S. Pat. No. 6,350,892).




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As illustrated in Scheme 12, cyclic ketals of Formula 1b3 (i.e. Formula 1b wherein X and Y are O, and R2a and R2b are taken together to form a 5- to 7-membered ring) can be prepared by treating the corresponding ketones of Formula 1a with haloalcohols (e.g., 2-chloroethanol or 2-bromopropanol) in the presence of a base such as potassium carbonate or potassium tert-butoxide and in as solvent such as acetonitrile or N,N-dimethylformamide (DMF). For reactions conditions see, Organic Letters 2006 8(17), 3745-3748.




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The method of Scheme 12 is also useful for preparing cyclic ketals stating from the corresponding ketone hydrate form. Scheme 13 illustrates a specific example where a ketone hydrate of Formula 1b4 (i.e. Formula 1b wherein L is CH2, J is phenyl (i.e. J-1), A is OCH2, R2aX and R2bY are OH and R1 is CF3) is reacted with 2-chloroethanol in the presence of potassium carbonate in acetonitrile at a temperature between about 25 to 70° C. to provide a compound of Formula 1b5 (i.e. Formula 1b wherein L is CH2, J is phenyl (i.e. J-1), A is OCH2, X and Y are O, R2a and R2b are taken together to form a 5-membered ring and R1 is CF3). Present Example 2 illustrates the method of Scheme 13.




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As shown in Scheme 14, Compounds of Formula 1b6 (i.e. compounds of Formula 1b wherein A is A1-A2-CR6aR6b) wherein A1 is N(R7a), O or S and A2 is a direct bond, or wherein A1 is CR6cR6d and A2 is N(R7b), O or S can be prepared by reacting compounds of Formula 9 wherein A1 is O, S or N(R7a) and A2 is a direct bond, or where A1 is CR6cR6d and A2 is O, S or N(R7b) with compounds of Formula 10. The reaction is typically run in a solvent such N,N-dimethylformamide (DMF) or dimethyl sulfoxide with a base such as cesium or potassium carbonate or sodium hydride at a temperature between about 20 to 80° C. The method of Scheme 14 is illustrated in Example 4, Step D.




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Compounds of Formula 10 can be prepared using commercial precursors and known methods. For example, as shown in Scheme 15, compounds of Formula 10a (i.e. Formula 10 wherein R6a and R6b are H, X and Y are O and R2a and R2b are taken together to form a 5-membered ring) can be prepared reacting compounds of Formula 11 with haloalcohols (e.g., 2-chloroethanol or 3-bromopropanol) under basic conditions (e.g., potassium tert-butoxide in a solvent such as N,N-dimethylformamide or tetrahydrofuran) to provide compounds of Formula 12. A variety of methods are disclosed in the chemical literature for the conversion of ketones to cyclic ketals and can be readily adapted to prepare compounds of Formula 12 (see, for example, G. Hilgetag and A. Martini, Ed., Preparative Organic Chemistry, pp 381-387: Wiley, New York, 1972, and references sited therein; also see present Example 4, Step A). The ester moiety of the resulting cyclic ketal of Formula 12 can be reduced to the corresponding alcohol of Formula 13 by standard methods known to one skilled in the art (Example 4, Step B illustrates a typical procedure). The hydroxy moiety in the compounds of Formula 13 can then be converted to a wide variety of R29 groups to provide compounds of Formula 10a. For example, a mesylate or tosylate group can be installed by treating the alcohol with methanesulfonyl chloride (mesyl chloride) or 4-toluenesulfonyl chloride (tosyl chloride) in the presence of a base such as triethylamine at a temperature between about 0 to 40° C. and in a solvent such as dichloromethane. A triflate group can be installed by treating the alcohol with triflic anhydride (CF3SO2)2O as illustrated in Example 4, Step C. Compounds of Formula 11 are known and can be prepared by methods known to one skilled in the art.




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Compounds of Formula 1c (i.e. Formula 1 wherein T is T-3 and X is O) can be prepared by reacting a compound of Formula 1a (i.e. Formula 1 wherein T is T-1 and W is O) wherein at least one of R6a and R6b is H with a compound of Formula 14 in the presence of a base, as illustrated in Scheme 16. Suitable bases include cesium or potassium carbonate in a solvent such as N,N-dimethylformamide (DMF) or dimethyl sulfoxide at temperatures from about 20 to 80° C. In some cases, the method of Scheme 16 results in a mixture of O-alkylated product (typically as a mixture of (E)- and (Z)-isomers), along with C-alkylated product. Purification can be achieved using standard techniques such as column chromatography (see Magnetic Resonance in Chemistry 1991, 29, 675-678). Compounds of Formula 14 are commercially available and can be easily synthesized by general methods known to one skilled in the art.




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The method of Scheme 16 is also useful for preparing compounds of Formula 1c stating from the corresponding ketone hydrate. Scheme 17 illustrates a specific example where a ketone hydrate of Formula 1b4 (i.e. Formula 1b wherein L is CH2, J is phenyl (i.e. J-1), A is OCH2, R2aX and R2bY are OH and R1 is CF3) is reacted with iodoethane in the presence of cesium carbonate in dimethyl sulfoxide at a temperature between about 25 to 75° C. to provide a compound of Formula 1c1 (i.e. Formula 1e wherein L is CH2, J is phenyl (i.e. J-1), A is O, R2d is H, XR2c is OCH2CH3 and R1 is CF3). Present Example 5 illustrates the method of Scheme 17.




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Compounds of Formula 1 wherein T is T-1 and W is S can be prepared from the corresponding compounds wherein W is O by treatment with phosphorus pentasulfide or 2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide (Lawesson's reagent) in solvents such as toluene, xylene or tetrahydrofuran. One skilled in the art will also recognize that the compounds of Formula 1 wherein T is T-1 and W is NR3 can be prepared from the compounds of Formula 1 wherein T is T-1 and W is O or S by treatment with an amine of Formula R3NH2 under dehydrating conditions.


The E-L-moieties present in the compounds of Formula 1 and the intermediate compounds of Formulae 2 through 7 and 9 are common organic functional groups whose methods of preparation have been documented in the literature. One skilled in the art will recognize that these well-known chemistry classes (esters, amides, sulfonamides, sulfones, ethers, carbamates, ureas, heterocycles) can be readily prepared by a variety of methods (see, for example, WO 2018/080859, WO 2018/118781, WO 2018/187553 and WO 2019/010192).


It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula 1.


One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.


Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. 1H NMR spectra are reported in ppm downfield from tetramethylsilane; “s” means singlet, “br s” means broad singlet, “d” means doublet, “dd” means doublet of doublets, “t” means triplet, “q” means quartet and “m” means multiplet. 19F NMR spectra are reported in ppm using trichlorofluoromethane as the reference.


Example 1
Preparation of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 1)
Step A: Preparation of ethyl 1-[(4-hydroxyphenyl)methyl]-1H-pyrazole-4-carboxylate

A mixture of ethyl 1H-pyrazole-4-carboxylate (1.40 g, 10 mmol), 4-(chloromethyl)phenyl acetate (2.0 g, 11 mmol) and potassium carbonate (1.6 g, 11 mmol) in N,N-dimethylformamide (10 mL) was stirred at room temperature for 16 h. Ethanol (10 mL) was added and the reaction mixture was heated at 65° C. for 16 h, cooled, and poured into ice water. The resulting precipitate was collected by filtration, washed with water and air dried. The resulting solid (2.0 g) was crystalized from acetonitrile to provide the title compound as a white solid melting at 113-115° C.



1H NMR (CDCl3): δ 1.32 (t, 3H), 3.10 (d, 1H), 4.10-4.40 (m, 5H), 5.24 (s, 2H), 6.91 (d, 2H), 7.22 (d, 2H), 7.83 (s, 1H), 7.93 (s, 1H).


Step B: Preparation of ethyl 1-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate

A mixture of ethyl 1-[(4-hydroxyphenyl)methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step A) (2.36 g, 9.6 mmol), 2-(trifluoromethyl)oxirane (1.3 g, 11.6 mmol) and cesium carbonate (50 mg, 0.15 mmol) in acetonitrile (20 mL) was heated at 65° C. After 3 days, the reaction mixture was cooled and concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 50% ethyl acetate in hexanes) to provide the title compound as a white solid (2.46 g).



1H NMR (CDCl3): δ 1.33 (t, 3H), 4.29 (q, 2H), 5.21 (s, 2H), 5.95 (br s, 1H), 6.76 (d, 2H), 7.09 (d, 2H), 7.84 (s, 1H), 7.95 (s, 1H). 19F NMR (CDCl3): δ −77.54.


Step C: Preparation of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate

A mixture of ethyl 1-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step B) (1.23 g, 3.4 mmol) and Dess-Martin periodinane (2.2 g, 5.2 mmol) in dichloromethane (20 mL) was stirred at room temperature for 16 h, and then concentrated under reduced pressure. The resulting material was dissolved in ethyl acetate and washed with sodium bisulfite solution (2 M aqueous solution), followed by saturated aqueous sodium bicarbonate solution. The organic layer was dried, filtered and the filtrate was concentrated under reduced pressure. The resulting tan solid (1.77 g) was crystalized from acetonitrile to provide the title compound, a compound of the present invention, as solid needles melting at 120-123° C.



1H NMR (CDCl3): δ 1.32 (t, 3H), 3.80 (br s, 1.7H), 4.18 (s, 2H), 4.28 (q, 2H), 5.25 (s, 2H), 6.95 (d, 2H), 7.22 (d, 2H), 7.82 (s, 1H), 7.95 (s, 1H). 19F NMR (CDCl3): δ −84.92.


Example 2
Preparation of ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 32)

A mixture of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Example 1) (1.07 g, 3.0 mmol), 2-chloroethanol (0.24 g, 3.0 mmol) and potassium carbonate (0.5 g, 3.6 mmol) in N,N-dimethylformamide (3.5 mL) was stirred at room temperature for 16 h, and then heated at 65° C. (briefly). After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The resulting material was diluted with diethyl ether and washed with saturated aqueous sodium chloride solution. The organic layer was dried, filtered and the filtrate was concentrated under reduced pressure to provide the title compound, a compound of the present invention, as a colorless oil (1.06 g).



1H NMR (CDCl3): δ 1.32 (t, 3H), 4.21 (s, 4H), 4.23 (s, 2H), 4.27 (q, 2H), 5.24 (s, 2H), 6.94 (d, 2H), 7.20 (d, 2H), 7.81 (s, 1H), 7.93 (s, 1H).



19F NMR (CDCl3): δ −81.39.


Example 3
Preparation of ethyl 1-[[4-[[4,4-dimethyl-2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]-phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 12)

The title compound was prepared by a procedure analogous to Example 2.



1H NMR (CDCl3): δ 1.32 (t, 3H), 1.13 (s, 3H), 1.45 (s, 3H), 3.95 (d, 1H), 4.00 (d, 1H), 4.18 (m, 2H), 4.27 (q, 2H), 5.24 (s, 2H), 6.94 (d, 2H), 7.20 (d, 2H), 7.81 (s, 1H), 7.93 (s, 1H).



19F NMR (CDCl3): δ −81.01.


Example 4
Alternative preparation of ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]-methyl]-1H-pyrazole-4-carboxylate (Compound 32)
Step A: Preparation of methyl 2-(trifluoromethyl)-1,3-dioxolane-2-carboxylate

To a mixture of methyl 3,3,3-trifluoro-2-oxopropanoate (31.2 g, 200 mmol) in petroleum ether (100 mL) was added 2-bromoethanol (25.0 g, 200 mmol) over a period of 15 minutes. The reaction mixture was stirred at room temperature for 30 minutes, then cooled to 5° C. and potassium carbonate (28 g, 200 mmol) was added with vigorous stirring. Stirring was continued for an additional 4 h at 5° C., and then the reaction mixture was allowed to warm to room temperature, diluted with diethyl ether (100 mL) and filtered. The filtrate was concentrated under reduced pressure, and the resulting material was dissolved in diethyl ether (200 mL) and washed with saturated aqueous sodium chloride solution (3×). The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to provide the title compound as a colorless oil (29 g).



1H NMR (CDCl3): δ 3.80 (s, 3H), 4.30 (m, 4H).



19F NMR (CDCl3): δ −80.52.


Step B: Preparation of 2-(trifluoromethyl)-1,3-dioxolane-2-methanol

To a mixture of methyl 2-(trifluoromethyl)-1,3-dioxolane-2-carboxylate (i.e. the product of Step A) (5 g, 25 mmol) in tetrahydrofuran (75 mL) was added sodium bis(2-methoxy-ethoxy)aluminum hydride (60% in toluene) (12.2 mL, 37.5 mmol). The reaction mixture was heated at 40° C. for 1.5 h, and then cooled to room temperature and a solution of ethyl acetate (3.30 g, 37.5 mmol) in tetrahydrofuran (15 mL) was added dropwise over a period of 15 minutes. The reaction mixture was stirred for 45 minutes and then concentrated under reduced pressure. The resulting material was diluted with diethyl ether (400 mL), washed with saturated aqueous sodium chloride solution (2×), dried over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to provide the title compound as an oil (3.8 g).



1H NMR (CDCl3): δ 2.59 (t, 1H), 3.82 (d, 2H), 4.19 (m, 4H).



19F NMR (CDCl3): δ −81.50.


Step C: Preparation of [2-(trifluoromethyl)-1,3-dioxolan-2-yl]methyl 1,1,1-trifluoro-methanesulfonate

A mixture of 2-(trifluoromethyl)-1,3-dioxolane-2-methanol (i.e. the product of Step B) (1.67 g, 9.70 mmol) and triethylamine (1.5 mL, 10.8 mmol) in dichloromethane (50 mL) was cooled to −78° C., and then a solution of trifluoromethanesulfonic anhydride (1.81 mL, 10.8 mmol) in dichloromethane (50 mL) was added over a period of 30 minutes. The reaction mixture was stirred at −78° C. for 1.5 h, and then water (50 mL) was added dropwise while allowing the reaction to warm to room temperature. The resulting mixture was partitioned between dichloromethane-water, and the organic layer washed with water, dried over magnesium sulfate and filtered. The filtrated was concentrated under reduced pressure to provide the title compound as a colorless solid (3.0 g).



1H NMR (CDCl3): δ 4.24 (m, 4H), 4.60 (br s, 2H).



19F NMR (CDCl3): δ −74.84, −81.50.


Step D: Preparation of ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]-phenyl]methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[(4-hydroxyphenyl)methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Example 1, Step A) (16.85 g, 68.0 mmol) and cesium carbonate (53.53 g, 164.5 mmol) in N,N-dimethylformamide (100 mL) was added [2-(trifluoromethyl)-1,3-dioxolan-2-yl]methyl 1,1,1-trifluoromethanesulfonate (i.e. the product of Step C) (24.9 g, 82.0 mmol). The reaction mixture was stirred for 24 h at room temperature, and then diluted with diethyl ether. The organic layer was washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 60% ethyl acetate in hexanes) to provide the title compound, a compound of the present invention, as a white solid (23 g) melting at 59-60° C.



1H NMR (CDCl3): δ 1.32 (t, 3H), 4.21 (s, 4H), 4.23 (s, 2H), 4.27 (q, 2H), 5.24 (s, 2H), 6.94 (d, 2H), 7.20 (d, 2H), 7.81 (s, 1H), 7.93 (s, 1H).



19F NMR (CDCl3): δ −81.39.


Example 5
Preparation of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 64)

A mixture of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Example 1) (1.0 g, 2.67 mmol), iodoethane (2.5 g, 16 mmol) and cesium carbonate (1.75 g, 5.37 mmol) in dimethyl sulfoxide (10 mL) was heated at 40° C. for 45 minutes. The reaction mixture was diluted with diethyl ether, washed with water and saturated aqueous sodium chloride solution, dried and filtered. The filtrate was concentrated under reduced pressure to provide the title compound, a compound of the present invention, as a white solid (0.80 g). A portion of the solid was further purified by silica gel chromatography (eluting with a gradient of 0 to 50% ethyl acetate in hexanes) to provide a solid melting at 59-60° C. A nuclear Overhauser effect (NOE) was observed between the trifluoromethyl moiety and the vinyl proton indicating a cis-configuration.



1H NMR (CDCl3): δ 1.30-1.40 (m, 6H), 4.17 (q, 2H), 4.27 (q, 2H), 5.28 (s, 2H), 6.78 (q, 1H), 7.05 (m, 2H), 7.29 (m, 2H), 7.86 (s, 1H), 7.94 (s, 1H).



19F NMR (CDCl3): δ −70.13.


Example 6
Preparation of ethyl 1-[[3-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 266)
Step A: Preparation of 3-(bromomethyl)phenol

A mixture of 1-(bromomethyl)-3-methoxybenzene (15.48 g, 76.99 mmol) in dichloromethane (150 mL) was cooled to −78° C., and then boron tribromide (1 M solution in dichloromethane) was added dropwise. The reaction mixture was allowed to warm to room temperature, stirred for 2 h, and then cooled to −20° C. and methanol (150 mL) was added dropwise. After warming to room temperature, the reaction mixture was concentrated under reduced pressure and the resulting material was diluted with dichloromethane and washed with saturated aqueous sodium bicarbonate solution. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (14.16 g).



1H NMR (CDCl3): δ 4.44 (s, 2H), 4.89 (s, 1H), 6.76 (dd, 1H), 6.87 (s, 1H), 6.95 (d, 1H), 7.19-7.23 (t, 1H).


Step B: Preparation of 3-(bromomethyl)phenyl acetate

A solution of 3-(bromomethyl)phenol (i.e. the product of Step A) (14.16 g, 75.7 mmol) in dichloromethane (130 mL) was cooled to 0° C., and then acetic anhydride was added (12.96 g, 12 mL, 126.9 mmol), followed by concentrated sulfuric acid (5 drops). The reaction mixture was allowed to warm to room temperature, stirred for 1 h, and then saturated aqueous sodium bicarbonate solution (300 mL, 318 mmol) was added. The organic layer was separated, washed with water, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure to provide the title compound as a solid (16.68 g).



1H NMR (CDCl3): δ 4.47 (s, 2H), 7.02-7.04 (m, 1H), 7.14 (s, 1H), 7.25 (m, 1H), 7.35 (t, 1H).


Step C: Preparation of ethyl 1-[[3-(acetyloxy)phenyl]methyl]-1H-pyrazole-4-carboxylate

To a mixture of 3-(bromomethyl)phenyl acetate (i.e. the product of Step B) (16.68 g, 72.8 mmol) in acetonitrile (300 mL) was added ethyl 1H-pyrazole-4-carboxylate (10.61 g, 75.7 mmol) followed by potassium carbonate (19.35 g, 140 mmol). The reaction mixture was heated at 70° C. overnight, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure to provide the title compound as a yellow oil (20.5 g).



1H NMR (CDCl3): δ 2.30 (s, 3H), 4.47 (s, 2H), 7.02 (dd, 1H), 7.15 (s, 1H), 7.25 (m, 1H).


Step D: Preparation of ethyl 1-[(3-hydroxyphenyl)methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[[3-(acetyloxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step C) (20.5 g, 72.8 mmol) in ethanol was added potassium carbonate (10.1 g, 73 mmol). The reaction mixture was heated at reflux for 3 h, cooled to room temperature and filtered. The filtrate was concentrated under reduced pressure and the resulting material was purified by MPLC silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (10.02 g).



1H NMR (CDCl3): δ 1.33 (t, 3H) 4.29 (q, 2H), 5.20 (br s, 1H), 5.25 (s, 2H), 6.66 (m, 1H), 6.78-6.81 (m, 2H), 7.21-7.24 (m, 1H), 7.87 (s, 1H), 7.94 (s, 1H).


Step E: Preparation of ethyl 1-[[3-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[(3-hydroxyphenyl)methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step D) (2.38 g 9.66 mmol) in acetonitrile (100 mL) was added 3-bromo-1,1,1-trifluoro-2-propanol (1.93 g, 1.04 mL, 10 mmol) followed by potassium carbonate (2.86 g, 20.7 mmol). The reaction mixture was heated at reflux for 48 h, cooled to room temperature, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by MPLC silica gel chromatography, (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound as a solid (2.75 g).



1H NMR (CDCl3): δ 1.33 (q, 3H), 4.1-4.4 (m, 5H), 5.27 (s, 2H), 6.80 (m, 1H), 6.87-6.89 (m, 2H), 7.28-7.31 (m, 1H), 7.88 (s, 1H), 7.94 (s, 1H).



19F NMR (CDCl3): δ −77.53.


Step F: Preparation of ethyl 1-[[3-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[[3-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step E) (5.7 g, 14.9 mmol) in dichloromethane (300 mL) was added Dess-Martin periodinane (9.13 g, 20.3 mmol) in one portion. After 3 h, the reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate and washed with sodium bisulfite solution (10% aqueous solution), saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was triturated with 1-chlorobutane to provide the title compound, a compound of the present invention, as a white solid (4.89 g).



1H NMR (DMSO-d6): δ 1.27 (t, 3H), 4.01 (s, 2H), 4.20 (m, 2H), 5.33 (s, 2H), 6.86-6.92 (m, 3H), 7.26-7.29 (m, 1H), 7.31 (s, 2H,), 7.87 (s, 1H), 8.48 (s, 1H).



19F NMR (DMSO-d6): δ −81.82.


Example 7
Preparation of ethyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate (Compound 265)

To a mixture of ethyl 1-[[3-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Example 6) (2.94 g, 7.85 mmol) in dimethyl sulfoxide (24 mL) was added iodoethane (2.39 g, 15.3 mmol). The reaction mixture was heated at 65° C., and then cesium carbonate (4.21 g, 12.92 mmol) was added. After 45 minutes, the reaction mixture was cooled to room temperature, and poured into diethyl ether/water (400 mL, 1:1 ratio). The organic layer was separated and washed with water, saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 0 to 100% ethyl acetate in hexanes) to provide the title compound, a compound of the present invention, as a white solid (2.59 g) melting at 41-43° C.



1H NMR (CDCl3): δ 1.32 (m, 6H), 4.16 (m, 2H,), 4.30 (m, 2H,), 5.31 (s, 2H,), 6.76 (s, 1H), 6.93 (m, 1H), 7.00-7.03 (m, 2H), 7.34-7.37 (m, 1H), 7.90 (s, 1H), 7.95 (s, 1H).



19F NMR (CDCl3): δ −70.09.


Example 8
Preparation of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenoxy]methyl]-1H-pyrazole-4-carboxylate (Compound 366)
Step A: Preparation of ethyl 1-(hydroxymethyl)-1H-pyrazole-4-carboxylate

A mixture of ethyl 1H-pyrazole-4-carboxylate (6.0 g, 43 mmol), formaldehyde (37% aqueous solution, 12 mL) and ethanol (50 mL) was heated at reflux overnight. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The resulting material was triturated with 1-chlorobutane to provide the title compound as a white solid (6.2 g).



1H NMR (DMSO-d6): δ 1.27 (t, 3H) 4.22 (q, 2H), 5.41 (s, 2H), 7.89 (s, 1H), 8.36 (s, 1H).


Step B: Preparation of ethyl 1-(chloromethyl)-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-(hydroxymethyl)-1H-pyrazole-4-carboxylate (i.e. the product of Step A) (6.2 g, 36 mmol) in dichloroethane (100 mL) was added N,N-dimethylformamide (2 drops), followed by thionyl chloride (5.3 mL, 73 mmol) dropwise. After 3 h, the reaction mixture, was concentrated under reduced pressure to provide the title compound as a yellow solid (6.2 g).



1H NMR (CDCl3): δ 1.35 (t, 3H), 4.31 (q, 2H), 5.85 (s, 2H), 7.99 (s, 1H), 8.11 (s, 1H).


Step C: Preparation of ethyl 1-[(4-methoxyphenoxy)methyl]-1H-pyrazole-4-carboxylate

A mixture of ethyl 1-(chloromethyl)-1H-pyrazole-4-carboxylate (i.e. the product of Step B) (2.0 g, 11 mmol), 4-methoxyphenol (1.24 g, 10 mmol), potassium carbonate (2.8 g, 20 mmol) and N,N-dimethylformamide (25 mL) was stirred at room temperature. After 3 days, the reaction mixture was poured into ice water (150 mL) and extracted with diethyl ether (2×100 mL). The combined organic layers were washed with water (50 mL), saturated aqueous sodium chloride solution (25 mL), dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 10 to 100% ethyl acetate in hexanes) to provide the title compound as a colorless oil (2.7 g).



1H NMR (CDCl3): δ 1.34 (t, 3H), 3.78 (s, 3H), 4.29 (q, 2H), 5.90 (s, 2H), 6.80-6.84 (m, 2H), 6.88-6.91 (m, 2H), 7.96 (s, 1H), 8.05 (s, 1H).


Step D: Preparation of ethyl 1-[(4-hydroxyphenoxy)methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[(4-methoxyphenoxy)methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step C) (1.7 g, 6.2 mmol) in dichloromethane (3 mL) was added boron tribromide solution (1 M in dichloromethane, 12.4 mL, 12.4 mmol). After 4 h, saturated aqueous ammonium chloride solution (25 mL) was added to the reaction mixture and stirring was continued for another 15 minutes. The reaction mixture was diluted with dichloromethane (25 mL) and saturated aqueous ammonium chloride solution (25 mL). The organic layer was separated and washed with saturated aqueous sodium bicarbonate solution (25 mL) and saturated aqueous sodium chloride solution (25 mL), drying over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to provide the title compound as a solid (1.65 g).



1H NMR (DMSO-d6): δ 1.26 (t, 3H), 4.21 (q, 2H), 5.76 (s, 1H), 5.96 (s, 2H), 6.62-6.71 (m, 2H), 6.82-6.88 (m, 2H), 7.93 (d, 1H), 8.48 (d, 1H).


Step E: Preparation of ethyl 1-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenoxy]methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[(4-hydroxyphenoxy)methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step D) (6.2 mmol) in acetonitrile (20 mL) was added 2-(trifluoromethyl)oxirane (0.62 mL, 7.6 mmol) and cesium carbonate (approximately 10 mg). The reaction mixture was heated at 75° C. overnight, and then cooled to room temperature and concentrated under reduced pressure. The resulting material was purified by silica gel chromatography (eluting with a gradient of 10 to 100% ethyl acetate in hexanes) to provide the title compound as a white solid (0.95 g).



1H NMR (DMSO-d6): δ 1.26 (t, 3H), 3.96-4.08 (m, 1H), 4.12 (dd, 1H), 4.22 (q, 2H), 4.33-4.36 (m, 1H), 6.04 (s, 2H), 6.62 (d, 1H), 6.88-6.97 (m, 2H), 7.00-7.03 (m, 2H), 7.95 (s, 1H), 8.54 (s, 1H).


Step F: Preparation of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenoxy]-methyl]-1H-pyrazole-4-carboxylate

To a mixture of ethyl 1-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenoxy]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Step E) (0.95 g, 2.5 mmol) in dichloromethane (25 mL) was added Dess-Martin periodinane (1.5 g, 3.5 mmol) in one portion. The reaction mixture was stirred for 2.5 h, and then saturated aqueous sodium thiosulfate solution (30 mL) was added and the mixture was concentrated under reduced pressure. The resulting mixture was extracted with ethyl acetate (150 mL) and the combined organic layers were washed with saturated aqueous sodium thiosulfate solution (50 mL), saturated aqueous sodium bicarbonate solution (50 mL) and saturated aqueous sodium chloride solution (25 mL), drying over magnesium sulfate and filtered. The filtered was concentrated under reduced pressure and the resulting material was triturated with dichloromethane to provide the title compound, a compound of the present invention, as a solid (0.65 g).



1H NMR (DMSO-d6): δ 1.26 (t, 3H), 3.98 (s, 2H), 4.21 (q, 2H), 6.03 (s, 2H), 6.86-6.94 (m, 2H), 6.95-7.06 (m, 2H), 7.27 (s, 2H), 7.94 (s, 1H), 8.53 (s, 1H).


Example 9
Preparation of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenoxy]methyl]-1H-pyrazole-4-carboxylate (Compound 364)

A mixture of iodoethane (2.7 mL, 34 mmol), potassium carbonate (0.84 g, 6.1 mmol) and dimethyl sulfoxide (7 mL) was stirred at room temperature for 20 minutes, and then a solution of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenoxy]methyl]-1H-pyrazole-4-carboxylate (i.e. the product of Example 8) (0.64 g, 1.6 mmol) in dimethyl sulfoxide (7 mL) was added portionwise over 20 minutes. After stirring at room temperature for 1.5 hours, the reaction mixture was poured into ice water (150 mL) and extracted with ethyl acetate (125 mL). The organic layer was washed with water (2×50 mL) and saturated aqueous sodium chloride solution (50 mL), drying over magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure and the resulting material was purified by silica gel chromatography (eluting with a gradient of 10 to 100% ethyl acetate in hexanes) to provide the title compound, a compound of the present invention, as a colorless oil (0.46 g).



1H NMR (DMSO-d6): δ 1.23-1.27 (m, 6H), 4.11 (q, 2H), 4.22 (q, 2H), 6.10 (s, 2H), 7.07-7.24 (m, 4H) 7.95 (s, 1H) 8.58 (s, 1H).


By the procedures described herein, together with methods known in the art, the following compounds of Tables 1, 1A-48A, 2, and 1B-48B can be prepared. The following abbreviations are used in the Tables: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, i-Pr means isopropyl, c-Pr means cyclopropyl, Bu means butyl, i-Bu means isobutyl, t-Bu means tert-butyl, and Ph means phenyl.









TABLE 1









embedded image







In the above formula, E is equal to E2, E2 is equal G—Z—, and G is optionally substituted with R13. The


definitions of G are as defined Exhibit A in the above Embodiments. In the column G, the number in parentheses


refers to the attachment point of the G-ring to Z. The (R13)x column refers to the substituent(s) attached to the


G-ring as shown in Exhibit A above. A dash “—” in the (R13)x column means that no R13 substituent is present


and the remaining valences on the G-ring are occupied by hydrogen atoms.


J is J-1, L is CH2 and Z is a direct bond.








G
(R13)x





G-1 (4)
—


G-1 (4)
2-Me


G-1 (4)
2-Et


G-1 (4)
2-n-Pr


G-1 (4)
2-i-Pr


G-1 (4)
2-c-Pr


G-1 (4)
2-n-Bu


G-1 (4)
2-i-Bu


G-1 (4)
2-t-Bu


G-1 (4)
2-F


G-1 (4)
2-Cl


G-1 (4)
2-Br


G-1 (4)
2-CF3


G-1 (4)
2-HO


G-1 (4)
2-N≡C


G-1 (4)
2-N≡CCH2


G-1 (4)
2-(MeO)


G-1 (4)
2-(MeOCH2)


G-1 (4)
2-(EtOCH2)


G-1 (4)
2-(CH(═O))


G-1 (4)
2-(HOC(═O))


G-1 (4)
2-(MeOC(═O))


G-1 (4)
2-(EtOC(═O))


G-1 (4)
2-(i-PrOC(═O))


G-1 (4)
2-(n-PrOC(═O))


G-1 (4)
2-(BuOC(═O))


G-1 (4)
2-(i-BuOC(═O))


G-1 (4)
2-(t-BuOC(═O))


G-1 (4)
2-(CF3CH2OC(═O)


G-1 (4)
2-(CH2═CHOC(═O))


G-1 (4)
2-(CH2═CHCH2OC(═O))


G-1 (4)
2-(CH2═CBrCH2OC(═O))


G-1 (4)
2-(CH2═CHCF2OC(═O))


G-1 (4)
2-(Me2C═CHCH2OC(═O))


G-1 (4)
2-(CH2═C(Me)CH2OC(═O))


G-1 (4)
2-(CH≡CCH2OC(═O))


G-1 (4)
2-(N≡CCH2OC(═O))


G-1 (4)
2-(MeNHC(═O))


G-1 (4)
2-(Me2NC(═O))


G-1 (4)
2-(MeNHC(═O))


G-1 (4)
2-(EtNHC(═O))


G-1 (4)
2-(PrNHC(═O))


G-1 (4)
2-(i-PrNHC(═O))


G-1 (4)
2-(BuNHC(═O))


G-1 (4)
2-(t-BuNHC(═O))


G-1 (4)
2-(i-BuNHC(═O))


G-1 (4)
2-(CF3CH2NHC(═O))


G-1 (4)
2-(c-PrCH2NHC(═O))


G-1 (4)
2-(MeOCH2NHC(═O))


G-1 (4)
2-(MeOCH2CH2NHC(═O))


G-1 (4)
2-(CH2═CHCH2NHC(═O))


G-1 (4)
2-(N≡CCH2NHC(═O))


G-1 (4)
2-(OH—N═CH)


G-1 (4)
2-(Me2NN═CH)


G-1 (4)
2-(MeOC(═O)NHN═CH)


G-1 (4)
2-(OHC(═O)CH2ON═CH)


G-1 (2)
—


G-1 (2)
4-Me


G-1 (2)
4-Et


G-1 (2)
4-n-Pr


G-1 (2)
4-i-Pr


G-1 (2)
4-c-Pr


G-1 (2)
4-n-Bu


G-1 (2)
4-i-Bu


G-1 (2)
4-t-Bu


G-1 (2)
4-F


G-1 (2)
4-Cl


G-1 (2)
4-Br


G-1 (2)
4-CF3


G-1 (2)
4-HO


G-1 (2)
4-N≡C


G-1 (2)
4-N≡CCH2


G-1 (2)
4-(MeO)


G-1 (2)
4-(MeOCH2)


G-1 (2)
4-(EtOCH2)


G-1 (2)
4-(CH(═O))


G-1 (2)
4-(HOC(═O))


G-1 (2)
4-(MeOC(═O))


G-1 (2)
4-(EtOC(═O))


G-1 (2)
4-(i-PrOC(═O))


G-1 (2)
4-(n-PrOC(═O))


G-1 (2)
4-(BuOC(═O))


G-1 (2)
4-(i-BuOC(═O))


G-1 (2)
4-(t-BuOC(═O))


G-1 (2)
4-(CF3CH2OC(═O)


G-1 (2)
4-(CH2═CHOC(═O))


G-1 (2)
4-(CH2═CHCH2OC(═O))


G-1 (2)
4-(CH2═CBrCH2OC(═O))


G-1 (2)
4-(CH2═CHCF2OC(═O))


G-1 (2)
4-(Me2C═CHCH2OC(═O))


G-1 (2)
4-(CH2═C(Me)CH2OC(═O))


G-1 (2)
4-(CH≡CCH2OC(═O))


G-1 (2)
4-(N≡CCH2OC(═O))


G-1 (2)
4-(MeNHC(═O))


G-1 (2)
4-(Me2NC(═O))


G-1 (2)
4-(MeNHC(═O))


G-1 (2)
4-(EtNHC(═O))


G-1 (2)
4-(PrNHC(═O))


G-1 (2)
4-(i-PrNHC(═O))


G-1 (2)
4-(BuNHC(═O))


G-1 (2)
4-(t-BuNHC(═O))


G-1 (2)
4-(i-BuNHC(═O))


G-1 (2)
4-(CF3CH2NHC(═O))


G-1 (2)
4-(c-PrCH2NHC(═O))


G-1 (2)
4-(MeOCH2NHC(═O))


G-1 (2)
4-(MeOCH2CH2NHC(═O))


G-1 (2)
4-(CH2═CHCH2NHC(═O))


G-1 (2)
4-(N≡CCH2NHC(═O))


G-1 (2)
4-(OH—N═CH)


G-1 (2)
4-(Me2NN═CH)


G-1 (2)
4-(MeOC(═O)NHN═CH)


G-1 (2)
4-(OHC(═O)CH2ON═CH)


G-3 (1)
—


G-3 (1)
4-Me


G-3 (1)
4-Et


G-3 (1)
4-n-Pr


G-3 (1)
4-i-Pr


G-3 (1)
4-c-Pr


G-3 (1)
4-n-Bu


G-3 (1)
4-i-Bu


G-3 (1)
4-t-Bu


G-3 (1)
4-F


G-3 (1)
4-Cl


G-3 (1)
4-Br


G-3 (1)
4-CF3


G-3 (1)
4-HO


G-3 (1)
4-N≡C


G-3 (1)
4-N≡CCH2


G-3 (1)
4-(MeO)


G-3 (1)
4-(MeOCH2)


G-3 (1)
4-(EtOCH2)


G-3 (1)
4-(CH(═O))


G-3 (1)
4-(HOC(═O))


G-3 (1)
4-(MeOC(═O))


G-3 (1)
4-(EtOC(═O))


G-3 (1)
4-(i-PrOC(═O))


G-3 (1)
4-(n-PrOC(═O))


G-3 (1)
4-(BuOC(═O))


G-3 (1)
4-(i-BuOC(═O))


G-3 (1)
4-(t-BuOC(═O))


G-3 (1)
4-(CF3CH2OC(═O)


G-3 (1)
4-(CH2═CHOC(═O))


G-3 (1)
4-(CH2═CHCH2OC(═O))


G-3 (1)
4-(CH2═CBrCH2OC(═O))


G-3 (1)
4-(CH2═CHCF2OC(═O))


G-3 (1)
4-(Me2C═CHCH2OC(═O))


G-3 (1)
4-(CH2═C(Me)CH2OC(═O))


G-3 (1)
4-(CH≡CCH2OC(═O))


G-3 (1)
4-(N≡CCH2OC(═O))


G-3 (1)
4-(MeNHC(═O))


G-3 (1)
4-(Me2NC(═O))


G-3 (1)
4-(MeNHC(═O))


G-3 (1)
4-(EtNHC(═O))


G-3 (1)
4-(PrNHC(═O))


G-3 (1)
4-(i-PrNHC(═O))


G-3 (1)
4-(BuNHC(═O))


G-3 (1)
4-(t-BuNHC(═O))


G-3 (1)
4-(i-BuNHC(═O))


G-3 (1)
4-(CF3CH2NHC(═O))


G-3 (1)
4-(c-PrCH2NHC(═O))


G-3 (1)
4-(MeOCH2NHC(═O))


G-3 (1)
4-(MeOCH2CH2NHC(═O))


G-3 (1)
4-(CH2═CHCH2NHC(═O))


G-3 (1)
4-(N≡CCH2NHC(═O))


G-3 (1)
4-(OH—N═CH)


G-3 (1)
4-(Me2NN═CH)


G-3 (1)
4-(MeOC(═O)NHN═CH)


G-3 (1)
4-(OHC(═O)CH2ON═CH)


G-9 (1)
—


G-9 (1)
3-Me


G-9 (1)
3-Et


G-9 (1)
3-n-Pr


G-9 (1)
3-i-Pr


G-9 (1)
3-c-Pr


G-9 (1)
3-n-Bu


G-9 (1)
3-i-Bu


G-9 (1)
3-t-Bu


G-9 (1)
3-F


G-9 (1)
3-Cl


G-9 (1)
3-Br


G-9 (1)
3-CF3


G-9 (1)
3-HO


G-9 (1)
3-N≡C


G-9 (1)
3-N≡CCH2


G-9 (1)
3-(MeO)


G-9 (1)
3-(MeOCH2)


G-9 (1)
3-(EtOCH2)


G-9 (1)
3-(CH(═O))


G-9 (1)
3-(HOC(═O))


G-9 (1)
3-(MeOC(═O))


G-9 (1)
3-(EtOC(═O))


G-9 (1)
3-(i-PrOC(═O))


G-9 (1)
3-(n-PrOC(═O))


G-9 (1)
3-(BuOC(═O))


G-9 (1)
3-(i-BuOC(═O))


G-9 (1)
3-(t-BuOC(═O))


G-9 (1)
3-(CF3CH2OC(═O)


G-9 (1)
3-(CH2═CHOC(═O))


G-9 (1)
3-(CH2═CHCH2OC(═O))


G-9 (1)
3-(CH2═CBrCH2OC(═O))


G-9 (1)
3-(CH2═CHCF2OC(═O))


G-9 (1)
3-(Me2C═CHCH2OC(═O))


G-9 (1)
3-(CH2═C(Me)CH2OC(═O))


G-9 (1)
3-(CH≡CCH2OC(═O))


G-9 (1)
3-(N≡CCH2OC(═O))


G-9 (1)
3-(MeNHC(═O))


G-9 (1)
3-(Me2NC(═O))


G-9 (1)
3-(MeNHC(═O))


G-9 (1)
3-(EtNHC(═O))


G-9 (1)
3-(PrNHC(═O))


G-9 (1)
3-(i-PrNHC(═O))


G-9 (1)
3-(BuNHC(═O))


G-9 (1)
3-(t-BuNHC(═O))


G-9 (1)
3-(i-BuNHC(═O))


G-9 (1)
3-(CF3CH2NHC(═O))


G-9 (1)
3-(c-PrCH2NHC(═O))


G-9 (1)
3-(MeOCH2NHC(═O))


G-9 (1)
3-(MeOCH2CH2NHC(═O))


G-9 (1)
3-(CH2═CHCH2NHC(═O))


G-9 (1)
3-(N≡CCH2NHC(═O))


G-9 (1)
3-(OH—N═CH)


G-9 (1)
3-(Me2NN═CH)


G-9 (1)
3-(MeOC(═O)NHN═CH)


G-9 (1)
3-(OHC(═O)CH2ON═CH)


G-12 (1)
—


G-12 (1)
4-Me


G-12 (1)
4-Et


G-12 (1)
4-n-Pr


G-12 (1)
4-i-Pr


G-12 (1)
4-c-Pr


G-12 (1)
4-n-Bu


G-12 (1)
4-i-Bu


G-12 (1)
4-t-Bu


G-12 (1)
4-F


G-12 (1)
4-Cl


G-12 (1)
4-Br


G-12 (1)
4-CF3


G-12 (1)
4-HO


G-12 (1)
4-N≡C


G-12 (1)
4-N≡CCH2


G-12 (1)
4-(MeO)


G-12 (1)
4-(MeOCH2)


G-12 (1)
4-(EtOCH2)


G-12 (1)
4-(CH(═O))


G-12 (1)
4-(HOC(═O))


G-12 (1)
4-(MeOC(═O))


G-12 (1)
4-(EtOC(═O))


G-12 (1)
4-(i-PrOC(═O))


G-12 (1)
4-(n-PrOC(═O))


G-12 (1)
4-(BuOC(═O))


G-12 (1)
4-(i-BuOC(═O))


G-12 (1)
4-(t-BuOC(═O))


G-12 (1)
4-(CF3CH2OC(═O)


G-12 (1)
4-(CH2═CHOC(═O))


G-12 (1)
4-(CH2═CHCH2OC(═O))


G-12 (1)
4-(CH2═CBrCH2OC(═O))


G-12 (1)
4-(CH2═CHCF2OC(═0))


G-12 (1)
4-(Me2C═CHCH2OC(═O))


G-12 (1)
4-(CH2═C(Me)CH2OC(═O))


G-12 (1)
4-(CH≡CCH2OC(═O))


G-12 (1)
4-(N≡CCH2OC(═O))


G-12 (1)
4-(MeNHC(═O))


G-12 (1)
4-(Me2NC(═O))


G-12 (1)
4-(MeNHC(═O))


G-12 (1)
4-(EtNHC(═O))


G-12 (1)
4-(PrNHC(═O))


G-12 (1)
4-(i-PrNHC(═O))


G-12 (1)
4-(BuNHC(═O))


G-12 (1)
4-(t-BuNHC(═O))


G-12 (1)
4-(i-BuNHC(═O))


G-12 (1)
4-(CF3CH2NHC(═O))


G-12 (1)
4-(c-PrCH2NHC(═O))


G-12 (1)
4-(MeOCH2NHC(═O))


G-12 (1)
4-(MeOCH2CH2NHC(═O))


G-12 (1)
4-(CH2═CHCH2NHC(═O))


G-12 (1)
4-(N≡CCH2NHC(═O))


G-12 (1)
4-(OH—N═CH)


G-12 (1)
4-(Me2NN═CH)


G-12 (1)
4-(MeOC(═O)NHN═CH)


G-12 (1)
4-(OHC(═O)CH2ON═CH)


G-12 (1)
5-Me, 3-(EtOC(═O))


G-12 (1)
3-Me


G-12 (1)
3-Et


G-12 (1)
3-n-Pr


G-12 (1)
3-i-Pr


G-12 (1)
3-c-Pr


G-12 (1)
3-n-Bu


G-12 (1)
3-i-Bu


G-12 (1)
3-t-Bu


G-12 (1)
3-F


G-12 (1)
3-Cl


G-12 (1)
3-Br


G-12 (1)
3-CF3


G-12 (1)
3-HO


G-12 (1)
3-N≡C


G-12 (1)
3-N≡CCH2


G-12 (1)
3-(MeO)


G-12 (1)
3-(MeOCH2)


G-12 (1)
3-(EtOCH2)


G-12 (1)
3-(CH(═O))


G-12 (1)
3-(HOC(═O))


G-12 (1)
3-(MeOC(═O))


G-12 (1)
3-(EtOC(═O))


G-12 (1)
3-(i-PrOC(═O))


G-12 (1)
3-(n-PrOC(═O))


G-12 (1)
3-(BuOC(═O))


G-12 (1)
3-(i-BuOC(═O))


G-12 (1)
3-(t-BuOC(═O))


G-12 (1)
3-(CF3CH2OC(═O)


G-12 (1)
3-(CH2═CHOC(═O))


G-12 (1)
3-(CH2═CHCH2OC(═O))


G-12 (1)
3-(CH2═CBrCH2OC(═O))


G-12 (1)
3-(CH2═CHCF2OC(═O))


G-12 (1)
3-(Me2C═CHCH2OC(═O))


G-12 (1)
3-(CH2═C(Me)CH2OC(═O))


G-12 (1)
3-(CH≡CCH2OC(═O))


G-12 (1)
3-(N≡CCH2OC(═O))


G-12 (1)
3-(MeNHC(═O))


G-12 (1)
3-(Me2NC(═O))


G-12 (1)
3-(MeNHC(═O))


G-12 (1)
3-(EtNHC(═O))


G-12 (1)
3-(PrNHC(═O))


G-12 (1)
3-(i-PrNHC(═O))


G-12 (1)
3-(BuNHC(═O))


G-12 (1)
3-(t-BuNHC(═O))


G-12 (1)
3-(i-BuNHC(═O))


G-12 (1)
3-(CF3CH2NHC(═O))


G-12 (1)
3-(c-PrCH2NHC(═O))


G-12 (1)
3-(MeOCH2NHC(═O))


G-12 (1)
3-(MeOCH2CH2NHC(═O))


G-12 (1)
3-(CH2═CHCH2NHC(═O))


G-12 (1)
3-(N≡CCH2NHC(═O))


G-12 (1)
3-(OH—N═CH)


G-12 (1)
3-(Me2NN═CH)


G-12 (1)
3-(MeOC(═O)NHN═CH)


G-12 (1)
3-(OHC(═O)CH2ON═CH)


G-13 (1)
—


G-13 (1)
5-Me


G-13 (1)
5-Et


G-13 (1)
5-n-Pr


G-13 (1)
5-i-Pr


G-13 (1)
5-c-Pr


G-13 (1)
5-n-Bu


G-13 (1)
5-i-Bu


G-13 (1)
5-t-Bu


G-13 (1)
5-F


G-13 (1)
5-Cl


G-13 (1)
5-Br


G-13 (1)
5-CF3


G-13 (1)
5-HO


G-13 (1)
5-N≡C


G-13 (1)
5-N≡CCH2


G-13 (1)
5-(MeO)


G-13 (1)
5-(MeOCH2)


G-13 (1)
5-(EtOCH2)


G-13 (1)
5-(CH(═O))


G-13 (1)
5-(HOC(═O))


G-13 (1)
5-(MeOC(═O))


G-13 (1)
5-(EtOC(═O))


G-13 (1)
5-(i-PrOC(═O))


G-13 (1)
5-(n-PrOC(═O))


G-13 (1)
5-(BuOC(═O))


G-13 (1)
5-(i-BuOC(═O))


G-13 (1)
5-(t-BuOC(═O))


G-13 (1)
5-(CF3CH2OC(═O)


G-13 (1)
5-(CH2═CHOC(═O))


G-13 (1)
5-(CH2═CHCH2OC(═O))


G-13 (1)
5-(CH2═CBrCH2OC(═O))


G-13 (1)
5-(CH2═CHCF2OC(═O))


G-13 (1)
5-(Me2C═CHCH2OC(═O))


G-13 (1)
5-(CH2═C(Me)CH2OC(═O))


G-13 (1)
5-(CH≡CCH2OC(═O))


G-13 (1)
5-(N≡CCH2OC(═O))


G-13 (1)
5-(MeNHC(═O))


G-13 (1)
5-(Me2NC(═O))


G-13 (1)
5-(MeNHC(═O))


G-13 (1)
5-(EtNHC(═O))


G-13 (1)
5-(PrNHC(═O))


G-13 (1)
5-(i-PrNHC(═O))


G-13 (1)
5-(BuNHC(═O))


G-13 (1)
5-(t-BuNHC(═O))


G-13 (1)
5-(i-BuNHC(═O))


G-13 (1)
5-(CF3CH2NHC(═O))


G-13 (1)
5-(c-PrCH2NHC(═O))


G-13 (1)
5-(MeOCH2NHC(═O))


G-13 (1)
5-(MeOCH2CH2NHC(═O))


G-13 (1)
5-(CH2═CHCH2NHC(═O))


G-13 (1)
5-(N≡CCH2NHC(═O))


G-13 (1)
5-(OH—N═CH)


G-13 (1)
5-(Me2NN═CH)


G-13 (1)
5-(MeOC(═O)NHN═CH)


G-13 (1)
5-(OHC(═O)CH2ON═CH)


G-17 (1)
—


G-17 (1)
4-Me


G-17 (1)
4-Et


G-17 (1)
4-n-Pr


G-17 (1)
4-i-Pr


G-17 (1)
4-c-Pr


G-17 (1)
4-n-Bu


G-17 (1)
4-i-Bu


G-17 (1)
4-t-Bu


G-17 (1)
4-F


G-17 (1)
4-Cl


G-17 (1)
4-Br


G-17 (1)
4-CF3


G-17 (1)
4-HO


G-17 (1)
4-N≡C


G-17 (1)
4-N≡CCH2


G-17 (1)
4-(MeO)


G-17 (1)
4-(MeOCH2)


G-17 (1)
4-(EtOCH2)


G-17 (1)
4-(CH(═O))


G-17 (1)
4-(HOC(═O))


G-17 (1)
4-(MeOC(═O))


G-17 (1)
4-(EtOC(═O))


G-17 (1)
4-(i-PrOC(═O))


G-17 (1)
4-(n-PrOC(═O))


G-17 (1)
4-(BuOC(═O))


G-17 (1)
4-(i-BuOC(═O))


G-17 (1)
4-(t-BuOC(═O))


G-17 (1)
4-(CF3CH2OC(═O)


G-17 (1)
4-(CH2═CHOC(═O))


G-17 (1)
4-(CH2═CHCH2OC(═O))


G-17 (1)
4-(CH2═CBrCH2OC(═O))


G-17 (1)
4-(CH2═CHCF2OC(═O))


G-17 (1)
4-(Me2C═CHCH2OC(═O))


G-17 (1)
4-(CH2═C(Me)CH2OC(═O))


G-17 (1)
4-(CH≡CCH2OC(═O))


G-17 (1)
4-(N≡CCH2OC(═O))


G-17 (1)
4-(MeNHC(═O))


G-17 (1)
4-(Me2NC(═O))


G-17 (1)
4-(MeNHC(═O))


G-17 (1)
4-(EtNHC(═O))


G-17 (1)
4-(PrNHC(═O))


G-17 (1)
4-(i-PrNHC(═O))


G-17 (1)
4-(BuNHC(═O))


G-17 (1)
4-(t-BuNHC(═O))


G-17 (1)
4-(i-BuNHC(═O))


G-17 (1)
4-(CF3CH2NHC(═O))


G-17 (1)
4-(c-PrCH2NHC(═O))


G-17 (1)
4-(MeOCH2NHC(═O))


G-17 (1)
4-(MeOCH2CH2NHC(═O))


G-17 (1)
4-(CH2═CHCH2NHC(═O))


G-17 (1)
4-(N≡CCH2NHC(═O))


G-17 (1)
4-(OH—N═CH)


G-17 (1)
4-(Me2NN═CH)


G-17 (1)
4-(MeOC(═O)NHN═CH)


G-17 (1)
4-(OHC(═O)CH2ON═CH)









The present disclosure also includes Tables 1A through 48A, each of which is constructed the same as Table 1 above, except that the row heading in Table 1 (i.e. “J is J-1, L is CH2 and Z is a direct bond”) is replaced with the respective row headings shown below.
















Table
Row Heading









 1A
J is J-1, L is CH2CH2 and Z is a direct bond.



 2A
J is J-1, L is CH2(Me) and Z is a direct bond.



 3A
J is J-1, L is (CH2)3 and Z is a direct bond.



 4A
J is J-1, L is CH2 and Z is O.



 5A
J is J-2, L is CH2 and Z is a direct bond.



 6A
J is J-2, L is CH2CH2 and Z is a direct bond.



 7A
J is J-2, L is CH2(Me) and Z is a direct bond.



 8A
J is J-2, L is (CH2)3 and Z is a direct bond.



 9A
J is J-2, L is CH2 and Z is O.



10A
J is J-6, L is CH2 and Z is a direct bond.



11A
J is J-6, L is CH2CH2 and Z is a direct bond.



12A
J is J-6, L is CH2(Me) and Z is a direct bond.



13A
J is J-6, L is (CH2)3 and Z is a direct bond.



14A
J is J-6, L is CH2 and Z is O.



15A
J is J-7, L is CH2 and Z is a direct bond.



16A
J is J-7, L is CH2CH2 and Z is a direct bond.



17A
J is J-7, L is CH2(Me) and Z is a direct bond.



18A
J is J-7, L is (CH2)3 and Z is a direct bond.



19A
J is J-7, L is CH2 and Z is O.



20A
J is J-8, L is CH2 and Z is a direct bond.



21A
J is J-8, L is CH2CH2 and Z is a direct bond.



22A
J is J-8, L is CH2(Me) and Z is a direct bond.



23A
J is J-8, L is (CH2)3 and Z is a direct bond.



24A
J is J-8, L is CH2 and Z is O.



25A
J is J-10, L is CH2 and Z is a direct bond.



26A
J is J-10, L is CH2CH2 and Z is a direct bond.



27A
J is J-10, L is CH2(Me) and Z is a direct bond.



28A
J is J-10, L is (CH2)3 and Z is a direct bond.



29A
J is J-10, L is CH2 and Z is O.



30A
J is J-14, L is CH2 and Z is a direct bond.



31A
J is J-14, L is CH2CH2 and Z is a direct bond.



32A
J is J-14, L is CH2(Me) and Z is a direct bond.



33A
J is J-14, L is (CH2)3 and Z is a direct bond.



34A
J is J-14, L is CH2 and Z is O.



35A
J is J-3, L is CH2 and Z is a direct bond.



36A
J is J-3, L is CH2CH2 and Z is a direct bond.



37A
J is J-3, L is CH2(Me) and Z is a direct bond.



38A
J is J-3, L is (CH2)3 and Z is a direct bond.



39A
J is J-3, L is CH2 and Z is O.



40A
J is J-4, L is CH2 and Z is a direct bond.



41A
J is J-4, L is CH2CH2 and Z is a direct bond.



42A
J is J-4, L is CH2(Me) and Z is a direct bond.



43A
J is J-4, L is (CH2)3 and Z is a direct bond.



44A
J is J-4, L is CH2 and Z is O.



45A
J is J-5, L is CH2 and Z is a direct bond.



46A
J is J-5, L is CH2CH2 and Z is a direct bond.



47A
J is J-5, L is CH2(Me) and Z is a direct bond.



48A
J is J-5, L is (CH2)3 and Z is a direct bond.

















TABLE 2









embedded image







In the above formula, E is equal to E2, E2 is equal G-Z-, and G is optionally substituted with R13. The


definitions of G are as defined Exhibit A in the above Embodiments. In the column G, the number in parentheses


refers to the attachment point of the G-ring to Z. The (R13)x column refers to the substituent(s) attached to the


G-ring as shown in Exhibit A above. A dash “—” in the (R13)x column means that no R13 substituent is present


and the remaining valences on the G-ring are occupied by hydrogen atoms.


J is J-1, L is CH2 and Z is a direct bond.








G
(R13)x





G-1 (4)
—


G-1 (4)
2-Me


G-1 (4)
2-Et


G-1 (4)
2-n-Pr


G-1 (4)
2-i-Pr


G-1 (4)
2-c-Pr


G-1 (4)
2-n-Bu


G-1 (4)
2-i-Bu


G-1 (4)
2-t-Bu


G-1 (4)
2-F


G-1 (4)
2-Cl


G-1 (4)
2-Br


G-1 (4)
2-CF3


G-1 (4)
2-HO


G-1 (4)
2-N≡C


G-1 (4)
2-N≡CCH2


G-1 (4)
2-(MeO)


G-1 (4)
2-(MeOCH2)


G-1 (4)
2-(EtOCH2)


G-1 (4)
2-(CH(═O))


G-1 (4)
2-(HOC(═O))


G-1 (4)
2-(MeOC(═O))


G-1 (4)
2-(EtOC(═O))


G-1 (4)
2-(i-PrOC(═O))


G-1 (4)
2-(n-PrOC(═O))


G-1 (4)
2-(BuOC(═O))


G-1 (4)
2-(i-BuOC(═O))


G-1 (4)
2-(t-BuOC(═O))


G-1 (4)
2-(CF3CH2OC(═O)


G-1 (4)
2-(CH2═CHOC(═O))


G-1 (4)
2-(CH2═CHCH2OC(═O))


G-1 (4)
2-(CH2═CBrCH2OC(═O))


G-1 (4)
2-(CH2═CHCF2OC(═O))


G-1 (4)
2-(Me2C═CHCH2OC(═O))


G-1 (4)
2-(CH2═C(Me)CH2OC(═O))


G-1 (4)
2-(CH≡CCH2OC(═O))


G-1 (4)
2-(N≡CCH2OC(═O))


G-1 (4)
2-(MeNHC(═O))


G-1 (4)
2-(Me2NC(═O))


G-1 (4)
2-(MeNHC(═O))


G-1 (4)
2-(EtNHC(═O))


G-1 (4)
2-(PrNHC(═O))


G-1 (4)
2-(i-PrNHC(═O))


G-1 (4)
2-(BuNHC(═O))


G-1 (4)
2-(t-BuNHC(═O))


G-1 (4)
2-(i-BuNHC(═O))


G-1 (4)
2-(CF3CH2NHC(═O))


G-1 (4)
2-(c-PrCH2NHC(═O))


G-1 (4)
2-(MeOCH2NHC(═O))


G-1 (4)
2-(MeOCH2CH2NHC(═O))


G-1 (4)
2-(CH2═CHCH2NHC(═O))


G-1 (4)
2-(N≡CCH2NHC(═O))


G-1 (4)
2-(OH-N═CH)


G-1 (4)
2-(Me2NN═CH)


G-1 (4)
2-(MeOC(═O)NHN═CH)


G-1 (4)
2-(OHC(═O)CH2ON═CH)


G-1 (2)
—


G-1 (2)
4-Me


G-1 (2)
4-Et


G-1 (2)
4-n-Pr


G-1 (2)
4-i-Pr


G-1 (2)
4-c-Pr


G-1 (2)
4-n-Bu


G-1 (2)
4-i-Bu


G-1 (2)
4-t-Bu


G-1 (2)
4-F


G-1 (2)
4-Cl


G-1 (2)
4-Br


G-1 (2)
4-CF3


G-1 (2)
4-HO


G-1 (2)
4-N≡C


G-1 (2)
4-N≡CCH2


G-1 (2)
4-(MeO)


G-1 (2)
4-(MeOCH2)


G-1 (2)
4-(EtOCH2)


G-1 (2)
4-(CH(═O))


G-1 (2)
4-(HOC(═O))


G-1 (2)
4-(MeOC(═O))


G-1 (2)
4-(EtOC(═O))


G-1 (2)
4-(i-PrOC(═O))


G-1 (2)
4-(n-PrOC(═O))


G-1 (2)
4-(BuOC(═O))


G-1 (2)
4-(i-BuOC(═O))


G-1 (2)
4-(t-BuOC(═O))


G-1 (2)
4-(CF3CH2OC(═O)


G-1 (2)
4-(CH2═CHOC(═O))


G-1 (2)
4-(CH2═CHCH2OC(═O))


G-1 (2)
4-(CH2═CBrCH2OC(═O))


G-1 (2)
4-(CH2═CHCF2OC(═O))


G-1 (2)
4-(Me2C═CHCH2OC(═O))


G-1 (2)
4-(CH2═C(Me)CH2OC(═O))


G-1 (2)
4-(CH≡CCH2OC(═O))


G-1 (2)
4-(N≡CCH2OC(═O))


G-1 (2)
4-(MeNHC(═O))


G-1 (2)
4-(Me2NC(═O))


G-1 (2)
4-(MeNHC(═O))


G-1 (2)
4-(EtNHC(═O))


G-1 (2)
4-(PrNHC(═O))


G-1 (2)
4-(i-PrNHC(═O))


G-1 (2)
4-(BuNHC(═O))


G-1 (2)
4-(t-BuNHC(═O))


G-1 (2)
4-(i-BuNHC(═O))


G-1 (2)
4-(CF3CH2NHC(═O))


G-1 (2)
4-(c-PrCH2NHC(═O))


G-1 (2)
4-(MeOCH2NHC(═O))


G-1 (2)
4-(MeOCH2CH2NHC(═O))


G-1 (2)
4-(CH2═CHCH2NHC(═O))


G-1 (2)
4-(N≡CCH2NHC(═O))


G-1 (2)
4-(OH-N═CH)


G-1 (2)
4-(Me2NN═CH)


G-1 (2)
4-(MeOC(═O)NHN═CH)


G-1 (2)
4-(OHC(═O)CH2ON═CH)


G-3 (1)
—


G-3 (1)
4-Me


G-3 (1)
4-Et


G-3 (1)
4-n-Pr


G-3 (1)
4-i-Pr


G-3 (1)
4-c-Pr


G-3 (1)
4-n-Bu


G-3 (1)
4-i-Bu


G-3 (1)
4-t-Bu


G-3 (1)
4-F


G-3 (1)
4-Cl


G-3 (1)
4-Br


G-3 (1)
4-CF3


G-3 (1)
4-HO


G-3 (1)
4-N≡C


G-3 (1)
4-N≡CCH2


G-3 (1)
4-(MeO)


G-3 (1)
4-(MeOCH2)


G-3 (1)
4-(EtOCH2)


G-3 (1)
4-(CH(═O))


G-3 (1)
4-(HOC(═O))


G-3 (1)
4-(MeOC(═O))


G-3 (1)
4-(EtOC(═O))


G-3 (1)
4-(i-PrOC(═O))


G-3 (1)
4-(n-PrOC(═O))


G-3 (1)
4-(BuOC(═O))


G-3 (1)
4-(i-BuOC(═O))


G-3 (1)
4-(t-BuOC(═O))


G-3 (1)
4-(CF3CH2OC(═O)


G-3 (1)
4-(CH2═CHOC(═O))


G-3 (1)
4-(CH2═CHCH2OC(═O))


G-3 (1)
4-(CH2═CBrCH2OC(═O))


G-3 (1)
4-(CH2═CHCF2OC(═O))


G-3 (1)
4-(Me2C═CHCH2OC(═O))


G-3 (1)
4-(CH2═C(Me)CH2OC(═O))


G-3 (1)
4-(CH≡CCH2OC(═O))


G-3 (1)
4-(N≡CCH2OC(═O))


G-3 (1)
4-(MeNHC(═O))


G-3 (1)
4-(Me2NC(═O))


G-3 (1)
4-(MeNHC(═O))


G-3 (1)
4-(EtNHC(═O))


G-3 (1)
4-(PrNHC(═O))


G-3 (1)
4-(i-PrNHC(═O))


G-3 (1)
4-(BuNHC(═O))


G-3 (1)
4-(t-BuNHC(═O))


G-3 (1)
4-(i-BuNHC(═O))


G-3 (1)
4-(CF3CH2NHC(═O))


G-3 (1)
4-(c-PrCH2NHC(═O))


G-3 (1)
4-(MeOCH2NHC(═O))


G-3 (1)
4-(MeOCH2CH2NHC(═O))


G-3 (1)
4-(CH2═CHCH2NHC(═O))


G-3 (1)
4-(N≡CCH2NHC(═O))


G-3 (1)
4-(OH-N═CH)


G-3 (1)
4-(Me2NN═CH)


G-3 (1)
4-(MeOC(═O)NHN═CH)


G-3 (1)
4-(OHC(═O)CH2ON═CH)


G-9 (1)
—


G-9 (1)
3-Me


G-9 (1)
3-Et


G-9 (1)
3-n-Pr


G-9 (1)
3-i-Pr


G-9 (1)
3-c-Pr


G-9 (1)
3-n-Bu


G-9 (1)
3-i-Bu


G-9 (1)
3-t-Bu


G-9 (1)
3-F


G-9 (1)
3-Cl


G-9 (1)
3-Br


G-9 (1)
3-CF3


G-9 (1)
3-HO


G-9 (1)
3-N≡C


G-9 (1)
3-N≡CCH2


G-9 (1)
3-(MeO)


G-9 (1)
3-(MeOCH2)


G-9 (1)
3-(EtOCH2)


G-9 (1)
3-(CH(═O))


G-9 (1)
3-(HOC(═O))


G-9 (1)
3-(MeOC(═O))


G-9 (1)
3-(EtOC(═O))


G-9 (1)
3-(i-PrOC(═O))


G-9 (1)
3-(n-PrOC(═O))


G-9 (1)
3-(BuOC(═O))


G-9 (1)
3-(i-BuOC(═O))


G-9 (1)
3-(t-BuOC(═O))


G-9 (1)
3-(CF3CH2OC(═O)


G-9 (1)
3-(CH2═CHOC(═O))


G-9 (1)
3-(CH2═CHCH2OC(═O))


G-9 (1)
3-(CH2═CBrCH2OC(═O))


G-9 (1)
3-(CH2═CHCF2OC(═O))


G-9 (1)
3-(Me2C═CHCH2OC(═O))


G-9 (1)
3-(CH2═C(Me)CH2OC(═O))


G-9 (1)
3-(CH≡CCH2OC(═O))


G-9 (1)
3-(N≡CCH2OC(═O))


G-9 (1)
3-(MeNHC(═O))


G-9 (1)
3-(Me2NC(═O))


G-9 (1)
3-(MeNHC(═O))


G-9 (1)
3-(EtNHC(═O))


G-9 (1)
3-(PrNHC(═O))


G-9 (1)
3-(i-PrNHC(═O))


G-9 (1)
3-(BuNHC(═O))


G-9 (1)
3-(t-BuNHC(═O))


G-9 (1)
3-(i-BuNHC(═O))


G-9 (1)
3-(CF3CH2NHC(═O))


G-9 (1)
3-(c-PrCH2NHC(═O))


G-9 (1)
3-(MeOCH2NHC(═O))


G-9 (1)
3-(MeOCH2CH2NHC(═O))


G-9 (1)
3-(CH2═CHCH2NHC(═O))


G-9 (1)
3-(N≡CCH2NHC(═O))


G-9 (1)
3-(OH-N═CH)


G-9 (1)
3-(Me2NN═CH)


G-9 (1)
3-(MeOC(═O)NHN═CH)


G-9 (1)
3-(OHC(═O)CH2ON═CH)


G-12 (1)
—


G-12 (1)
4-Me


G-12 (1)
4-Et


G-12 (1)
4-n-Pr


G-12 (1)
4-i-Pr


G-12 (1)
4-c-Pr


G-12 (1)
4-n-Bu


G-12 (1)
4-i-Bu


G-12 (1)
4-t-Bu


G-12 (1)
4-F


G-12 (1)
4-Cl


G-12 (1)
4-Br


G-12 (1)
4-CF3


G-12 (1)
4-HO


G-12 (1)
4-N≡C


G-12 (1)
4-N≡CCH2


G-12 (1)
4-(MeO)


G-12 (1)
4-(MeOCH2)


G-12 (1)
4-(EtOCH2)


G-12 (1)
4-(CH(═O))


G-12 (1)
4-(HOC(═O))


G-12 (1)
4-(MeOC(═O))


G-12 (1)
4-(EtOC(═O))


G-12 (1)
4-(i-PrOC(═O))


G-12 (1)
4-(n-PrOC(═O))


G-12 (1)
4-(BuOC(═O))


G-12 (1)
4-(i-BuOC(═O))


G-12 (1)
4-(t-BuOC(═O))


G-12 (1)
4-(CF3CH2OC(═O)


G-12 (1)
4-(CH2═CHOC(═O))


G-12 (1)
4-(CH2═CHCH2OC(═O))


G-12 (1)
4-(CH2═CBrCH2OC(═O))


G-12 (1)
4-(CH2═CHCF2OC(═O))


G-12 (1)
4-(Me2C═CHCH2OC(═O))


G-12 (1)
4-(CH2═C(Me)CH2OC(═O))


G-12 (1)
4-(CH≡CCH2OC(═O))


G-12 (1)
4-(N≡CCH2OC(═O))


G-12 (1)
4-(MeNHC(═O))


G-12 (1)
4-(Me2NC(═O))


G-12 (1)
4-(MeNHC(═O))


G-12 (1)
4-(EtNHC(═O))


G-12 (1)
4-(PrNHC(═O))


G-12 (1)
4-(i-PrNHC(═O))


G-12 (1)
4-(BuNHC(═O))


G-12 (1)
4-(t-BuNHC(═O))


G-12 (1)
4-(i-BuNHC(═O))


G-12 (1)
4-(CF3CH2NHC(═O))


G-12 (1)
4-(c-PrCH2NHC(═O))


G-12 (1)
4-(MeOCH2NHC(═O))


G-12 (1)
4-(MeOCH2CH2NHC(═O))


G-12 (1)
4-(CH2═CHCH2NHC(═O))


G-12 (1)
4-(N≡CCH2NHC(═O))


G-12 (1)
4-(OH-N═CH)


G-12 (1)
4-(Me2NN═CH)


G-12 (1)
4-(MeOC(═O)NHN═CH)


G-12 (1)
4-(OHC(═O)CH2ON═CH)


G-12 (1)
5-Me, 3-(EtOC(═O))


G-12 (1)
3-Me


G-12 (1)
3-Et


G-12 (1)
3-n-Pr


G-12 (1)
3-i-Pr


G-12 (1)
3-c-Pr


G-12 (1)
3-n-Bu


G-12 (1)
3-i-Bu


G-12 (1)
3-t-Bu


G-12 (1)
3-F


G-12 (1)
3-Cl


G-12 (1)
3-Br


G-12 (1)
3-CF3


G-12 (1)
3-HO


G-12 (1)
3-N≡C


G-12 (1)
3-N≡CCH2


G-12 (1)
3-(MeO)


G-12 (1)
3-(MeOCH2)


G-12 (1)
3-(EtOCH2)


G-12 (1)
3-(CH(═O))


G-12 (1)
3-(HOC(═O))


G-12 (1)
3-(MeOC(═O))


G-12 (1)
3-(EtOC(═O))


G-12 (1)
3-(i-PrOC(═O))


G-12 (1)
3-(n-PrOC(═O))


G-12 (1)
3-(BuOC(═O))


G-12 (1)
3-(i-BuOC(═O))


G-12 (1)
3-(t-BuOC(═O))


G-12 (1)
3-(CF3CH2OC(═O)


G-12 (1)
3-(CH2═CHOC(═O))


G-12 (1)
3-(CH2═CHCH2OC(═O))


G-12 (1)
3-(CH2═CBrCH2OC(═O))


G-12 (1)
3-(CH2═CHCF2OC(═O))


G-12 (1)
3-(Me2C═CHCH2OC(═O))


G-12 (1)
3-(CH2═C(Me)CH2OC(═O))


G-12 (1)
3-(CH≡CCH2OC(═O))


G-12 (1)
3-(N≡CCH2OC(═O))


G-12 (1)
3-(MeNHC(═O))


G-12 (1)
3-(Me2NC(═O))


G-12 (1)
3-(MeNHC(═O))


G-12 (1)
3-(EtNHC(═O))


G-12 (1)
3-(PrNHC(═O))


G-12 (1)
3-(i-PrNHC(═O))


G-12 (1)
3-(BuNHC(═O))


G-12 (1)
3-(t-BuNHC(═O))


G-12 (1)
3-(i-BuNHC(═O))


G-12 (1)
3-(CF3CH2NHC(═O))


G-12 (1)
3-(c-PrCH2NHC(═O))


G-12 (1)
3-(MeOCH2NHC(═O))


G-12 (1)
3-(MeOCH2CH2NHC(═O))


G-12 (1)
3-(CH2═CHCH2NHC(═O))


G-12 (1)
3-(N≡CCH2NHC(═O))


G-12 (1)
3-(OH-N═CH)


G-12 (1)
3-(Me2NN═CH)


G-12 (1)
3-(MeOC(═O)NHN═CH)


G-12 (1)
3-(OHC(═O)CH2ON═CH)


G-13 (1)
—


G-13 (1)
5-Me


G-13 (1)
5-Et


G-13 (1)
5-n-Pr


G-13 (1)
5-i-Pr


G-13 (1)
5-c-Pr


G-13 (1)
5-n-Bu


G-13 (1)
5-i-Bu


G-13 (1)
5-t-Bu


G-13 (1)
5-F


G-13 (1)
5-Cl


G-13 (1)
5-Br


G-13 (1)
5-CF3


G-13 (1)
5-HO


G-13 (1)
5-N≡C


G-13 (1)
5-N≡CCH2


G-13 (1)
5-(MeO)


G-13 (1)
5-(MeOCH2)


G-13 (1)
5-(EtOCH2)


G-13 (1)
5-(CH(═O))


G-13 (1)
5-(HOC(═O))


G-13 (1)
5-(MeOC(═O))


G-13 (1)
5-(EtOC(═O))


G-13 (1)
5-(i-PrOC(═O))


G-13 (1)
5-(n-PrOC(═O))


G-13 (1)
5-(BuOC(═O))


G-13 (1)
5-(i-BuOC(═O))


G-13 (1)
5-(t-BuOC(═O))


G-13 (1)
5-(CF3CH2OC(═O)


G-13 (1)
5-(CH2═CHOC(═O))


G-13 (1)
5-(CH2═CHCH2OC(═O))


G-13 (1)
5-(CH2═CBrCH2OC(═O))


G-13 (1)
5-(CH2═CHCF2OC(═O))


G-13 (1)
5-(Me2C═CHCH2OC(═O))


G-13 (1)
5-(CH2═C(Me)CH2OC(═O))


G-13 (1)
5-(CH≡CCH2OC(═O))


G-13 (1)
5-(N≡CCH2OC(═O))


G-13 (1)
5-(MeNHC(═O))


G-13 (1)
5-(Me2NC(═O))


G-13 (1)
5-(MeNHC(═O))


G-13 (1)
5-(EtNHC(═O))


G-13 (1)
5-(PrNHC(═O))


G-13 (1)
5-(i-PrNHC(═O))


G-13 (1)
5-(BuNHC(═O))


G-13 (1)
5-(t-BuNHC(═O))


G-13 (1)
5-(i-BuNHC(═O))


G-13 (1)
5-(CF3CH2NHC(═O))


G-13 (1)
5-(c-PrCH2NHC(═O))


G-13 (1)
5-(MeOCH2NHC(═O))


G-13 (1)
5-(MeOCH2CH2NHC(═O))


G-13 (1)
5-(CH2═CHCH2NHC(═O))


G-13 (1)
5-(N≡CCH2NHC(═O))


G-13 (1)
5-(OH-N═CH)


G-13 (1)
5-(Me2NN═CH)


G-13 (1)
5-(MeOC(═O)NHN═CH)


G-13 (1)
5-(OHC(═O)CH2ON═CH)


G-17 (1)
—


G-17 (1)
4-Me


G-17 (1)
4-Et


G-17 (1)
4-n-Pr


G-17 (1)
4-i-Pr


G-17 (1)
4-c-Pr


G-17 (1)
4-n-Bu


G-17 (1)
4-i-Bu


G-17 (1)
4-t-Bu


G-17 (1)
4-F


G-17 (1)
4-Cl


G-17 (1)
4-Br


G-17 (1)
4-CF3


G-17 (1)
4-HO


G-17 (1)
4-N≡C


G-17 (1)
4-N≡CCH2


G-17 (1)
4-(MeO)


G-17 (1)
4-(MeOCH2)


G-17 (1)
4-(EtOCH2)


G-17 (1)
4-(CH(═O))


G-17 (1)
4-(HOC(═O))


G-17 (1)
4-(MeOC(═O))


G-17 (1)
4-(EtOC(═O))


G-17 (1)
4-(i-PrOC(═O))


G-17 (1)
4-(n-PrOC(═O))


G-17 (1)
4-(BuOC(═O))


G-17 (1)
4-(i-BuOC(═O))


G-17 (1)
4-(t-BuOC(═O))


G-17 (1)
4-(CF3CH2OC(═O)


G-17 (1)
4-(CH2═CHOC(═O))


G-17 (1)
4-(CH2═CHCH2OC(═O))


G-17 (1)
4-(CH2═CBrCH2OC(═O))


G-17 (1)
4-(CH2═CHCF2OC(═O))


G-17 (1)
4-(Me2C═CHCH2OC(═O))


G-17 (1)
4-(CH2═C(Me)CH2OC(═O))


G-17 (1)
4-(CH≡CCH2OC(═O))


G-17 (1)
4-(N≡CCH2OC(═O))


G-17 (1)
4-(MeNHC(═O))


G-17 (1)
4-(Me2NC(═O))


G-17 (1)
4-(MeNHC(═O))


G-17 (1)
4-(EtNHC(═O))


G-17 (1)
4-(PrNHC(═O))


G-17 (1)
4-(i-PrNHC(═O))


G-17 (1)
4-(BuNHC(═O))


G-17 (1)
4-(t-BuNHC(═O))


G-17 (1)
4-(i-BuNHC(═O))


G-17 (1)
4-(CF3CH2NHC(═O))


G-17 (1)
4-(c-PrCH2NHC(═O))


G-17 (1)
4-(MeOCH2NHC(═O))


G-17 (1)
4-(MeOCH2CH2NHC(═O))


G-17 (1)
4-(CH2═CHCH2NHC(═O))


G-17 (1)
4-(N≡CCH2NHC(═O))


G-17 (1)
4-(OH-N═CH)


G-17 (1)
4-(Me2NN═CH)


G-17 (1)
4-(MeOC(═O)NHN═CH)


G-17 (1)
4-(OHC(═O)CH2ON═CH)









The present disclosure also includes Tables 1B through 48B, each of which is constructed the same as Table 2 above, except that the row heading in Table 2 (i.e. “J is J-1, L is CH2, and Z is a direct bond”) is replaced with the respective row headings shown below.
















Table
Row Heading









 1B
J is J-1, L is CH2CH2 and Z is a direct bond.



 2B
J is J-1, L is CH2(Me) and Z is a direct bond.



 3B
J is J-1, L is (CH2)3 and Z is a direct bond.



 4B
J is J-1, L is CH2 and Z is O.



 5B
J is J-2, L is CH2 and Z is a direct bond.



 6B
J is J-2, L is CH2CH2 and Z is a direct bond.



 7B
J is J-2, L is CH2(Me) and Z is a direct bond.



 8B
J is J-2, L is (CH2)3 and Z is a direct bond.



 9B
J is J-2, L is CH2 and Z is O.



10B
J is J-6, L is CH2 and Z is a direct bond.



11B
J is J-6, L is CH2CH2 and Z is a direct bond.



12B
J is J-6, L is CH2(Me) and Z is a direct bond.



13B
J is J-6, L is (CH2)3 and Z is a direct bond.



14B
J is J-6, L is CH2 and Z is O.



15B
J is J-7, L is CH2 and Z is a direct bond.



16B
J is J-7, L is CH2CH2 and Z is a direct bond.



17B
J is J-7, L is CH2(Me) and Z is a direct bond.



18B
J is J-7, L is (CH2)3 and Z is a direct bond.



19B
J is J-7, L is CH2 and Z is O.



20B
J is J-8, L is CH2 and Z is a direct bond.



21B
J is J-8, L is CH2CH2 and Z is a direct bond.



22B
J is J-8, L is CH2(Me) and Z is a direct bond.



23B
J is J-8, L is (CH2)3 and Z is a direct bond.



24B
J is J-8, L is CH2 and Z is O.



25B
J is J-10, L is CH2 and Z is a direct bond.



26B
J is J-10, L is CH2CH2 and Z is a direct bond.



27B
J is J-10, L is CH2(Me) and Z is a direct bond.



28B
J is J-10, L is (CH2)3 and Z is a direct bond.



29B
J is J-10, L is CH2 and Z is O.



30B
J is J-14, L is CH2 and Z is a direct bond.



31B
J is J-14, L is CH2CH2 and Z is a direct bond.



32B
J is J-14, L is CH2(Me) and Z is a direct bond.



33B
J is J-14, L is (CH2)3 and Z is a direct bond.



34B
J is J-14, L is CH2 and Z is O.



35B
J is J-3, L is CH2 and Z is a direct bond.



36B
J is J-3, L is CH2CH2 and Z is a direct bond.



37B
J is J-3, L is CH2(Me) and Z is a direct bond.



38B
J is J-3, L is (CH2)3 and Z is a direct bond.



39B
J is J-3, L is CH2 and Z is O.



40B
J is J-4, L is CH2 and Z is a direct bond.



41B
J is J-4, L is CH2CH2 and Z is a direct bond.



42B
J is J-4, L is CH2(Me) and Z is a direct bond.



43B
J is J-4, L is (CH2)3 and Z is a direct bond.



44B
J is J-4, L is CH2 and Z is O.



45B
J is J-5, L is CH2 and Z is a direct bond.



46B
J is J-5, L is CH2CH2 and Z is a direct bond.



47B
J is J-5, L is CH2(Me) and Z is a direct bond.



48B
J is J-5, L is (CH2)3 and Z is a direct bond.










Formulation/Utility

A compound of Formula 1 of this invention (including N-oxides and salts thereof), or a mixture (i.e. composition) comprising the compound with at least one additional fungicidal compound as described in the Summary of the Invention, will generally be used as a fungicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.


The mixtures of component (a) (i.e. at least one compound of Formula 1, N-oxides, or salts thereof) with component (b) (e.g., selected from (b1) to (b54) and salts thereof as described above) and/or one or more other biologically active compound or agent (i.e. insecticides, other fungicides, nematocides, acaricides, herbicides and other biological agents) can be formulated in a number of ways, including:

    • (i) component (a), component (b) and/or one or more other biologically active compounds or agents can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, e.g., as a tank mix; or
    • (ii) component (a), component (b) and/or one or more other biologically active compounds or agents can be formulated together in the proper weight ratio.


Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspoemulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.


The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film-forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.


Of note is a composition embodiment wherein granules of a solid composition comprising a compound of Formula 1 (or an N-oxide or salt thereof) is mixed with granules of a solid composition comprising component (b). These mixtures can be further mixed with granules comprising additional agricultural protectants. Alternatively, two or more agricultural protectants (e.g., a component (a) (Formula 1) compound, a component (b) compound, an agricultural protectant other than component (a) or (b)) can be combined in the solid composition of one set of granules, which is then mixed with one or more sets of granules of solid compositions comprising one or more additional agricultural protectants. These granule mixtures can be in accordance with the general granule mixture disclosure of PCT Patent Publication WO 94/24861 or more preferably the homogeneous granule mixture teaching of U.S. Pat. No. 6,022,552.


Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.


The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.














Weight Percent











Active





Ingredient
Diluent
Surfactant





Water-Dispersible and Water-
0.001-90
 0-99.999
0-15


soluble Granules, Tablets and





Powders





Oil Dispersions, Suspensions,
   1-50
40-99
0-50


Emulsions, Solutions





(including Emulsifiable





Concentrates)





Dusts
   1-25
70-99
0-5


Granules and Pellets
0.001-95
 5-99.999
0-15


High Strength Compositions
  90-99
 0-10
0-2









Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.


Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.


The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.


Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides; alkyl polysaccharides; and glucamides such as mixtures of octyl-N-methylglucamide and decyl-N-methylglucamide (e.g., products is obtainable under the Synergen® GA name from Clariant).


Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.


Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.


Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.


Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.


The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 m can be wet milled using media mills to obtain particles with average diameters below 3 μm. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. Pat. No. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 m range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. Pat. Nos. 4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.


One embodiment of the present invention relates to a method for controlling fungal pathogens, comprising diluting the fungicidal composition of the present invention (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other fungicide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of said diluted composition.


Although a spray composition formed by diluting with water a sufficient concentration of the present fungicidal composition can provide sufficient efficacy for controlling fungal pathogens, separately formulated adjuvant products can also be added to spray tank mixtures. These additional adjuvants are commonly known as “spray adjuvants” or “tank-mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture. Adjuvants can be anionic or nonionic surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents. Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, penetration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization and degradation. To obtain optimal performance, adjuvants are selected with regard to the properties of the active ingredient, formulation and target (e.g., crops, insect pests).


The amount of adjuvants added to spray mixtures is generally in the range of about 0.1% to 2.5% by volume. The application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare. Representative examples of spray adjuvants include: Adigor® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.


One method of seed treatment is by spraying or dusting the seed with a compound of the invention (i.e. as a formulated composition) before sowing the seeds. Compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present invention comprises a biologically effective amount of a compound of Formula 1 and a film former or adhesive agent. Seeds can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listed therein.


For further information regarding the art of formulation, see T. S. Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture” in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. Also see U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, U K, 2000.


In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Active ingredient refers to the compounds in Index Tables A-L disclosed herein. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be constructed as merely illustrative, and not limiting of the disclosure in any way whatsoever.


Example A
High Strength Concentrate


















Compound 263
98.5%



silica aerogel
0.5%



synthetic amorphous fine silica
1.0%










Wettable Powder


















Compound 330
65.0%



dodecylphenol polyethylene glycol ether
 2.0%



sodium ligninsulfonate
 4.0%



sodium silicoaluminate
 6.0%



montmorillonite (calcined)
23.0%










Example C
Granule


















Compound 64
10.0%



attapulgite granules (low volatile matter, 0.71/0.30 mm;
90.0%



U.S.S. No. 25-50 sieves)










Example D
Extruded Pellet


















Compound 32
25.0%



anhydrous sodium sulfate
10.0%



crude calcium ligninsulfonate
 5.0%



sodium alkylnaphthalenesulfonate
 1.0%



calcium/magnesium bentonite
59.0%










Example E
Emulsifiable Concentrate


















Compound 64
10.0%



polyoxyethylene sorbitol hexoleate
20.0%



C6-C10 fatty acid methyl ester
70.0%










Example F
Microemulsion


















Compound 331
 5.0%



polyvinylpyrrolidone-vinyl acetate copolymer
30.0%



alkylpolyglycoside
30.0%



glyceryl monooleate
15.0%



water
20.0%










Example G
Seed Treatment















Compound 297
20.00%


polyvinylpyrrolidone-vinyl acetate copolymer
 5.00%


montan acid wax
 5.00%


calcium ligninsulfonate
 1.00%


polyoxyethylene/polyoxypropylene block copolymers
 1.00%


stearyl alcohol (POE 20)
 2.00%


polyorganosilane
 0.20%


colorant red dye
 0.05%


water
65.75%









Example H
Fertilizer Stick


















Compound 126
 2.50%



pyrrolidone-styrene copolymer
 4.80%



tristyrylphenyl 16-ethoxylate
 2.30%



talc
 0.80%



corn starch
 5.00%



slow-release fertilizer
36.00%



kaolin
38.00%



water
10.60%










Example I
Suspension Concentrate















Compound 163
  35%


butyl polyoxyethylene/polypropylene block copolymer
 4.0%


stearic acid/polyethylene glycol copolymer
 1.0%


styrene acrylic polymer
 1.0%


xanthan gum
 0.1%


propylene glycol
 5.0%


silicone based defoamer
 0.1%


1,2-benzisothiazolin-3-one
 0.1%


water
53.7%









Example J
Emulsion in Water















Compound 71
10.0%


butyl polyoxyethylene/polypropylene block copolymer
 4.0%


stearic acid/polyethylene glycol copolymer
 1.0%


styrene acrylic polymer
 1.0%


xanthan gum
 0.1%


propylene glycol
 5.0%


silicone based defoamer
 0.1%


1,2-benzisothiazolin-3-one
 0.1%


aromatic petroleum based hydrocarbon
 20.0


water
58.7%









Example K
Oil Dispersion


















Compound 229
  25%



polyoxyethylene sorbitol hexaoleate
  15%



organically modified bentonite clay
 2.5%



fatty acid methyl ester
57.5%










Example L
Suspoemulsion















Compound 127
10.0%


imidacloprid
 5.0%


butyl polyoxyethylene/polypropylene block copolymer
 4.0%


stearic acid/polyethylene glycol copolymer
 1.0%


styrene acrylic polymer
 1.0%


xanthan gum
 0.1%


propylene glycol
 5.0%


silicone based defoamer
 0.1%


1,2-benzisothiazolin-3-one
 0.1%


aromatic petroleum based hydrocarbon
20.0%


water
53.7%









Water-soluble and water-dispersible formulations are typically diluted with water to form aqueous compositions before application. Aqueous compositions for direct applications to the plant or portion thereof (e.g., spray tank compositions) typically contain at least about 1 ppm or more (e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.


Seed is normally treated at a rate of from about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed (i.e. from about 0.0001 to 1% by weight of the seed before treatment). A flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent.


The compositions of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound. The compounds and/or compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Ascomycota, Basidiomycota, Zygomycota phyla, and the fungal-like Oomycota class. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops. These pathogens include but are not limited to those listed in Table 1-1. For Ascomycetes and Basidiomycetes, names for both the sexual/teleomorph/perfect stage as well as names for the asexual/anamorph/imperfect stage (in parentheses) are listed where known. Synonymous names for pathogens are indicated by an equal sign. For example, the sexual/teleomorph/perfect stage name Phaeosphaeria nodorum is followed by the corresponding asexual/anamorph/imperfect stage name Stagonospora nodorum and the synonymous older name Septoria nodorum.










TABLE 1-1







 
Ascomycetes in the order Pleosporales including




Alternaria solani, A. alternata and A. brassicae,




Guignardia bidwellii, Venturia inaequalis, Pyrenophora





tritici-repentis (Dreschlera tritici-repentis=




Helminthosporium tritici-repentis) and Pyrenophora




teres (Dreschlera teres=Helminthosporium




teres), Corynespora cassiicola, Phaeosphaeria




nodorum (Stagonospora nodorum=Septoria




nodorum), Cochliobolus carbonum and C. heterostrophus,




Leptosphaeria biglobosa and L.




maculans;




Ascomycetes in the order Mycosphaerellales including




Mycosphaerella graminicola (Zymoseptoria




tritici = Septoria tritici), M. berkeleyi (Cercosporidium




personatum), M. arachidis (Cercospora




arachidicola), Passalora sojina (Cercospora sojina),




Cercospora zeae-maydis and C. beticola;



Ascomycetes in the order Erysiphales (the powdery



mildews) such as Blumeria graminis f.sp. tritici



and Blumeria graminis f.sp. hordei, Erysiphe




polygoni, E. necator (= Uncinula necator),




Podosphaera fuliginea (= Sphaerotheca fuliginea), and




Podosphaera leucotricha (= Sphaerotheca




fuliginea);



Ascomycetes in the order Helotiales such as Botryotinia




fuckeliana (Botrytis cinerea), Oculimacula




yallundae (= Tapesia yallundae; anamorph Helgardia




herpotrichoides = Pseudocercosporella





herpetrichoides), Monilinia fructicola, Sclerotinia




sclerotiorum, Sclerotinia minor, and Sclerotinia




homoeocarpa;




Ascomycetes in the order Hypocreales such as




Giberella zeae (Fusarium graminearum), G.




monoliformis (Fusarium moniliforme), Fusarium




solani and Verticillium dahliae;



Ascomycetes in the order Eurotiales such as




Aspergillus flavus and A. parasiticus;



Ascomycetes in the order Diaporthales such as




Cryptosphorella viticola (= Phomopsis viticola),




Phomopsis longicolla, and Diaporthe phaseolorum;



Other Ascomycete pathogens including Magnaporthe




grisea, Gaeumannomyces graminis,





Rhynchosporium secalis, and anthracnose pathogens such as




Glomerella acutata (Colletotrichum




acutatum), G. graminicola (C. graminicola) and




G. lagenaria (C. orbiculare);



Basidiomycetes in the order Urediniales (the rusts) including




Puccinia recondita, P. striiformis,





Puccinia hordei, P. graminis and P. arachidis),




Hemileia vastatrix and Phakopsora pachyrhizi;



Basidiomycetes in the order Ceratobasidiales such as




Thanatophorum cucumeris (Rhizoctonia solani)



and Ceratobasidium oryzae-sativae (Rhizoctonia oryzae);



Basidiomycetes in the order Polyporales such as




Athelia rolfsii (Sclerotium rolfsii);



Basidiomycetes in the order Ustilaginales such as Ustilago maydis;



Zygomycetes in the order Mucorales such as Rhizopus stolonifer;



Oomycetes in the order Pythiales, including Phytophthora




infestans, P. megasperma, P. parasitica,





P. sojae, P. cinnamomi and P. capsici, and Pythium



pathogens such as Pythium aphanidermatum, P.




graminicola, P. irregulare, P. ultimum and P. dissoticum;



Oomycetes in the order Peronosporales such as




Plasmopara viticola, P. halstedii, Peronospora





hyoscyami (=Peronospora tabacina), P. manshurica,




Hyaloperonospora parasitica (=Peronospora




parasitica), Pseudoperonospora cubensis and Bremia lactucae;



and other genera and species closely related



to all of the above pathogens.









In addition to their fungicidal activity, the compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species. By controlling harmful microorganisms, the compositions of this invention are useful for improving (i.e. increasing) the ratio of beneficial to harmful microorganisms in contact with crop plants or their propagules (e.g., seeds, corms, bulbs, tubers, cuttings) or in the agronomic environment of the crop plants or their propagules.


Compositions of this invention are useful in treating all plants, plant parts and seeds. Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants or seeds (transgenic plants or seeds) are those in which a heterologous gene (transgene) has been stably integrated into the plant's or seed's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.


Genetically modified plant cultivars which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance.


Treatment of genetically modified plants and seeds with compounds of the invention may result in super-additive or enhanced effects. For example, reduction in application rates, broadening of the activity spectrum, increased tolerance to biotic/abiotic stresses or enhanced storage stability may be greater than expected from just simple additive effects of the application of compounds of the invention on genetically modified plants and seeds.


Compounds and compositions of this invention are useful in seed treatments for protecting seeds from plant diseases. In the context of the present disclosure and claims, treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention. This seed treatment protects the seed from soil-borne disease pathogens and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed. The seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingredient within the developing plant. Seed treatments can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance such as glyphosate acetyltransferase, which provides resistance to glyphosate. Seed treatments with compounds and compositions of this invention can also increase vigor of plants growing from the seed.


Compounds and compositions of this invention are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.


Furthermore, the compounds and compositions of this invention are useful in treating postharvest diseases of fruits and vegetables caused by fungi, oomycetes and bacteria. These infections can occur before, during and after harvest. For example, infections can occur before harvest and then remain dormant until some point during ripening (e.g., host begins tissue changes in such a way that infection can progress or conditions become conducive for disease development); also infections can arise from surface wounds created by mechanical or insect injury. In this respect, the compositions of this invention can reduce losses (i.e. losses resulting from quantity and quality) due to postharvest diseases which may occur at any time from harvest to consumption. Treatment of postharvest diseases with compounds of the invention can increase the period of time during which perishable edible plant parts (e.g., fruits, seeds, foliage, stems, bulbs, tubers) can be stored refrigerated or un-refrigerated after harvest, and remain edible and free from noticeable or harmful degradation or contamination by fungi or other microorganisms. Treatment of edible plant parts before or after harvest with compounds of the invention can also decrease the formation of toxic metabolites of fungi or other microorganisms, for example, mycotoxins such as aflatoxins.


Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruits, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to seeds to protect the seeds and seedlings developing from the seeds. The compounds can also be applied through irrigation water to treat plants. Control of postharvest pathogens which infect the produce before harvest is typically accomplished by field application of a compound of this invention, and in cases where infection occurs after harvest the compounds can be applied to the harvested crop as dips, sprays, fumigants, treated wraps and box liners.


The compounds and compositions of this invention can also be applied using an unmanned aerial vehicle (UAV) for the dispension of the compositions disclosed herein over a planted area. In some embodiments the planted area is a crop-containing area. In some embodiments, the crop is selected from a monocot or dicot. In some embodiments, the crop is selected form rice, corn, barley, sobean, wheat, vegetable, tobacco, tea tree, fruit tree and sugar cane. In some embodiments, the compositions disclosed herein are formulated for spraying at an ultra-low volume. Products applied by drones may use water or oil as the spray carrier. Typical spray volume (including product) used for drone applications globally. 5.0 liters/ha-100 liters/ha (approximately 0.5-10 gpa). This includes the range of ultra low spray volume (ULV) to low spray volume (LV). Although not common there may be situations where even lower spray volumes could be used as low as 1.0 liter/ha (0.1 gpa).


Suitable rates of application (e.g., fungicidally effective amounts) of component (a) (i.e. at least one compound selected from compounds of Formula 1, N-oxides and salts thereof) as well as suitable rates of application (e.g., biologically effective amounts, fungicidally effective amounts or insecticidally effective amounts) for the mixtures and compositions comprising component (a) according to this invention can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, the population structure of the pathogen to be controlled, ambient moisture and temperature and should be determined under actual use conditions. One skilled in the art can easily determine through simple experimentation the fungicidally effective amount necessary for the desired level of plant disease control. Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed. One skilled in the art can easily determine through simple experimentation the application rates of component (a), and mixtures and compositions thereof, containing particular combinations of active ingredients according to this invention needed to provide the desired spectrum of plant protection and control of plant diseases and optionally other plant pests.


Compounds and compositions of the present invention may also be useful for increasing vigor of a crop plant. This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a composition comprising a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e. biologically effective amount). Typically the compound of Formula 1 is applied in a formulated composition. Although the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant. The locus relevant to this method most commonly comprises the growth medium (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown. Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.


Increased crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of vegetative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e. yield quality); (d) enhanced ability of the crop to withstand or prevent plant disease infections and arthropod, nematode or mollusk pest infestations; and (e) increased ability of the crop to withstand environmental stresses such as exposure to thermal extremes, suboptimal moisture or phytotoxic chemicals.


The compounds and compositions of the present invention may increase the vigor of treated plants compared to untreated plants by preventing and/or curing plant diseases caused by fungal plant pathogens in the environment of the plants. In the absence of such control of plant diseases, the diseases reduce plant vigor by consuming plant tissues or sap, or transmitting plant pathogens such as viruses. Even in the absence of fungal plant pathogens, the compounds of the invention may increase plant vigor by modifying metabolism of plants. Generally, the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the invention if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.


Of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising plant diseases caused by fungal plant pathogens. Also of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising plant diseases caused by fungal plant pathogens. Also of note is a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising an amount of moisture less than ideal for supporting growth of the crop plant.


Compounds and compositions of this invention can also be mixed with one or more other biologically active compounds or agents including fungicides, insecticides, nematicides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Thus the present invention also pertains to a composition comprising a compound of Formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.


As mentioned in the Summary of the Invention, one aspect of the present invention is a fungicidal composition comprising (i.e. a mixture or combination of) a compound of Formula 1, an N-oxide, or a salt thereof (i.e. component (a)), and at least one other fungicide (i.e. component (b)). Of note is such a combination where the other fungicidal active ingredient has different site of action from the compound of Formula 1. In certain instances, a combination with at least one other fungicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise a fungicidally effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.


Examples of component (b) fungicides include acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper hydroxide, copper oxychloride, copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M), dinocap, dithianon, dithiolanes, dodemorph, dodine, dipymetitrone, econazole, edifenphos, enoxastrobin (also known as enestroburin), epoxiconazole, etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenaminstrobin, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, flometoquin, florylpicoxamid, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, flumorph, fluopicolide, fluopimomide, fluopyram, flouroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fthalide, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isoconazole, isofetamid, isoprothiolane, isoflucypram, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandepropamid, mandestrobin, maneb, mepanipyrim, mepronil, meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), mefentrifluconazole, metconazole, methasulfocarb, metiram, metominostrobin, metrafenone, miconazole, myclobutanil, naftifine, neo-asozin, nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, pefurazoate, penconazole, pencycuron, penflufen, penthiopyrad, phosphorous acid (including salts thereof, e.g., fosetyl-aluminum), picarbutrazox, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamacarb, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, pyrrolnitrin, quinconazole, quinofumelin (Registry Number 861647-84-9) quinomethionate, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolnifanide, tolprocarb, tolyfluanid, triadimefon, triadimenol, triarimol, triticonazole, triazoxide, tribasic copper sulfate, tricyclazole, triclopyricarb, tridemorph, trifloxystrobin, triflumizole, triforine, trimorphamide, uniconazole, uniconazole-P, validamycin, valifenalate (also known as valiphenal), vinclozolin, zineb, ziram, zoxamide, N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)-ethyl]-1H-1,2,4-triazole-1-ethanol, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)-amino]butanamide, N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide, N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-(3′,4′-difluoro[1,1′-biphenyl]-2-yl)-3-(trifluoromethyl)-2-pyrazinecarboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 5,8-di-fluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-quinazo-linamine, 1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)-methoxy]-4-pyrimidinamine, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]-ethoxy]imino]methyl]benzeneacetamide, and [[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl 2-methylpropanoate. Therefore of note is a fungicidal composition comprising as component (a) a compound of Formula 1 (or an N-oxide or salt thereof) and as component (b) at least one fungicide selected from the preceding list.


Of particular note are combinations of compounds of Formula 1 (or an N-oxide or salt thereof) (i.e. Component (a) in compositions) with component (b) compounds selected from aminopyrifen (Registry Number 1531626-08-0), azoxystrobin, benzovindiflupyr, bixafen, captan, carpropamid, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, dichlobentiazox (Registry Number 957144-77-3), diethofencarb, difenoconazole, dimethomorph, dipymetitrone, epoxiconazole, ethaboxam, fenarimol, fenhexamid, fluazinam, fludioxonil, fluindapyr, fluopyram, flusilazole, flutianil, flutriafol, fluxapyroxad, folpet, ipflufenoquin (Registry Number 1314008-27-9), iprodione, isofetamid, isoflucypram, isopyrazam, kresoxim-methyl, mancozeb, mandestrobin, meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), mefentrifluconazole, metconazole, metrafenone, metyltetraprole (Registry Number 1472649-01-6), myclobutanil, oxathiapiprolin, penflufen, penthiopyrad, phosphorous acid (including salts thereof, e.g., fosetyl-aluminum), picoxystrobin, propiconazole, proquinazid, prothioconazole, pyridachlometyl (Registry Number 1358061-55-8), pyraclostrobin, pyrapropoyne (Registry Number 1803108-03-3), pyrimethanil, sedaxane spiroxamine, sulfur, tebuconazole, thiophanate-methyl, trifloxystrobin, zoxamide, α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol, N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, 3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, 1,1-di-methylethyl N-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine, (αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol, rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole, rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione, and rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiran-yl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole (i.e. as Component (b) in compostions).


Generally preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower use rate or broader spectrum of plant pathogens controlled) or resistance management are mixtures of a compound of Formula 1, an N-oxide, or salt thereof, with a fungicidal compound selected from the group: amisulbrom, azoxystrobin, benzovindiflupyr, bixafen, boscalid, carbendazim, carboxin, chlorothalonil, copper hydroxide, cymoxanil, cyproconazole, difenoconazole, dimethomorph, dimoxystrobin, epoxiconazole, fenpropidin, fenpropimorph, florylpicoxamid, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, ipfentrifluconazole, iprodione, kresoxim-methyl, mancozeb, metalaxyl, mefenoxam, mefentrifluconazole, metconazole, metominostrobin, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyriofenone, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and triticonazole.


In the fungicidal compositions of the present invention, component (a) (i.e. at least one compound selected from compounds of Formula 1, N-oxides, and salts thereof) and component (b) are present in fungicidally effective amounts. The weight ratio of component (a) to component (b) (i.e. one or more additional fungicidal compounds) is generally between about 1:3000 to about 3000:1, and more typically between about 1:500 and about 500:1. Of note are compositions where in the weight ratio of component (a) to component (b) is from about 125:1 to about 1:125. With many fungicidal compounds of component (b), these compositions are particularly effective for controlling plant diseases caused by fungal plant pathogens. Of particular note are compositions wherein the weight ratio of component (a) to component (b) is from about 25:1 to about 1:25, or from about 5:1 to about 1:5. One skilled in the art can easily determine through simple experimentation the weight ratios and application rates of fungicidal compounds necessary for the desired spectrum of fungicidal protection and control. It will be evident that including additional fungicidal compounds in component (b) may expand the spectrum of plant diseases controlled beyond the spectrum controlled by component (a) alone. Furthermore, Tables A1 through A21 and C1 through C21 exemplify weight ratios for combinations of fungicidal compounds of the present invention. Table B1 lists typical, more typical and most typical ranges of ratios involving particular fungicidal compounds of component (b).


Specific mixtures (compound numbers refer to compounds in Index Tables A through L) are listed in Tables A1 through A21. In Table A1, each line below the column headings “Component (a)” and “Component (b)” specifically discloses a mixture of Component (a), (i.e. Compound 32), with a Component (b) fungicidal compound. The entries under the heading “Illustrative Ratios” disclose three specific weight ratios of Component (a) to Component (b) for the disclosed mixture. For example, the first line of Table A1 discloses a mixture of Compound 32 with acibenzolar-S-methyl and lists weight ratios of Compound 32 relative to acibenzolar-S-methyl of 1:1, 1:4 or 1:18.











TABLE A1





Component (a)
Component (b)
Illustrative Ratios(*)



















Compound 32
acibenzolar-S-methyl
1:1
1:4
1:18


Compound 32
aldimorph
7:1
3:1
1:1


Compound 32
ametoctradin
3:1
1:1
1:3


Compound 32
amisulbrom
1:1
1:2
1:6


Compound 32
anilazine
22:1
8:1
4:1


Compound 32
azaconazole
2:1
1:2
1:4


Compound 32
azoxystrobin
3:1
1:1
1:3


Compound 32
benalaxyl
1:1
1:2
1:6


Compound 32
benalaxyl-M
1:1
1:3
1:8


Compound 32
benodanil
4:1
2:1
1:2


Compound 32
benomyl
11:1
4:1
1:1


Compound 32
benthiavalicarb
1:1
1:4
1:12


Compound 32
benthiavalicarb-isopropyl
1:1
1:4
1:12


Compound 32
bethoxazin
15:1
5:1
2:1


Compound 32
binapacryl
15:1
5:1
2:1


Compound 32
biphenyl
15:1
5:1
2:1


Compound 32
bitertanol
3:1
1:1
1:2


Compound 32
bixafen
2:1
1:1
1:3


Compound 32
blasticidin-S
1:4
1:12
1:30


Compound 32
Bordeaux mixture
45:1
15:1
5:1



(tribasic copper sulfate)





Compound 32
boscalid
4:1
2:1
1:2


Compound 32
bromuconazole
3:1
1:1
1:3


Compound 32
bupirimate
1:3
1:10
1:30


Compound 32
captafol
15:1
5:1
2:1


Compound 32
captan
15:1
5:1
2:1


Compound 32
carbendazim
11:1
4:1
2:1


Compound 32
carboxin
4:1
2:1
1:2


Compound 32
carpropamid
3:1
1:1
1:3


Compound 32
chloroneb
100:1
35:1
14:1


Compound 32
chlorothalonil
15:1
5:1
2:1


Compound 32
chlozolinate
11:1
4:1
2:1


Compound 32
clotrimazole
3:1
1:1
1:3


Compound 32
copper hydroxide
45:1
15:1
5:1


Compound 32
copper oxychloride
45:1
15:1
5:1


Compound 32
cyazofamid
1:1
1:2
1:6


Compound 32
cyflufenamid
1:2
1:6
1:24


Compound 32
cymoxanil
1:1
1:2
1:5


Compound 32
cyproconazole
1:1
1:2
1:6


Compound 32
cyprodinil
4:1
2:1
1:2


Compound 32
dichlofluanid
15:1
5:1
2:1


Compound 32
diclocymet
15:1
5:1
2:1


Compound 32
diclomezine
3:1
1:1
1:3


Compound 32
dicloran
15:1
5:1
2:1


Compound 32
diethofencarb
7:1
2:1
1:2


Compound 32
difenoconazole
1:1
1:3
1:12


Compound 32
diflumetorim
15:1
5:1
2:1


Compound 32
dimethirimol
1:3
1:8
1:30


Compound 32
dimethomorph
3:1
1:1
1:2


Compound 32
dimoxystrobin
2:1
1:1
1:4


Compound 32
diniconazole
1:1
1:3
1:8


Compound 32
diniconazole-M
1:1
1:3
1:12


Compound 32
dinocap
2:1
1:1
1:3


Compound 32
dithianon
5:1
2:1
1:2


Compound 32
dodemorph
7:1
3:1
1:1


Compound 32
dodine
10:1
4:1
2:1


Compound 32
edifenphos
3:1
1:1
1:3


Compound 32
enestroburin
2:1
1:1
1:4


Compound 32
epoxiconazole
1:1
1:3
1:7


Compound 32
etaconazole
1:1
1:3
1:7


Compound 32
ethaboxam
2:1
1:1
1:3


Compound 32
ethirimol
7:1
3:1
1:1


Compound 32
etridiazole
7:1
2:1
1:2


Compound 32
famoxadone
2:1
1:1
1:4


Compound 32
fenamidone
2:1
1:1
1:4


Compound 32
fenaminstrobin
3:1
1:1
1:3


Compound 32
fenarimol
1:2
1:7
1:24


Compound 32
fenbuconazole
1:1
1:3
1:10


Compound 32
fenfuram
4:1
1:1
1:2


Compound 32
fenhexamid
10:1
4:1
2:1


Compound 32
fenoxanil
15:1
4:1
1:1


Compound 32
fenpiclonil
15:1
5:1
2:1


Compound 32
fenpropidin
7:1
2:1
1:1


Compound 32
fenpropimorph
7:1
2:1
1:1


Compound 32
fenpyrazamine
3:1
1:1
1:3


Compound 32
fentin salt such as fentin
3:1
1:1
1:3



acetate, fentin chloride






or fentin hydroxide





Compound 32
ferbam
30:1
10:1
4:1


Compound 32
ferimzone
7:1
2:1
1:2


Compound 32
fluazinam
3:1
1:1
1:2


Compound 32
fludioxonil
2:1
1:1
1:4


Compound 32
flumetover
3:1
1:1
1:2


Compound 32
flumorph
3:1
1:1
1:3


Compound 32
fluopicolide
1:1
1:2
1:6


Compound 32
fluopyram
3:1
1:1
1:3


Compound 32
fluoroimide
37:1
14:1
5:1


Compound 32
fluoxastrobin
1:1
1:2
1:6


Compound 32
fluquinconazole
1:1
1:2
1:4


Compound 32
flusilazole
3:1
1:1
1:3


Compound 32
flusulfamide
15:1
5:1
2:1


Compound 32
flutianil
1:1
1:2
1:6


Compound 32
flutolanil
4:1
1:1
1:2


Compound 32
flutriafol
1:1
1:2
1:4


Compound 32
fluxapyroxad
2:1
1:1
1:3


Compound 32
folpet
15:1
5:1
2:1


Compound 32
fosetyl-aluminum
30:1
12:1
5:1


Compound 32
fuberidazole
11:1
4:1
2:1


Compound 32
furalaxyl
1:1
1:2
1:6


Compound 32
furametpyr
15:1
5:1
2:1


Compound 32
guazatine
15:1
5:1
2:1


Compound 32
hexaconazole
1:1
1:2
1:5


Compound 32
hymexazol
75:1
25:1
9:1


Compound 32
imazalil
1:1
1:2
1:5


Compound 32
imibenconazole
1:1
1:2
1:5


Compound 32
iminoctadine
15:1
4:1
1:1


Compound 32
iodocarb
15:1
5:1
2:1


Compound 32
ipconazole
1:1
1:2
1:5


Compound 32
iprobenfos
15:1
5:1
2:1


Compound 32
iprodione
15:1
5:1
2:1


Compound 32
iprovalicarb
2:1
1:1
1:3


Compound 32
isoprothiolane
45:
15:1
5:1


Compound 32
isopyrazam
2:1
1:1
1:3


Compound 32
isotianil
2:1
1:1
1:3


Compound 32
kasugamycin
1:2
1:7
1:24


Compound 32
kresoxim-methyl
2:1
1:1
1:4


Compound 32
mancozeb
22:1
7:1
3:1


Compound 32
mandipropamid
2:1
1:1
1:4


Compound 32
maneb
22:1
7:1
3:1


Compound 32
mepanipyrim
6:1
2:1
1:1


Compound 32
mepronil
1:1
1:2
1:6


Compound 32
meptyldinocap
2:1
1:1
1:3


Compound 32
metalaxyl
1:1
1:2
1:6


Compound 32
metalaxyl-M
1:1
1:4
1:12


Compound 32
metconazole
1:1
1:2
1:6


Compound 32
methasulfocarb
15:1
5:1
2:1


Compound 32
metiram
15:1
5:1
2:1


Compound 32
metominostrobin
3:1
1:1
1:3


Compound 32
metrafenone
2:1
1:1
1:4


Compound 32
myclobutanil
1:1
1:3
1:8


Compound 32
naftifine
15:1
5:1
2:1


Compound 32
neo-asozin (ferric
15:1
5:1
2:1



methanearsonate)





Compound 32
nuarimol
3:1
1:1
1:3


Compound 32
octhilinone
15:1
4:1
1:1


Compound 32
ofurace
1:1
1:2
1:6


Compound 32
orysastrobin
3:1
1:1
1:3


Compound 32
oxadixyl
1:1
1:2
1:6


Compound 32
oxolinic acid
7:1
2:1
1:2


Compound 32
oxpoconazole
1:1
1:2
1:5


Compound 32
oxycarboxin
4:1
1:1
1:2


Compound 32
oxytetracycline
3:1
1:1
1:3


Compound 32
pefurazoate
15:1
5:1
2:1


Compound 32
penconazole
1:2
1:6
1:15


Compound 32
pencycuron
11:1
4:1
2:1


Compound 32
penflufen
2:1
1:1
1:3


Compound 32
penthiopyrad
2:1
1:1
1:3


Compound 32
phosphorous acid or a salt thereof
15:1
6:1
2:1


Compound 32
phthalide
15:1
6:1
2:1


Compound 32
picoxystrobin
1:1
1:2
1:5


Compound 32
piperalin
3:1
1:1
1:3


Compound 32
polyoxin
3:1
1:1
1:3


Compound 32
probenazole
3:1
1:1
1:3


Compound 32
prochloraz
7:1
2:1
1:2


Compound 32
procymidone
11:1
4:1
2:1


Compound 32
propamocarb or propamocarb-
10:1
4:1
2:1



hydrochloride





Compound 32
propiconazole
1:1
1:2
1:5


Compound 32
propineb
11:1
4:1
2:1


Compound 32
proquinazid
1:1
1:3
1:12


Compound 32
prothiocarb
3:1
1:1
1:3


Compound 32
prothioconazole
1:1
1:2
1:5


Compound 32
pyraclostrobin
2:1
1:1
1:4


Compound 32
pyrametostrobin
2:1
1:1
1:4


Compound 32
pyraoxystrobin
2:1
1:1
1:4


Compound 32
pyrazophos
15:1
4:1
1:1


Compound 32
pyribencarb
4:1
1:1
1:2


Compound 32
pyributicarb
15:1
4:1
1:1


Compound 32
pyrifenox
3:1
1:1
1:3


Compound 32
pyrimethanil
3:1
1:1
1:2


Compound 32
pyriofenone
2:1
1:1
1:4


Compound 32
pyrisoxazole
3:1
1:1
1:3


Compound 32
pyroquilon
3:1
1:1
1:3


Compound 32
pyrrolnitrin
15:1
5:1
2:1


Compound 32
quinconazole
1:1
1:2
1:4


Compound 32
quinomethionate
15:1
5:1
2:1


Compound 32
quinoxyfen
1:1
1:2
1:6


Compound 32
quintozene
15:1
5:1
2:1


Compound 32
silthiofam
2:1
1:1
1:4


Compound 32
simeconazole
1:1
1:2
1:5


Compound 32
spiroxamine
5:1
2:1
1:2


Compound 32
streptomycin
3:1
1:1
1:3


Compound 32
sulfur
75:1
25:1
9:1


Compound 32
tebuconazole
1:1
1:2
1:5


Compound 32
tebufloquin
3:1
1:1
1:3


Compound 32
tecloftalam
15:1
5:1
2:1


Compound 32
tecnazene
15:1
5:1
2:1


Compound 32
terbinafine
15:1
5:1
2:1


Compound 32
tetraconazole
1:1
1:2
1:5


Compound 32
thiabendazole
11:1
4:1
2:1


Compound 32
thifluzamide
3:1
1:1
1:3


Compound 32
thiophanate
11:1
4:1
2:1


Compound 32
thiophanate-methyl
11:1
4:1
2:1


Compound 32
thiram
37:1
14:1
5:1


Compound 32
tiadinil
2:1
1:1
1:3


Compound 32
tolclofos-methyl
37:1
14:1
5:1


Compound 32
tolnifanide
3:1
1:1
1:3


Compound 32
tolylfluanid
15:1
5:1
2:1


Compound 32
triadimefon
1:1
1:2
1:5


Compound 32
triadimenol
1:1
1:2
1:5


Compound 32
triarimol
1:2
1:7
1:24


Compound 32
triazoxide
15:1
5:1
2:1


Compound 32
tricyclazole
3:1
1:1
1:3


Compound 32
tridemorph
7:1
2:1
1:1


Compound 32
trifloxystrobin
2:1
1:1
1:4


Compound 32
triflumizole
3:1
1:1
1:3


Compound 32
triforine
3:1
1:1
1:3


Compound 32
trimorphamide
7:1
2:1
1:2


Compound 32
triticonazole
1:1
1:2
1:5


Compound 32
uniconazole
1:1
1:2
1:5


Compound 32
validamycin
3:1
1:1
1:3


Compound 32
valifenalate
2:1
1:1
1:4


Compound 32
vinclozolin
15:1
6:1
2:1


Compound 32
zineb
37:1
14:1
5:1


Compound 32
ziram
37:1
14:1
5:1


Compound 32
zoxamide
2:1
1:1
1:4


Compound 32
5-chloro-6-(2,4,6-trifluorophenyl)-
1:1
1:2
1:6



7-(4-methylpiperidin-






1-yl)[1,2,4]triazolo[1,5-






a]pyrimidine (DPX-BAS600F)





Compound 32
N-[2-[4-[[3-(4-chlorophenyl)-
2:1
1:1
1:4



2-propyn-1-yl]oxy]-3-methoxy-






phenyl]ethyl]-3-methyl-2-






[(methylsulfonyl)amino]-






butanamide





Compound 32
N-[2-[4-[[3-(4-chlorophenyl)-2-
2:1
1:1
1:4



propyn-1-yl]oxy]-3-methoxy-






phenyl]ethyl]-3-methyl-2-






[(ethylsulfonyl)amino]butanamide





Compound 32
4-fluorophenyl N-[1-[[1-(4-
2:1
1:1
1:4



cyanophenyl)ethyl]sulfonyl]-






methyl]propyl]carbamate





Compound 32
N-[[(cyclopropylmethoxy)amino]
1:2
1:7
1:24



[6-(difluoromethoxy)-






2,3-difluorophenyl]






methylene]benzeneacetamide





Compound 32
a-[methoxyimino]-N-methyl-
3:1
1:1
1:3



2-[1-[3-(trifluoromethyl)-






phenyl]ethoxylimino]






methyl]benzeneacetamide





Compound 32
N′-[4-[4-chloro-3-
3:1
1:1
1:3



(trifluoromethyl)phenoxy]-






2,5-dimethyl-






phenyl]-N-ethyl-N-






methylmethanimidamide





(*) Ratios of Component (a) relative to Component (b) by weight.






Tables A2 through A21 are each constructed the same as Table A1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Thus, for example, in Table A2 the entries below the “Component (a)” column heading all recite “Compound 64”, and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 64 with acibenzolar-S-methyl. Tables A3 through A21 are constructed similarly.


















Table
Component (a)
Table
Component (a)



Number
Column Entry
Number
Column Entry









A2
Compound 64
A12
Compound 221



A3
Compound 71
A13
Compound 229



A4
Compound 126
A14
Compound 231



A5
Compound 127
A15
Compound 262



A6
Compound 132
A16
Compound 263



A7
Compound 162
A17
Compound 265



A8
Compound 163
A18
Compound 297



A9
Compound 171
A19
Compound 330



A10
Compound 186
A20
Compound 331



A11
Compound 218
A21
Compound 364










Table B1 lists specific combinations of a Component (b) compound with Component (a) illustrative of the mixtures, compositions and methods of the present invention. The first column of Table B1 lists the specific Component (b) compound (e.g., “acibenzolar-S-methyl” in the first line). The second, third and fourth columns of Table B1 lists ranges of weight ratios for rates at which the Component (a) compound is typically applied to a field-grown crop relative to Component (b). Thus, for example, the first line of Table B1 discloses the combination of a compound of Component (a) with acibenzolar-S-methyl is typically applied in a weight ratio of the Component (a) to Component (b) of between 2:1 to 1:180. The remaining lines of Table B1 are to be construed similarly. Of particular note is a composition comprising a mixture of any one of the compounds listed in Embodiment 238 as Component (a) with a compound listed in the Component (b) column of Table B1 according to the weight ratios disclosed in Table B1. Table B1 thus supplements the specific ratios disclosed in Tables A1 through A21 with ranges of ratios for these combinations.












TABLE B1








Most



Typical
Typical
Typical



Weight
Weight
Weight


Component (b)
Ratio
Ratio
Ratio







acibenzolar-S-methyl
2:1 to 1:180
1:1 to 1:60
1:1 to 1:18


aldimorph
30:1 to 1:3
10:1 to 1:1
7:1 to 1:1


ametoctradin
9:1 to 1:18
3:1 to 1:6
3:1 to 1:3


amisulbrom
6:1 to 1:18
2:1 to 1:6
1:1 to 1:6


anilazine
90:1 to 2:1
30:1 to 4:1
22:1 to 4:1


azaconazole
7:1 to 1:18
2:1 to 1:6
2:1 to 1:4


azoxystrobin
9:1 to 1:12
3:1 to 1:4
3:1 to 1:3


benalaxyl
4:1 to 1:18
1:1 to 1:6
1:1 to 1:6


benalaxyl-M
4:1 to 1:36
1:1 to 1:12
1:1 to 1:8


benodanil
18:1 to 1:6
6:1 to 1:2
4:1 to 1:2


benomyl
45:1 to 1:4
15:1 to 1:1
11:1 to 1:1


benthiavalicarb or
2:1 to 1:36
1:1 to 1:12
1:1 to 1:12


benthiavalicarb-isopropyl





bethoxazin
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


binapacryl
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


biphenyl
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


bitertanol
15:1 to 1:5
5:1 to 1:2
3:1 to 1:2


bixafen
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


blasticidin-S
3:1 to 1:90
1:1 to 1:30
1:4 to 1:30


boscalid
18:1 to 1:6
6:1 to 1:2
4:1 to 1:2


bromuconazole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


bupirimate
3:1 to 1:90
1:1 to 1:30
1:3 to 1:30


captafol
90:1 to 1:4
30:1 to 1:2
15:1 to 2:1


captan
90:1 to 1:4
30:1 to 1:2
15:1 to 2:1


carbendazim
45:1 to 1:4
15:1 to 1:2
11:1 to 2:1


carboxin
18:1 to 1:6
6:1 to 1:2
4:1 to 1:2


carpropamid
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


chloroneb
300:1 to 2:1
100:1 to 4:1
100:1 to 14:1


chlorothalonil
90:1 to 1:4
30:1 to 1:2
15:1 to 2:1


chlozolinate
45:1 to 1:2
15:1 to 2:1
11:1 to 2:1


clotrimazole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


copper salts such as
450:1 to 1:1
150:1 to 4:1
45:1 to 5:1


Bordeaux mixture





(tribasic copper





sulfate), copper





oxychloride, copper





sulfate and copper





hydroxide





cyazofamid
4:1 to 1:18
1:1 to 1:6
1:1 to 1:6


cyflufenamid
1:1 to 1:90
1:2 to 1:30
1:2 to 1:24


cymoxanil
6:1 to 1:18
2:1 to 1:6
1:1 to 1:5


cyproconazole
4:1 to 1:18
1:1 to 1:6
1:1 to 1:6


cyprodinil
22:1 to 1:9
7:1 to 1:3
4:1 to 1:2


dichlofluanid
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


diclocymet
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


diclomezine
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


dicloran
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


diethofencarb
22:1 to 1:9
7:1 to 1:3
7:1 to 1:2


difenoconazole
4:1 to 1:36
1:1 to 1:12
1:1 to 1:12


diflumetorim
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


dimethirimol
3:1 to 1:90
1:1 to 1:30
1:3 to 1:30


dimethomorph
9:1 to 1:6
3:1 to 1:2
3:1 to 1:2


dimoxystrobin
9:1 to 1:18
3:1 to 1:6
2:1 to 1:4


diniconazole
3:1 to 1:36
1:1 to 1:12
1:1 to 1:8


diniconazole M
3:1 to 1:90
1:1 to 1:30
1:1 to 1:12


dinocap
7:1 to 1:9
2:1 to 1:3
2:1 to 1:3


dithianon
15:1 to 1:4
5:1 to 1:2
5:1 to 1:2


dodemorph
30:1 to 1:3
10:1 to 1:1
7:1 to 1:1


dodine
30:1 to 1:2
10:1 to 2:1
10:1 to 2:1


edifenphos
30:1 to 1:9
10:1 to 1:3
3:1 to 1:3


enestroburin
9:1 to 1:18
3:1 to 1:6
2:1 to 1:4


epoxiconazole
3:1 to 1:36
1:1 to 1:12
1:1 to 1:7


etaconazole
3:1 to 1:36
1:1 to 1:12
1:1 to 1:7


ethaboxam
7:1 to 1:9
2:1 to 1:3
2:1 to 1:3


ethirimol
30:1 to 1:3
10:1 to 1:1
7:1 to 1:1


etridiazole
30:1 to 1:9
10:1 to 1:3
7:1 to 1:2


famoxadone
9:1 to 1:18
3:1 to 1:6
2:1 to 1:4


fenamidone
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


fenaminstrobin
9:1 to 1:18
3:1 to 1:6
3:1 to 1:3


fenarimol
3:1 to 1:90
1:1 to 1:30
1:2 to 1:24


fenbuconazole
3:1 to 1:30
1:1 to 1:10
1:1 to 1:10


fenfuram
18:1 to 1:6
6:1 to 1:2
4:1 to 1:2


fenhexamid
30:1 to 1:2
10:1 to 2:1
10:1 to 2:1


fenoxanil
150:1 to 1:36
50:1 to 1:12
15:1 to 1:1


fenpiclonil
75:1 to 1:9
25:1 to 1:3
15:1 to 2:1


fenpropidin
30:1 to 1:3
10:1 to 1:1
7:1 to 1:1


fenpropimorph
30:1 to 1:3
10:1 to 1:1
7:1 to 1:1


fenpyrazamine
100:1 to 1:100
10:1 to 1:10
3:1 to 1:3


fentin salt such as the
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


acetate, chloride or





hydroxide





ferbam
300:1 to 1:2
100:1 to 2:1
30:1 to 4:1


ferimzone
30:1 to 1:5
10:1 to 1:2
7:1 to 1:2


fluazinam
22:1 to 1:5
7:1 to 1:2
3:1 to 1:2


fludioxonil
7:1 to 1:12
2:1 to 1:4
2:1 to 1:4


flumetover
9:1 to 1:6
3:1 to 1:2
3:1 to 1:2


flumorph
9:1 to 1:18
3:1 to 1:6
3:1 to 1:3


fluopicolide
3:1 to 1:18
1:1 to 1:6
1:1 to 1:6


fluopyram
15:1 to 1:90
5:1 to 1:30
3:1 to 1:3


fluoromide
150:1 to 2:1
50:1 to 4:1
37:1 to 5:1


fluoxastrobin
4:1 to 1:18
1:1 to 1:6
1:1 to 1:6


fluquinconazole
4:1 to 1:12
1:1 to 1:4
1:1 to 1:4


flusilazole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


flusulfamide
90:1 to 1:2
30:1 to 2:1
15:1 to 2:1


flutianil
7:1 to 1:36
2:1 to 1:12
1:1 to 1:6


flutolanil
18:1 to 1:6
6:1 to 1:2
4:1 to 1:2


flutriafol
4:1 to 1:12
1:1 to 1:4
1:1 to 1:4


fluxapyroxad
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


folpet
90:1 to 1:4
30:1 to 1:2
15:1 to 2:1


fosetyl-aluminum
225:1 to 2:1
75:1 to 5:1
30:1 to 5:1


fuberidazole
45:1 to 1:4
15:1 to 1:2
11:1 to 2:1


furalaxyl
15:1 to 1:45
5:1 to 1:15
1:1 to 1:6


furametpyr
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


guazatine or iminoctadine
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


hexaconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


hymexazol
225:1 to 2:1
75:1 to 4:1
75:1 to 9:1


imazalil
7:1 to 1:18
2:1 to 1:6
1:1 to 1:5


imibenconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


iodocarb
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


ipconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


iprobenfos
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


iprodione
120:1 to 1:2
40:1 to 2:1
15:1 to 2:1


iprovalicarb
9:1 to 1:9
3:1 to 1:3
2:1 to 1:3


isoprothiolane
150:1 to 2:1
50:1 to 4:1
45:1 to 5:1


isopyrazam
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


isotianil
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


kasugamycin
7:1 to 1:90
2:1 to 1:30
1:2 to 1:24


kresoxim-methyl
7:1 to 1:18
2:1 to 1:6
2:1 to 1:4


mancozeb
180:1 to 1:3
60:1 to 2:1
22:1 to 3:1


mandipropamid
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


maneb
180:1 to 1:3
60:1 to 2:1
22:1 to 3:1


mepanipyrim
18:1 to 1:3
6:1 to 1:1
6:1 to 1:1


mepronil
7:1 to 1:36
2:1 to 1:12
1:1 to 1:6


meptyldinocap
7:1 to 1:9
2:1 to 1:3
2:1 to 1:3


metalaxyl
15:1 to 1:45
5:1 to 1:15
1:1 to 1:6


metalaxyl-M
7:1 to 1:90
2:1 to 1:30
1:1 to 1:12


metconazole
3:1 to 1:18
1:1 to 1:6
1:1 to 1:6


methasulfocarb
150:1 to 1:36
50:1 to 1:12
15:1 to 1:1


metiram
150:1 to 1:36
50:1 to 1:12
15:1 to 1:1


metominostrobin
9:1 to 1:12
3:1 to 1:4
3:1 to 1:3


metrafenone
6:1 to 1:12
2:1 to 1:4
2:1 to 1:4


myclobutanil
5:1 to 1:26
1:1 to 1:9
1:1 to 1:8


naftifine
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


neo-asozin (ferric
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


methanearsonate)





nuarimol
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


octhilinone
150:1 to 1:36
50:1 to 1:12
15:1 to 1:1


ofurace
15:1 to 1:45
5:1 to 1:15
1:1 to 1:6


orysastrobin
9:1 to 1:12
3:1 to 1:4
3:1 to 1:3


oxadixyl
15:1 to 1:45
5:1 to 1:15
1:1 to 1:6


oxolinic acid
30:1 to 1:9
10:1 to 1:3
7:1 to 1:2


oxpoconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


oxycarboxin
18:1 to 1:6
6:1 to 1:2
4:1 to 1:2


oxytetracycline
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


pefurazoate
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


penconazole
1:1 to 1:45
1:2 to 1:15
1:2 to 1:15


pencycuron
150:1 to 1:2
50:1 to 2:1
11:1 to 2:1


penflufen
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


penthiopyrad
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


phosphorous acid
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


and salts thereof





phthalide
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


picoxystrobin
7:1 to 1:18
2:1 to 1:6
1:1 to 1:5


piperalin
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


polyoxin
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


probenazole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


prochloraz
22:1 to 1:4
7:1 to 1:1
7:1 to 1:2


procymidone
45:1 to 1:3
15:1 to 1:1
11:1 to 2:1


propamocarb or
30:1 to 1:2
10:1 to 2:1
10:1 to 2:1


propamocarb-





hydrochloride





propiconazole
4:1 to 1:18
1:1 to 1:6
1:1 to 1:5


propineb
45:1 to 1:2
15:1 to 2:1
11:1 to 2:1


proquinazid
3:1 to 1:36
1:1 to 1:12
1:1 to 1:12


prothiocarb
9:1 to 1:18
3:1 to 1:6
3:1 to 1:3


prothioconazole
6:1 to 1:18
2:1 to 1:6
1:1 to 1:5


pyraclostrobin
9:1 to 1:18
3:1 to 1:6
2:1 to 1:4


pyrametostrobin
9:1 to 1:18
3:1 to 1:6
2:1 to 1:4


pyraoxystrobin
9:1 to 1:18
3:1 to 1:6
2:1 to 1:4


pyrazophos
150:1 to 1:36
50:1 to 1:12
15:1 to 1:1


pyribencarb
15:1 to 1:6
5:1 to 1:2
4:1 to 1:2


pyrifenox
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


pyrimethanil
30:1 to 1:6
10:1 to 1:2
3:1 to 1:2


pyriofenone
6:1 to 1:12
2:1 to 1:4
2:1 to 1:4


pyrisoxazole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


pyroquilon
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


pyrrolnitrin
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


quinconazole
4:1 to 1:12
1:1 to 1:4
1:1 to 1:4


quinmethionate
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


quinoxyfen
4:1 to 1:18
1:1 to 1:6
1:1 to 1:6


quintozene
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


silthiofam
7:1 to 1:18
2:1 to 1:6
2:1 to 1:4


simeconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


spiroxamine
22:1 to 1:4
7:1 to 1:2
5:1 to 1:2


streptomycin
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


sulfur
300:1 to 3:1
100:1 to 9:1
75:1 to 9:1


tebuconazole
7:1 to 1:18
2:1 to 1:6
1:1 to 1:5


tebufloquin
100:1 to 1:100
10:1 to 1:10
3:1 to 1:3


tecloftalam
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


tecnazene
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


terbinafine
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


tetraconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


thiabendazole
45:1 to 1:4
15:1 to 1:2
11:1 to 2:1


thifluzamide
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


thiophanate
45:1 to 1:3
15:1 to 2:1
11:1 to 2:1


thiophanate-methyl
45:1 to 1:3
15:1 to 2:1
11:1 to 2:1


thiram
150:1 to 1:2
50:1 to 2:1
37:1 to 5:1


tiadinil
12:1 to 1:9
4:1 to 1:3
2:1 to 1:3


tolclofos-methyl
150:1 to 1:2
50:1 to 2:1
37:1 to 5:1


tolnifanide
15:1 to 1:18
5:1 to 1:6
3:1 to 1:3


tolylfluanid
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


triadimefon
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


triadimenol
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


triarimol
3:1 to 1:90
1:1 to 1:30
1:2 to 1:24


triazoxide
150:1 to 1:36
50:1 to 1:12
15:1 to 2:1


tricyclazole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


tridemorph
30:1 to 1:3
10:1 to 1:1
7:1 to 1:1


trifloxystrobin
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


triflumizole
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


triforine
15:1 to 1:9
5:1 to 1:3
3:1 to 1:3


trimorphamide
45:1 to 1:9
15:1 to 1:3
7:1 to 1:2


triticonazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


uniconazole
15:1 to 1:36
5:1 to 1:12
1:1 to 1:5


validamycin
150:1 to 1:36
50:1 to 1:12
3:1 to 1:3


valifenalate
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


vinclozolin
120:1 to 1:2
40:1 to 2:1
15:1 to 2:1


zineb
150:1 to 1:2
50:1 to 2:1
37:1 to 5:1


ziram
150:1 to 1:2
50:1 to 2:1
37:1 to 5:1


zoxamide
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


5-chloro-6-(2,4,6-
15:1 to 1:36
5:1 to 1:12
1:1 to 1:6


trifluorophenyl)-





7-(4-methylpiperidin-





1-yl)[1,2,4]triazolo-





[1,5-a]pyrimidine





(DPX-BAS600F)





N-[2-[4-[[3-(4-
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


chlorophenyl)-2-propyn-





1-yl]oxy]-3-





methoxyphenyl]ethyl]-





3-methyl-2-





[(methylsulfonyl)amino]-





butanamide





N-[2-[4-[[3-(4-
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


chlorophenyl)-2-propyn-1-





yl]oxy]-3-





methoxyphenyl]ethyl]-





3-methyl-





2-[(ethylsulfonyl)ami-





no]butanamide





4-fluorophenyl N-[1-
6:1 to 1:18
2:1 to 1:6
2:1 to 1:4


[[[1-(4-cyanophenyl)-





ethyl]sulfonyl]methyl]pro-





pyl]carbamate





N-[[(cyclopropyl-
1:1 to 1:90
1:2 to 1:30
1:2 to 1:24


methoxy)amino][6-





(difluoromethoxy)-





2,3-difluorophenyl]-





methylene]benzeneacetamide





α-[methoxyimino]-
9:1 to 1:18
3:1 to 1:6
3:1 to 1:3


N-methyl-2-[[1-[3-





(trifluoromethyl)phe-





nyl]ethoxy]imino]-





methyl]benzeneacetamide





N′-[4-[4-chloro-3-
15:1 to 1:18
5:1 to 1:6
3:1 to 1:3


(trifluoromethyl)-





phenoxy]-2,5-





dimethylphenyl]-N-ethyl-





N-methylmethanimidamide









As already noted, the present invention includes embodiments wherein in the composition comprising components (a) and (b), component (b) comprises at least one fungicidal compound from each of two groups selected from (b1) through (b54). Tables C1 through C21 list specific mixtures (compound numbers refer to compounds in Index Tables A through L) to illustrate embodiments wherein component (b) includes at least one fungicidal compound from each of two groups selected from (b1) through (b54). In Table C1, each line below the column headings “Component (a)” and “Component (b)” specifically discloses a mixture of Component (a), which is Compound 32, with at least two Component (b) fungicidal compounds. The entries under the heading “Illustrative Ratios” disclose three specific weight ratios of Component (a) to each Component (b) fungicidal compound in sequence for the disclosed mixture. For example, the first line discloses a mixture of Compound 32 with cyproconazole and azoxystrobin and lists weight ratios of Compound 32 to cyproconazole to azoxystrobin of 1:1:1, 2:1:1 or 3:1:1.












TABLE C1





Component (a)
Component (b)

Illustrative Ratios(*)




















Compound 32
cyproconazole
azoxystrobin
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
kresoxim-methyl
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
picoxystrobin
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
pyraclostrobin
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
pyrametrostrobin
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
pyraoxystrobin
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
trifloxystrobin
1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
bixafen
1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
boscalid
1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
cyflufenamid
1:2:1
2:2:1
3:2:1













Compound 32
cyproconazole
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
cyproconazole
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
cyproconazole
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
cyproconazole
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
difenconazole
azoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
kresoxim-methyl

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
picoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
pyraclostrobin

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
pyrametostrobin

1:1:1
2:1:1
3:1:1


Compound 32
difenoconazole
pyraoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
trifloxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
bixafen

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
boscalid

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
cyflufenamid

1:2:1
2:2:1
3:2:1


Compound 32
difenconazole
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
difenconazole
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
difenconazole
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
difenconazole
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
epoxiconazole
azoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
kresoxim-methyl

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
picoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
pyraclostrobin

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
pyrametostrobin

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
pyraoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
trifloxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
bixafen

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
boscalid

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
cyflufenamid

1:2:1
2:2:1
3:2:1


Compound 32
epoxiconazole
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
epoxiconazole
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
epoxiconazole
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
epoxiconazole
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
metconazole
azoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
kresoxim-methyl

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
picoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
pyraclostrobin

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
pyrametostrobin

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
pyraoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
trifloxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
bixafen

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
boscalid

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
cyflufenamid

1:2:1
2:2:1
3:2:1


Compound 32
metconazole
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
metconazole
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
metconazole
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
metconazole
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
myclobutanil
azoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
kresoxim-methyl

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
picoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
pyraclostrobin

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
pyrametostrobin

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
pyraoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
trifloxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
bixafen

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
boscalid

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
cyflufenamid

1:2:1
2:2:1
3:2:1


Compound 32
myclobutanil
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
myclobutanil
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
myclobutanil
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
myclobutanil
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
prothioconazole
azoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
kresoxim-methyl

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
picoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
pyraclostrobin

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
pyrametostrobin

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
pyraoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
trifloxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
bixafen

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
boscalid

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
cyflufenamid

1:2:1
2:2:1
3:2:1


Compound 32
prothioconazole
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
prothioconazole
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
prothioconazole
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
prothioconazole
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
tebuconazole
azoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
kresoxim-methyl

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
picoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
pyraclostrobin

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
pyrametostrobin

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
pyraoxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
trifloxystrobin

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
bixafen

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
boscalid

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
cyflufenamid

1:2:1
2:2:1
3:2:1


Compound 32
tebuconazole
fluopyram

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
isopyrazam

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
metrafenone

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
penthiopyrad

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
proquinazid

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
pyriofenone

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
quinoxyfen

1:1:1
2:1:1
3:1:1


Compound 32
tebuconazole
sedaxane

1:1:2
2:1:2
3:1:2


Compound 32
tebuconazole
picoxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1


Compound 32
tebuconazole
trifloxystrobin
proquinazid
1:1:1:1
2:1:1:1
3:1:1:1





(*)Ratios of Component (a) relative to Component (b) in sequence, by weight.






Tables C2 through C21 are each constructed the same as Table C1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Thus, for example, in Table C2 the entries below the “Component (a)” column heading all recite “Compound 64”, and the first line in below the column headings in Table C2 specifically discloses a mixture of Compound 64 with cyproconazole and azoxystrobin, and the illustrative weight ratios of 1:1:1, 2:1:1 and 3:1:1 of Compound 64:cyproconazole:azoxystrobin. Tables C3 through C21 are constructed similarly.















Table
Component (a)
Table
Component (a)


Number
Column Entry
Number
Column Entry







C2
Compound 64
C12
Compound 221


C3
Compound 71
C13
Compound 229


C4
Compound 126
C14
Compound 231


C5
Compound 127
C15
Compound 262


C6
Compound 132
C16
Compound 263


C7
Compound 162
C17
Compound 265


C8
Compound 163
C18
Compound 297


C9
Compound 171
C19
Compound 330


C10
Compound 186
C20
Compound 331


C11
Compound 218
C21
Compound 364









Of note is a composition of the present invention comprising a compound of Formula 1 (or an N-oxide or salt thereof) with at least one other fungicidal compound that has a different site of action from the compound of Formula 1. In certain instances, a combination with at least one other fungicidal compound having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can advantageously comprise at least one fungicidal active compound selected from the group consisting of (b1) through (b54) as described above, having a similar spectrum of control but a different site of action.


Compositions of component (a), or component (a) with component (b), can be further mixed with one or more other biologically active compounds or agents including insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Thus the present invention also pertains to a composition comprising a fungicidally effective amount of component (a), or a mixture of component (a) with component (b), and a biologically effective amount of at least one additional biologically active compound or agent and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can also be separately formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For compositions of the present invention, one or more other biologically active compounds or agents can be formulated together with one or both of components (a) and (b) to form a premix, or one or more other biologically active compounds or agents can be formulated separately from components (a) and (b) and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.


Examples of such biologically active compounds or agents with which compositions of component (a), or component (a) with component (b), can be formulated are: insecticides such as abamectin, acephate, acequinocyl, acetamiprid, acrinathrin, acynonapyr, afidopyropen ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate), amidoflumet, amitraz, avermectin, azadirachtin, azinphos-methyl, benfuracarb, bensultap, benzpyrimoxan, bifenthrin, kappa-bifenthrin, bifenazate, bistrifluron, borate, broflanilide, buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chloroprallethrin, chlorpyrifos, chlorpyrifos-e, chlorpyrifos-methyl, chromafenozide, clofentezin, chloroprallethrin, clothianidin, cyantraniliprole (3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), cyclaniliprole (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide), cycloprothrin, cycloxaprid ((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-Epoxy-1H-imidazo[1,2-a]azepine), cyenopyrafen, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dicloromesotiaz, dieldrin, diflubenzuron, dimefluthrin, dimehypo, dimethoate, dimpropyridaz, dinotefuran, diofenolan, emamectin, emamectin benzoate, endosulfan, esfenvalerate, ethiprole, etofenprox, epsilon-metofluthrin, etoxazole, fenbutatin oxide, fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flometoquin (2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinyl methyl carbonate), flonicamid, fluazaindolizine, flubendiamide, flucythrinate, flufenerim, flufenoxuron, flufenoxystrobin (methyl (αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate), fluensulfone (5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole), fluhexafon, fluopyram, flupiprole (1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile), flupyradifurone (4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone), flupyrimin, fluvalinate, tau-fluvalinate, fluxametamide, fonophos, formetanate, fosthiazate, gamma-cyhalothrin, halofenozide, heptafluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate), hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidal soaps, isofenphos, isocycloseram, kappa-tefluthrin, lambda-cyhalothrin, lufenuron, malathion, meperfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl (1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate), metaflumizone, metaldehyde, methamidophos, methidathion, methiocarb, methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide, epsilon-metofluthrin, epsilon-momfluorothrin, monocrotophos, monofluorothrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate), nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl, oxazosulfyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite, protrifenbute, pyflubumide (1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide), pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin (methyl (αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate), pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad, spirodiclofen, spiromesifen, spiropidion, spirotetramat, sulprofos, sulfoxaflor (N-[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-2-sulfanylidene]cyanamide), tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, kappa-tefluthrin, terbufos, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, tetramethylfluthrin ([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl 2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen (3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin, triazamate, trichlorfon, triflumezopyrim (2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidinium inner salt), triflumuron, tyclopyrazoflor, zeta-cypermethrin, Bacillus thuringiensis delta-endotoxins, entomopathogenic bacteria, entomopathogenic viruses or entomopathogenic fungi.


One embodiment of biological agents for mixing with compounds of this disclosure include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta-endotoxins of Bacillus thuringiensis such as MVP® and MVPII® bioinsecticides prepared by the CellCap® process (CellCap®, MVP® and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).


General references for these agricultural protectants (i.e. insecticides, fungicides, nematocides, acaricides, herbicides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U. K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U. K., 2001.


For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to component (a), or a mixture of component (a) with component (b), is generally between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:100 and about 3000:1, or between about 1:30 and about 300:1 (for example ratios between about 1:1 and about 30:1). It will be evident that including these additional components may expand the spectrum of diseases controlled beyond the spectrum controlled by component (a), or a mixture of component (a) with component (b).


Component (a) compounds and/or combinations thereof with component (b) compounds and/or one or more other biologically active compounds or agents can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins). The effect of the exogenously applied present component (a) alone or in combination with component (b) may be synergistic with the expressed toxin proteins.


Of note is the combination or the composition comprising component (a), or components (a) and (b), as described in the Summary of the Invention further comprising at least one invertebrate pest control compound or agent (e.g., insecticide, acaricide). Of particular note is a composition comprising component (a) and at least one (i.e. one or more) invertebrate pest control compound or agent, which then can be subsequently combined with component (b) to provide a composition comprising components (a) and (b) and the one or more invertebrate pest control compounds or agents. Alternatively without first mixing with component (b), a biologically effective amount of the composition comprising component (a) with at least one invertebrate pest control agent can be applied to a plant or plant seed (directly or through the environment of the plant or plant seed) to protect the plant or plant seed from diseases caused by fungal pathogens and injury caused by invertebrate pests.


For embodiments where one or more of invertebrate pest control compounds are used, the weight ratio of these compounds (in total) to the component (a) compounds is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity.


Of note is a composition of the present invention which comprises in addition to a component (a) compound, alone or in combination with component (b), at least one invertebrate pest control compound or agent selected from the group consisting abamectin, acetamiprid, acrinathrin, acynonapyr, afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin, buprofezin, broflanilide, cadusafos, carbaryl, cartap, chlorantraniliprole, chloroprallethrin, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, epsilon-metofluthrin, esfenvalerate, ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flometoquin, fluxametamide, flonicamid, flubendiamide, fluensulfone, flufenoxuron, flufenoxystrobin, flufensulfone, flupiprole, flupyrimin, flupyradifurone, fluvalinate, formetanate, fosthiazate, gamma-cyhalothrin, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isocycloseram, kappa-tefluthrin, lambda-cyhalothrin, lufenuron, meperfluthrin, metaflumizone, methiodicarb, methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin, nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim, triflumuron, tyclopyrazoflor, zeta-cypermethrin, Bacillus thuringiensis delta-endotoxins, all strains of Bacillus thuringiensis and all strains of nucleo polyhedrosis viruses.


In certain instances, combinations of a a component (a) compound of this invention, alone or in mixture with component (b), with other biologically active (particularly fungicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. When an enhanced effect of fungicidal active ingredients occurs at application rates giving agronomically satisfactory levels of fungal control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.


Table D1 lists specific combinations of invertebrate pest control agents with Compound 32 (compound numbers refer to compounds in Index Tables A through L) as a component (a) compound illustrative of mixtures and compositions comprising these active ingredients and methods using them according to the present invention. The second column of Table D1 lists the specific invertebrate pest control agents (e.g., “Abamectin” in the first line). The third column of Table D1 lists the mode of action (if known) or chemical class of the invertebrate pest control agents. The fourth column of Table D1 lists embodiment(s) of ranges of weight ratios for rates at which the invertebrate pest control agent is typically applied relative to Compound 32 alone or in combination with component (b) (e.g., “50:1 to 1:50” of abamectin relative to a Compound 32 by weight). Thus, for example, the first line of Table D1 specifically discloses the combination of Compound 32 with abamectin is typically applied in a weight ratio between 50:1 to 1:50. The remaining lines of Table D1 are to be construed similarly. Thus, for example, the first line of Table D1 specifically discloses the combination of Compound 32 with abamectin is typically applied in a weight ratio between 50:1 to 1:50. The remaining lines of Table D1 are to be construed similarly.












TABLE D1





Table
Invertebrate Pest Control
Mode of Action or Chemical
Typical


Number
Agent
Class
Weight Ratio







Compound 32
Abamectin
macrocyclic lactones
50:1 to 1:50


Compound 32
Acetamiprid
neonicotinoids
150:1 to 1:200


Compound 32
Amitraz
octopamine receptor ligands
200:1 to 1:100


Compound 32
Avermectin
macrocyclic lactones
50:1 to 1:50


Compound 32
Azadirachtin
ecdysone agonists
100:1 to 1:120


Compound 32
Beta-cyfluthrin
sodium channel modulators
150:1 to 1:200


Compound 32
Bifenthrin
sodium channel modulators
100:1 to 1:10


Compound 32
Buprofezin
chitin synthesis inhibitors
500:1 to 1:50


Compound 32
Cartap
nereistoxin analogs
100:1 to 1:200


Compound 32
Chlorantraniliprole
ryanodine receptor ligands
100:1 to 1:120


Compound 32
Chlorfenapyr
mitochondrial electron transport
300:1 to 1:200




inhibitors



Compound 32
Chlorpyrifos
cholinesterase inhibitors
500:1 to 1:200


Compound 32
Clothianidin
neonicotinoids
100:1 to 1:400


Compound 32
Cyantraniliprole
ryanodine receptor ligands
100:1 to 1:120


Compound 32
Cyfluthrin
sodium channel modulators
150:1 to 1:200


Compound 32
Cyhalothrin
sodium channel modulators
150:1 to 1:200


Compound 32
Cypermethrin
sodium channel modulators
150:1 to 1:200


Compound 32
Cyromazine
chitin synthesis inhibitors
400:1 to 1:50


Compound 32
Deltamethrin
sodium channel modulators
50:1 to 1:400


Compound 32
Dieldrin
cyclodiene insecticides
200:1 to 1:100


Compound 32
Dinotefuran
neonicotinoids
150:1 to 1:200


Compound 32
Diofenolan
molting inhibitor
150:1 to 1:200


Compound 32
Emamectin
macrocyclic lactones
50:1 to 1:10


Compound 32
Endosulfan
cyclodiene insecticides
200:1 to 1:100


Compound 32
Esfenvalerate
sodium channel modulators
100:1 to 1:400


Compound 32
Ethiprole
GABA-regulated chloride channel
200:1 to 1:100




blockers



Compound 32
Fenothiocarb

150:1 to 1:200


Compound 32
Fenoxycarb
juvenile hormone mimics
500:1 to 1:100


Compound 32
Fenvalerate
sodium channel modulators
150:1 to 1:200


Compound 32
Fipronil
GABA-regulated chloride channel
150:1 to 1:100




blockers



Compound 32
Flonicamid

200:1 to 1:100


Compound 32
Flubendiamide
ryanodine receptor ligands
100:1 to 1:120


Compound 32
Flufenoxuron
chitin synthesis inhibitors
200:1 to 1:100


Compound 32
Hexaflumuron
chitin synthesis inhibitors
300:1 to 1:50


Compound 32
Hydramethylnon
mitochondrial electron transport
150:1 to 1:250




inhibitors



Compound 32
Imidacloprid
neonicotinoids
1000:1 to 1:1000


Compound 32
Indoxacarb
sodium channel modulators
200:1 to 1:50


Compound 32
Lambda-cyhalothrin
sodium channel modulators
50:1 to 1:250


Compound 32
Lufenuron
chitin synthesis inhibitors
500:1 to 1:250


Compound 32
Meperfluthrin
sodium channel modulators
100:1 to 1:400


Compound 32
Metaflumizone

200:1 to 1:200


Compound 32
Methomyl
cholinesterase inhibitors
500:1 to 1:100


Compound 32
Methoprene
juvenile hormone mimics
500:1 to 1:100


Compound 32
Methoxyfenozide
ecdysone agonists
50:1 to 1:50


Compound 32
Nitenpyram
neonicotinoids
150:1 to 1:200


Compound 32
Nithiazine
neonicotinoids
150:1 to 1:200


Compound 32
Novaluron
chitin synthesis inhibitors
500:1 to 1:150


Compound 32
Oxamyl
cholinesterase inhibitors
200:1 to 1:200


Compound 32
Pymetrozine

200:1 to 1:100


Compound 32
Pyrethrin
sodium channel modulators
100:1 to 1:10


Compound 32
Pyridaben
mitochondrial electron transport
200:1 to 1:100




inhibitors



Compound 32
Pyridalyl

200:1 to 1:100


Compound 32
Pyriproxyfen
juvenile hormone mimics
500:1 to 1:100


Compound 32
Ryanodine
ryanodine receptor ligands
100:1 to 1:120


Compound 32
Spinetoram
macrocyclic lactones
150:1 to 1:100


Compound 32
Spinosad
macrocyclic lactones
500:1 to 1:10


Compound 32
Spirodiclofen
lipid biosynthesis inhibitors
200:1 to 1:200


Compound 32
Spiromesifen
lipid biosynthesis inhibitors
200:1 to 1:200


Compound 32
Sulfoxaflor

200:1 to 1:200


Compound 32
Tebufenozide
ecdysone agonists
500:1 to 1:250


Compound 32
Tetramethylfluthrin
sodium channel modulators
100:1 to 1:40


Compound 32
Thiacloprid
neonicotinoids
100:1 to 1:200


Compound 32
Thiamethoxam
neonicotinoids
1250:1 to 1:1000


Compound 32
Thiodicarb
cholinesterase inhibitors
500:1 to 1:400


Compound 32
Thiosultap-sodium

150:1 to 1:100


Compound 32
Tralomethrin
sodium channel modulators
150:1 to 1:200


Compound 32
Triazamate
cholinesterase inhibitors
250:1 to 1:100


Compound 32
Triflumuron
chitin synthesis inhibitors
200:1 to 1:100


Compound 32

Bacillus thuringiensis

biological agents
50:1 to 1:10


Compound 32

Bacillus thuringiensis delta-
biological agents
50:1 to 1:10



endotoxin




Compound 32
NPV (e.g., Gemstar)
biological agents
50:1 to 1:10









Tables D2 through D21 are each constructed the same as Table D1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Thus, for example, in Table D2 the entries below the “Component (a)” column heading all recite “Compound 64”, and the first line in below the column headings in Table D2 specifically discloses a mixture of Compound 64 with abamectin. Tables D3 through D21 are constructed similarly.















Table
Component (a)
Table
Component (a)


Number
Column Entry
Number
Column Entry







D2
Compound 64
D12
Compound 221


D3
Compound 71
D13
Compound 229


D4
Compound 126
D14
Compound 231


D5
Compound 127
D15
Compound 262


D6
Compound 132
D16
Compound 263


D7
Compound 162
D17
Compound 265


D8
Compound 163
D18
Compound 297


D9
Compound 171
D19
Compound 330


D10
Compound 186
D20
Compound 331


D11
Compound 218
D21
Compound 364









Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria and fungi that have the ability to provide protection from the harmful effects of plant pathogenic fungi or bacteria and/or soil born animals such as nematodes. Bacteria exhibiting nematicidal properties may include but are not limited to Bacillus firmus, Bacillus cereus, Bacillus subtillis and Pasteuria penetrans. A suitable Bacillus firmus strain is strain CNCM I-1582 (GB-126) which is commercially available as BioNem™. A suitable Bacillus cereus strain is strain NCMM I-1592. Both Bacillus strains are disclosed in U.S. Pat. No. 6,406,690. Other suitable bacteria exhibiting nematicidal activity are B. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteria exhibiting fungicidal properties may include but are not limited to B. pumilus strain GB34. Fungal species exhibiting nematicidal properties may include but are not limited to Myrothecium verrucaria, Paecilomyces lilacinus and Purpureocillium lilacinum.


Seed treatments can also include one or more nematicidal agents of natural origin such as the elicitor protein called harpin which is isolated from certain bacterial plant pathogens such as Erwinia amylovora. An example is the Harpin-N-Tek seed treatment technology available as N-Hibit™ Gold CST.


Seed treatments can also include one or more species of legume-root nodulating bacteria such as the microsymbiotic nitrogen-fixing bacteria Bradyrhizobium japonicum. These inocculants can optionally include one or more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod) factors produced by rhizobia bacteria during the initiation of nodule formation on the roots of legumes. For example, the Optimize® brand seed treatment technology incorporates LCO Promoter Technology™ in combination with an inocculant.


Seed treatments can also include one or more isoflavones which can increase the level of root colonization by mycorrhizal fungi. Mycorrhizal fungi improve plant growth by enhancing the root uptake of nutrients such as water, sulfates, nitrates, phosphates and metals. Examples of isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin and pratensein. Formononetin is available as an active ingredient in mycorrhizal inocculant products such as PHC Colonize® AG.


Seed treatments can also include one or more plant activators that induce systemic acquired resistance in plants following contact by a pathogen. An example of a plant activator which induces such protective mechanisms is acibenzolar-S-methyl.


In the present fungicidal compositions, the Formula 1 compounds of component (a) can work synergically with the additional fungicidal compounds of component (b) to provide such beneficial results as broadening the spectrum of plant diseases controlled, extending duration of preventative and curative protection, and suppressing proliferation of resistant fungal pathogens. In particular embodiments, compositions are provided in accordance with this invention that comprise proportions of component (a) and component (b) that are especially useful for controlling particular fungal diseases (such as Alternaria solani, Blumeria graminis f. sp. tritici, Botrytis cinerea, Puccinia recondita f. sp. tritici, Rhizoctonia solani, Septoria nodorum, Septoria tritici).


Mixtures of fungicides may also provide significantly better disease control than could be predicted based on the activity of the individual components. This synergism has been described as “the cooperative action of two components of a mixture, such that the total effect is greater or more prolonged than the sum of the effects of the two (or more) taken independently” (see P. M. L. Tames, Neth. J. Plant Pathology 1964, 70, 73-80). In methods providing plant disease control in which synergy is exhibited from a combination of active ingredients (e.g., fungicidal compounds) applied to the plant or seed, the active ingredients are applied in a synergistic weight ratio and synergistic (i.e. synergistically effective) amounts. Measures of disease control, inhibition and prevention cannot exceed 100%. Therefore expression of substantial synergism typically requires use of application rates of active ingredients wherein the active ingredients separately provide much less than 100% effect, so that their additive effect is substantially less than 100% to allow the possibility of increase in effect as result of synergism. On the other hand, application rates of active ingredients that are too low may show not show much activity in mixtures even with the benefit of synergism. One skilled in the art can easily identify and optimize through simple experimentation the weight ratios and application rates (i.e. amounts) of fungicidal compounds providing synergy.


The presence of a synergistic effect between two active ingredients was established with the aid of the Colby equation (see Colby, S. R. “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds, (1967), 15, 20-22):







p
=

A
+
B
-

[


A
×
B


1
⁢
0
⁢
0


]



.




Using the method of Colby, the presence of a synergistic interaction between two active ingredients is established by first calculating the predicted activity, p, of the mixture based on activities of the two components applied alone. If p is lower than the experimentally established effect, synergism has occurred. In the equation above, A is the fungicidal activity in percentage control of one component applied alone at rate x. The B term is the fungicidal activity in percentage control of the second component applied at rate y. The equation estimates p, the expected fungicidal activity of the mixture of A at rate x with B at rate y if their effects are strictly additive and no interaction has occurred.


The following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A through L below for compound descriptions. The following abbreviations are used in the Index Tables: Me means methyl, Et means ethyl, n-Pr means n-propyl, i-Pr means iso-propyl, c-Pr means cyclopropyl, n-Bu means n-butyl, i-Bu means iso-butyl, c-Bu means cyclobutyl, c-hexyl means cyclohexyl, Ph means phenyl, MeO means methoxy and EtO means ethoxy. The abbreviation “Cmpd. No.” stands for “Compound Number”, and the abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared. The abbreviation “m.p.” stands for melting point. The numerical value reported in the column “MS” is the molecular weight of the highest isotopic abundance positively charged parent ion (M+1) formed by addition of H+ (molecular weight of 1) to the molecule having the highest isotopic abundance, or the highest isotopic abundance negatively charged ion (M−1) formed by loss of H+ (molecular weight of 1). The presence of molecular ions containing one or more higher atomic weight isotopes of lower abundance (e.g., 37Cl, 81Br) is not reported. The reported MS peaks were observed by mass spectrometry using electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI).









INDEX TABLE A









embedded image

















Cmpd. No.
R13
L
A
NMR
MS





1 (Ex.1)
EtOC(═O)
CH2
OCH2
*



5
EtOC(═O)
CH2
OCH(Me)
*



35
EtOC(═O)
CH(Me)
OCH2
*



36
c-PrCH2NHC(═O)
CH2
OCH2
*
400 (M + 1)


37
MeOC(═O)
CH2
OCH2
*
361 (M + 1)


38
CH2═CHCF2OC(═O)
CH2
OCH2

423 (M + 1)


39
i-PrOC(═O)
CH2
OCH2
*
389 (M + 1)


40
CH2═C(Me)CH2OC(═O)
CH2
OCH2
*
401 (M + 1)


42
n-PrOC(═O)
CH2
OCH2
*
389 (M + 1)


43
CH2═CHCH2OC(═O)
CH2
OCH2
*
387 (M + 1)


44
HC≡CCH2OC(═O)
CH2
OCH2
*
385 (M + 1)


45
CF3CH2OC(═O)
CH2
OCH2
*
429 (M + 1)


46
CF3CF2CH2OC(═O)
CH2
OCH2
*
479 (M + 1)


47
PhCH2OC(═O)
CH2
OCH2
*
437 (M + 1)


48
CH3(CH2)5OC(═O)
CH2
OCH2
*
431 (M + 1)


49
3,4-di-Cl-PhCH2OC(═O)
CH2
OCH2
*
505 (M + 1)


50
3,4-di-F-PhCH2OC(═O)
CH2
OCH2
*
473 (M + 1)


51
EtOC(═O)
CH2
CH(OH)CH2
*



66
EtOC(═O)
CH2
CH2CH2
*
355 (M + 1)


131
EtOC(═O)
CH2CH2
OCH2
*



206
N≡C
CH2
OCH2
*



227
EtOC(═O)
CH2
OCH2
*



286
EtOC(═O)
(CH2)3
OCH2
*
403 (M + 1)


322
Br
CH2
OCH2
*
383 (M + 1)


329
HOC(═O)
CH2
OCH2
*
327 (M − 1)


381
EtOC(═O)
CH2
N(C≡N)CH2

381 (M + 1)


388
CF3
CH2
OCH2

351 (M − 1)


389
NO2
CH2
OCH2

346 (M − 1)





*See Index Table M for 19F NMR data.













INDEX TABLE A1









embedded image

















Cmpd. No.
R13
L
(R8)q
NMR
MS





264
EtOC(═O)
CH2
3-F
*



376
EtOC(═O)
CH2
2-F

393 (M + 1)


409
EtOC(═O)
CH2
3-I

501 (M + 1)


431
EtOC(═O)
CH2
2,3-di-F

411 (M + 1)


444
EtOC(═O)
CH2
3-Me

389 (M + 1)


455
NO2
CH2
3-F

346 (M − 1)


456
CF3
CH2
3-F

369 (M − 1)


459
EtOC(═O)
CH2
3-Cl

409 (M + 1)


465
EtOC(═O)
CH2
2,3,5,6-tetrafluoro

447 (M + 1)





*See Index Table M for 19FNMR data.













INDEX TABLE A2









embedded image

















Cmpd. No.
R13
L
A
MS
m.p. (° C.)















68
CF3CH2NHC(═O)
CH2
OCH2
445 (M + 1)
116-120


69
c-PrCH2NHC(═O)
CH2
OCH2
417 (M + 1)






135


embedded image


CH2
OCH2
453 (M + 1)






136
EtOC(═O)
CH2
OCH2
392 (M + 1)






215


embedded image


CH2
OCH2
403 (M + 1)
140-144





223
MeOCH2CH2NHC(═O)
CH2
OCH2
421 (M + 1)
















INDEX TABLE B









embedded image







A dash “—” in the L column means that L is a direct bond.













Cmpd. No.
E
L
A
NMR
MS
m.p. (° C.)
















2
CF3C(OH)2CH2O
—
OCH2
*

105-109


29
CH3CH2S(═O)2
CH2
OCH2
*




30
1-indolyl
CH2
CH2CH2

332 (M + 1)



31
MeS(═O)2
—
OCH2
*

102-106


33
MeOC(═O)NHN═CH
—
OCH2
*

140-145


34
Me2NS(═O)2
—
OCH2
*

142-146


41
3-(Me2NC(═O))-4,5-dihydro-5-isoxazolyl
—
OCH2
*




80
CH3C(═O)
—
OCH2
*




97
EtOC(═O)CH═CHCH2O
—
OCH2
*




142
N≡C
—
OCH2
*




177
HC(═O)
—
OCH2
*




229
MeOC(═O)
—
OCH2

279 (M − 1)



233
3-(EtOC(═O))-1H-pyrazol-1-yl
CH2
OCH2
*




234
5-(EtOC(═O))-1H-pyrazol-1-yl
CH2
OCH2
*




247
5-(c-PrCH2NHC(═O))-2-oxazolyl
CH2
OCH2

401 (M + 1)



256
5-(c-PrCH2NHC(═O))-2-thiazolyl
CH2
OCH2

417 (M + 1)
126-130


274
5-(CF3CH2NHC(═O))-2-oxazolyl
CH2
OCH2

429 (M + 1)
75-79


277
5-(CF3CH2NHC(═O))-2-thiazolyl
CH2
OCH2

445 (M + 1)
110-114


280
NO2
—
OCH2
*




295
5-(F2CHCH2NHC(═O))-2-thiazolyl
CH2
OCH2

427 (M + 1)



366 (Ex. 8)
4-(EtOC(═O))-1H-pyrazol-1-yl-CH2O
—
OCH2
**




369
CH3
—
OCH(C(═O)OMe
*







384


embedded image


—
OCH2

320 (M + 1)






387
CF3
—
OCH2

271 (M − 1)



396
CH3
—
OCH2
*




432
MeO
CH2
OCH2
*





*See Index Table M for 19F NMR data.


**See Index Table N for 1H NMR data.













INDEX TABLE C









embedded image


















Cmpd. No.
R13
L
A
M
NMR
MS
















3
n-PrOC(═O)
CH2
OCH2
CH2
*
415 (M + 1)


4
EtOC(═O)
CH2
OCH2
C(═O)
*
415 (M + 1)


6
EtOC(═O)
CH2
OCH(Me)
CH2
*



7 [Note 1]
EtOC(═O)
CH2
OCH2
CH(Me)
*



8 [Note 2]
EtOC(═O)
CH2
OCH2
CH(Me)
*



12 (Ex. 3)
EtOC(═O)
CH2
OCH2
C(Me)2
*



13
MeOC(═O)
CH2
OCH2
CH2
*
387 (M + 1)


14
i-PrOC(═O)
CH2
OCH2
CH2
*
415 (M + 1)


15
HC≡CCH2OC(═O)
CH2
OCH2
CH2
*
411 (M + 1)


16
CH3(CH2)5OC(═O)
CH2
OCH2
CH2
*
457 (M + 1)


17
3,4-di-Cl-PhCH2OC(═O)
CH2
OCH2
CH2
*
531 (M + 1)


18
3,4-di-F-PhCH2OC(═O)
CH2
OCH2
CH2
*
499 (M + 1)


26
EtOC(═O)
CH(CH3)
OCH2
CH2
*
413 (M − 1)


32 (Ex. 2)
EtOC(═O)
CH2
OCH2
CH2
*



and (Ex. 4)








67
EtOC(═O)
CH2
CH2CH2
CH2
*
397 (M − 1)


93
HOC(═O)
CH2
OCH2
CH2
*



115
EtOC(═O)
CH2
SCH2
CH2

417 (M + 1)


125
n-BuOC(═O)
CH2
OCH2
CH2

429 (M + 1)


126
i-BuOC(═O)
CH2
OCH2
CH2
*
429 (M + 1)


127
c-PrCH2OC(═O)
CH2
OCH2
CH2
*
427 (M + 1)


133
EtOC(═O)
CH2CH2
OCH2
CH2
*



134
CF3CH2OC(═O)
CH2
OCH2
CH2
*
453 (M − 1)


141
EtOC(═O)
CH2
CH2OCH2
CH2
*



161
Cl(CH2)3OC(═O)
CH2
OCH2
CH2
*
449 (M + 1)


162
MeOCH2CH2OC(═O)
CH2
OCH2
CH2
*
431 (M + 1)


163
CH3C≡CCH2OC(═O)
CH2
OCH2
CH2
*
425 (M + 1)


164
N≡CCH2NHC(═O)
CH2
OCH2
CH2
*
411 (M + 1)


169
CH3C(═O)CH2OC(═O)
CH2
OCH2
CH2
*
429 (M + 1)


170
PhC(═O)CH2OC(═O)
CH2
OCH2
CH2
*
491 (M + 1)


171
N≡C(CH2)3OC(═O)
CH2
OCH2
CH2
*
440 (M + 1)


172
N≡CCH2OC(═0)
CH2
OCH2
CH2
*



188
CH2═CHCH2OC(═O)
CH2
OCH2
CH2

413 (M + 1)


197
CF3CH2NHC(═O)
CH2
OCH2
CH2
*
454 (M + 1)


198
Me2NC(═O)
CH2
OCH2
CH2
*
400 (M + 1)


199
2-pyridyl-CH2OC(═O)
CH2
OCH2
CH2
*
464 (M + 1)


200
3-pyridyl-CH2OC(═O)
CH2
OCH2
CH2
*
464 (M + 1)


201
4-pyridyl-CH2OC(═O)
CH2
OCH2
CH2
*
464 (M + 1)


202
c-hexyl-C(═O)CH2OC(═O)
CH2
OCH2
CH2
*
497 (M + 1)


203
MeOC(═O)CH2OC(═O)
CH2
OCH2
CH2
*
445 (M + 1)


204
1,3-dioxolan-2-yl-CH2OC(═O)
CH2
OCH2
CH2
*
459 (M + 1)


209
N≡C
CH2
OCH2
CH2
*



228
CH2═C(CH3)CH2OC(═O)
CH2
OCH2
CH2
*
427 (M + 1)


240
EtOCH2
CH2
OCH2
CH2
*
387 (M + 1)


249
c-BuCH2OC(═O)
CH2
OCH2
CH2
*
441 (M + 1)


272
c-hexyl-CH2OC(═O)
CH2
OCH2
CH2
*
469 (M + 1)


284
c-pentyl-CH2OC(═O)
CH2
OCH2
CH2
*
455 (M + 1)


285 [Note 4]
CH3CH═CHCH2OC(═O)
CH2
OCH2
CH2
*
427 (M + 1)


296
EtOC(═O)
(CH2)3
OCH2
CH2
*
429 (M + 1)


318
c-BuOC(═O)
CH2
OCH2
CH2
*
427 (M + 1)


319
EtOC(═O)
CH2
OCF2
CH2
*
437 (M + 1)


443
EtOC(═O)
CH2
NHCH2
CH2
*





*See Index Table M for 19F NMR data.


Note 1: 87:13 mixture of diastereomers.


Note 2: 33:67 mixture of diastereomers.


Note 4: 60:40 mixture of cis-trans isomers.













INDEX TABLE D









embedded image

















Cmpd. No.
T
NMR
MS







  9


embedded image


*








 10


embedded image


*








 20


embedded image


*








 21


embedded image


*
400 (M + 1)







 52


embedded image


*








187


embedded image



429 (M + 1)







*See Index Table M for 19F NMR data.













INDEX TABLE E









embedded image







A dash “—” in the L column means that L is a direct bond.












Cmpd. No.
E
L
A
NMR
MS





 22
3-(Me2NC(═O))-4,5-dihydro-5-isoxazolyl
—
OCH2
*



 23
CH3CH2S(═O)2
CH2
OCH2
*



 24
CH3S(═O)2
—
OCH2
*



 25
(Me)2NS(═O)2
—
OCH2
*



 27
MeOC(═O)NHN═CH
—
OCH2
*






 28


embedded image


—
OCH2
*






 76
i-BuS(═O)2NH
CH2
OCH2

396 (M − 1)


 77
c-hexyl-NHC(═S)NH
CH2
OCH2

419 (M + 1)


 78
EtOC(═O)NH
CH2
OCH2

350 (M + 1)


 98
N≡C
—
OCH2
*
274 (M + 1)


112
i-BuOC(═O)NH
CH2
OCH2
*



160
5-(EtOC(═O)-1-indazolyl
CH2
OCH2
*



166
NO2
—
OCH2
*



173
5-(CF3)-1,2,4-oxadiazol-3-yl
—
OCH2

385 (M + 1)


174
NH2
CH2
OCH2
*



175
i-PrC(═O)NH
CH2
OCH2

348 (M + 1)


176
c-PrC(═O)NH
CH2
OCH2
*



178
OH
CH2
OCH2

301







(M + 23)


179
3-CF3-PhC(═O)NH
CH2
OCH2
*



189
MeOC(═O)
—
OCH2
*
307 (M + 1)


190
Ph
—
OCH2
*



191
PhO
—
OCH2
*



192
Ph
CH2
OCH2
*



207
CF3S(═O)2NH
CH2
OCH2

408 (M − 1)


212
CF3CH2C(═O)NH
CH2
OCH2

388 (M + 1)


214
MeOCH(CH3)C(═O)NH
CH2
OCH2
*



232
3-(EtOC(═O))-1H-pyrazol-1-yl
CH2
OCH2
*



235
i-PrC(═O)N(OMe)
CH2
OCH2
*



236
c-PrC(═O)N(OMe)
CH2
OCH2
*



237
n-PrC(═O)N(OMe)
CH2
OCH2
*



238
t-BuOC(═O)N(OMe)
CH2
OCH2

430







(M + 23)


239
N≡C
CH2
OCH2
*



281
2-(MeS)-4-pyrimidinyl
CH2
OCH2

387 (M + 1)


282
2-(MeS(═O)2)-4-pyrimidinyl
CH2
OCH2

419 (M + 1)


283
2-(F2CHCH2O)-4-pyrimidinyl
CH2
OCH2

421 (M + 1)





289


embedded image


CH2
OCH2
*






290


embedded image


CH2
OCH2
*






314


embedded image


CH2
OCH2

457 (M + 1)





372


embedded image


—
OCH2

346 (M + 1)





382


embedded image


—


396 (M + 1)





411


embedded image


—
OCH2

375 (M + 1)





*See Index Table M for 19F NMR data.













INDEX TABLE E1









embedded image


















Cmpd. No.
R13
M
L
A
MS
m.p. (° C.)





 70
4-(CF3CH2NHC(═O))
S
CH2
OCH2
471 (M + 1)



 71
4-(c-PrCH2NHC(═O))
S
CH2
OCH2
443 (M + 1)
88-92


137
4-(EtOC(═O))
S
CH2
OCH2
418 (M + 1)
74-78


248
5-(c-PrCH2NHC(═O))
O
CH2
OCH2
427 (M + 1)



257
5-(CF3CH2NHC(═O))
O
CH2
OCH2
455 (M + 1)
 99-103


259
5-(c-PrCH2NHC(═O))
S
CH2
OCH2
443 (M + 1)
117-121


275
5-(CF3CH2NHC(═O))
S
CH2
OCH2
471 (M + 1)
















INDEX TABLE F









embedded image







A dash “—” in the R13 column means no R13


substituent is present and the remaining carbon valence is occupied by


a hydrogen atom. A dash “—” in the L column means that L is a direct bond. Unless otherwise indicated, the


configuration of substituents about the double bond in the above structure is as shown in the structure.














Cmpd.





MS
m.p.


No.
R13
L
A
R2c
NMR
(M + 1)
(° C.)





 53
EtOC(═O)
CH2
O
CH3
*




 54
EtOC(═O)
CH2
O
CH2CH2OMe
*




 55
EtOC(═O)
CH2
O
CH2CH═CH2
*




 56
EtOC(═O)
CH2
O
CH2C≡CH
*




 57
EtOC(═O)
CH2
O
CH(CH3)2
*




 64 (Ex. 5)
EtOC(═O)
CH2
O
CH2CH3
*

58-59


 65
EtOC(═O)
CH2
O
CH2CH2CH3
*




 89
t-BuOC(═O)
CH2
O
CH2CH3
*




106
CF3CH2NHC(═O)
CH2
O
CH2CH3


109-113


107
N≡CCH2NHC(═O)
CH2
O
CH2CH3


114-118


116
HOC(═O)
CH2
O
CH2CH3
*

127-131


117
c-PrCH2NHC(═O)
CH2
O
CH2CH3


106-110


118
i-PrNHC(═O)
CH2
O
CH2CH3


114-118


132
EtOC(═O)
(CH2)2
O
CH2CH3
*




138
MeOC(═O)
CH2
O
CH2CH3


105-109


139
i-PrOC(═O)
CH2
O
CH2CH3

399



140
EtOC(═O)
CH2
CH2
CH2CH3
*




145
EtOC(═O)
CH2
O
CH2CH2OH
*




151
—
CH2
O
CH2CH3
*




167
EtOC(═O)
CH2
CH2O
CH2CH3
*




180
Cl
CH2
O
CH2CH3
*




182
CF3
CH2
O
CH2CH3
*




183
Br
CH2
O
CH2CH3
*




185
CH≡CCH2OC(═O)
CH2
O
CH2CH3


69-73


186
PhCH2OC(═O)
CH2
O
CH2CH3


63-67


205
N≡C
CH2
O
CH2CH3
*




216
MeC(═O)CH2OC(═O)
CH2
O
CH2CH3


64-68


217
n-PrOC(═O)
CH2
O
CH2CH3

399



218
n-BuOC(═O)
CH2
O
CH2CH3

413



219
i-BuOC(═O)
CH2
O
CH2CH3

413



220
c-PrCH2OC(═O)
CH2
O
CH2CH3

411



221
Cl(CH2)3OC(═O)
CH2
O
CH2CH3

433



222
MeOCH2CH2OC(═O)
CH2
O
CH2CH3


79-83


242
CH2═C(Me)CH2OC(═O)
CH2
O
CH2CH3

411



243
CH3C≡CCH2OC(═O)
CH2
O
CH2CH3


105-109


244
PhC(═O)CH2OC(═O)
CH2
O
CH2CH3


114-118


245
N≡CCH2CH2OC(═O)
CH2
O
CH2CH3
*

81-85


246
CH2═CHCH2OC(═O)
CH2
O
CH2CH3

397



267
EtOC(═O)
CH(Me)
O
CH2CH3
*




294
EtOC(═O)
(CH2)3
O
CH2CH3
*
413



298
EtOC(═O)
CH2
O
CH2CH3
*




316
EtOC(═O)
—
O
CH2CH3

371



328
HOC(═O)
(CH2)2
O
CH2CH3
*




354
MeOC(═O)
(CH2)2
O
CH2CH3
*
385



380
EtOC(═O)
CH2
N(C≡N)
CH2CH3

371



400
EtOC(═O)
CH2
O
CH2C≡N

396



413
c-propyl-NHC(═O)
CH2
O
CH2CH3

396



414
CH3NHC(═O)
CH2
O
CH2CH3

370



422
EtOC(═O)
CH2
O
S(═O)2CF3

489



427
MeOC(═O)CH2NHC(═O)
CH2
O
CH2CH3

428



428
c-pentyl-NHC(═O)
CH2
O
CH2CH3

424



435
2-pyrimidinyl-CH2NHC(═O)
CH2
O
CH2CH3

448



436
CF2HCH2NHC(═O)
CH2
O
CH2CH3

420



437
CH3CH2NHC(═O)
CH2
O
CH2CH3

384



438
(CH3CH2)2NC(═O)
CH2
O
CH2CH3

412





*See Index Table M for 19F NMR data.













INDEX TABLE F1









embedded image







Unless otherwise indicated, the configuration of substituents about


the double bond in the above structure is as shown in the structure.














Cmpd.





MS
m.p.


No.
R13
L
(R8)q
R2c
NMR
(M + 1)
(° C.)





262
EtOC(═O)
CH2
3-F
CH2CH3
*




344
EtOC(═O)
CH2
3-Br
CH2CH3
*
463
88-89


374
EtOC(═O)
CH2
3-I
CH2CH3

511



375
EtOC(═O)
CH2
2-F
CH2CH3

403



410
EtOC(═O)
CH2
3-Me
CH2CH3

399



416
EtOC(═O)
CH2
3-C≡N
CH2CH3

410



430
EtOC(═O)
CH2
2,3-di-F
CH2CH3

421



458
EtOC(═O)
CH2
3-Cl
CH2CH3

419



464
EtOC(═O)
CH2
2,3,5,6-
CH2CH3

457






tetrafluoro





*See Index Table M for 19F NMR data.













INDEX TABLE G









embedded image







A dash “—” in the L column means that L is a direct bond.


Unless otherwise indicated, the configuration of substituents about the


double bond in the above structure is as shown in the structure.














Cmpd. No.
E
L
A
R2d
R2c
NMR
MS





 58


embedded image


—
O
H
CH2CH3
*






 60
CH3S(═O)2
—
O
H
CH2CH3
*



 61
(Me)2NS(═O)2
—
O
H
CH2CH3
*



 62
CH3CH2S(═O)2
CH2
O
H
CH2CH3
*



 72
HOC(═O)
—
O
H
CH2CH3
*
275 (M − 1)


 73
i-PrOC(═O)
—
O
H
CH2CH3
*
318 (M + 1)


 74
CH2═CHCH2OC(═O)
—
O
H
CH2CH3
*
317 (M + 1)


 75
CH≡CCH2OC(═O)
—
O
H
CH2CH3
*
313 (M − 1)


 79
CH3C(═O)
—
O
H
CH2CH3
*






 83


embedded image


CH2
O
H
CH2CH3
*
401 (M + 1)





 84


embedded image


CH2
O
H
CH2CH3
*
401 (M + 1)





 85
5-(CH3OC(═O))-1H-imidazol-1-yl
CH2
O
H
CH2CH3
*
371 (M + 1)


 86
4-(CH3OC(═O))-1H-imidazol-1-yl
CH2
O
H
CH2CH3
*
371 (M + 1)





 87


embedded image


CH2
O
H
CH2CH3
*
364 (M + 1)





 88


embedded image


CH2
O
H
CH2CH3
*
364 (M + 1)





 90
3-(EtOC(═O)-5-(MeO))-1H-pyrazol-1-yl
CH2
O
H
CH2CH3
*
415 (M + 1)





 91


embedded image


CH2
O
H
CH2CH3
*
420 (M + 1)





 92


embedded image


CH2
O
H
CH2CH3
*
360 (M + 1)





 94
n-PrOC(═O)
—
O
H
CH2CH3
*



 95
EtOC(═O)
—
O
H
CH2CH3
*
305 (M + 1)


 96
EtOC(═O)CH═CHCH2O
—
O
H
CH2CH3
*



 99
NH2C(═O)
—
O
H
CH2CH3
*
274 (M + 1)


100
c-PrNHC(═O)
—
O
H
CH2CH3
*
316 (M + 1)


101
i-PrNHC(═O)
—
O
H
CH2CH3
*
318 (M + 1)


102
CH≡CCH2NHC(═O)
—
O
H
CH2CH3
*
314 (M + 1)


103
CH2═CHCH2NHC(═O)
—
O
H
CH2CH3
*
316 (M + 1)


104
n-PrNHC(═O)
—
O
H
CH2CH3
*
318 (M + 1)


105
MeNHC(═O)
—
O
H
CH2CH3
*
290 (M + 1)


109
t-BuOC(═O)NH
CH2
O
H
CH2CH3

261 (M + 1)


110
NH2
CH2
O
H
CH2CH3

262 (M + 1)


111
EtOC(═O)NH
CH2
O
H
CH2CH3
*



113
CF3CH2C(═O)NH
CH2
O
H
CH2CH3
*



114
MeOCH(CH3)C(═O)NH
CH2
O
H
CH2CH3
*






119


embedded image


CH2
O
H
CH2CH3
*
386 (M + 1)





120


embedded image


CH2
O
H
CH2CH3
*
386 (M + 1)





121


embedded image


CH2
O
H
CH2CH3
*
386 (M + 1)





143


embedded image


—
O
H
CH2CH3
*






144
N≡C
—
O
H
CH2CH3
*



148
HC(═O)
—
O
H
CH2CH3




149
EtS(═O)2NH
CH2
O
H
CH2CH3
*



150
EtC(═O)NH
CH2
O
H
CH2CH3
*



152
3,5-di-Me-1H-pyrazol-1-yl
CH2
O
H
CH2CH3
*
341 (M + 1)


153
4-(EtOC(═O))-1H-imidazol-1-yl
CH2
O
H
CH2CH3
*
385 (M + 1)


154
N≡C
CH2
O
H
CH2CH3
*



155
N≡CS
CH2
O
H
CH2CH3
*



156
1H-imidazol-1-yl
CH2
O
H
CH2CH3
*
313 (M + 1)





184


embedded image


CH2
O
H
CH2CH3
*






193
NH2C(═O)O
CH2
O
H
CH2CH3
*



195
OH
CH2
O
H
CH2CH3
*



196
EtNHC(═O)O
CH2
O
H
CH2CH3
*



210
i-PrC(═O)NH
CH2
O
H
CH2CH3
*
332 (M + 1)


211
c-PrC(═O)NH
CH2
O
H
CH2CH3

331 (M + 1)





224


embedded image


CH2
O
H
CH2CH3
*
330 (M + 1)





225


embedded image


CH2
O
H
CH2CH3
*
358 (M + 1)





226


embedded image


CH2
O
H
CH2CH3
*
380 (M + 1)





230
MeOC(═O)
—
O
H
CH2CH3
*
291 (M + 1)


268
4-(EtOC(═O))-1-piperidinyl
CH2
O
H
CH2CH3
*
402 (M + 1)


269
3-(EtOC(═O))-1-piperidinyl
CH2
O
H
CH2CH3
*
402 (M + 1)


270
4-(EtOC(═O))-pyridin-1-yl
CH2
O
H
CH2CH3
*



[Note 7]









271
3-(EtOC(═O))-pyridin-1-yl
CH2
O
H
CH2CH3
*



[Note 7]












278


embedded image


—
O
H
CH2CH3
*






279
NO2
—
O
H
CH2CH3
*






287


embedded image


CH2
O
H
CH2CH3
*






288


embedded image


CH2
O
H
CH2CH3
*






297
4-(EtOC(═O))-1H-pyrazol-1-yl-CH2O
CH2
O
H
CH2CH3
*
412 (M − 1)





306


embedded image


CH2
O
H
CH2CH3

405 (M + 1)





307


embedded image


CH2
O
H
CH2CH3

403 (M + 1)





308


embedded image


CH2
O
H
CH2CH3

371 (M + 1)





309
4-(MeOC(═O))-1-piperidinyl
CH2
O
H
CH2CH3
*
388 (M + 1)


310
3-(MeOC(═O))-1-pyrrolidinyl
CH2
O
H
CH2CH3
*
374 (M + 1)


311
4-(N≡C)-1-piperidinyl
CH2
O
H
CH2CH3
*
355 (M + 1)


312
4-(MeO)-1-piperidinyl
CH2
O
H
CH2CH3
*
360 (M + 1)





313


embedded image


CH2
O
H
CH2CH3

441 (M + 1)





364
4-(EtOC(═O))-1H-pyrazol-1-yl-CH2O
—
O
H
CH2CH3

401 (M + 1)


(Ex. 9)









371
c-PrC(═O)NH
—
O
H
CH2CH3

316 (M + 1)





373


embedded image


—
O
H
CH2CH3

330 (M + 1)





379
2-F-PhC(═O)O
—
O
H
CH2CH3

371 (M + 1)





383


embedded image


—
O
H
CH2CH3

380 (M + 1)





412


embedded image


—
O
H
CH2CH3

359 (M + 1)





426
4-(2,4-di-F-PhNHC(═O))-1H-pyrazol-1-yl
—
O

CH2CH3

468 (M + 1)


433
MeO
CH2
O
H
CH2CH3
*



434
ClCH2
—
O
H
CH2CH3
**



445
MeC(═O)S
CH2
O
H
CH2CH3
*



461
2-F-PhC(═O)NH
—
O
H
CH2CH3

370 (M + 1)





*See Index Table M for 19F NMR data.


**See Index Table N for 1H NMR data.


Note 7: HBr salt.













INDEX TABLE H









embedded image







Unless otherwise indicated, the configuration of substituents about the double bond in the above


structure is as shown in the structure.














Cmpd. No.
R13
L
A
R2d
R2c
NMR
MS





158
3-CH3
CH2
O
H
CH2CH3
*
371 (M + 1)


181
3-CF3
CH2
O
H
CH2CH3
*
379 (M − 1)


231
3-(EtOC(═O))
CH2
O
H
CH2CH3
*



241
5-(EtOC(═O))
CH2
O
H
CH2CH3
*



250
5-(MeOC(═O))
CH2
O
H
CH2CH3
*
371 (M + 1)


251
3-(MeOC(═O))
CH2
O
H
CH2CH3
*
371 (M + 1)


252
5-(t-BuOC(═O))
CH2
O
H
CH2CH3
*
411 (M − 1)


253
3-(t-BuOC(═O))
CH2
O
H
CH2CH3
*
411 (M − 1)


291
3-(CH2═CHCH2OC(═O))
CH2
O
H
CH2CH3
*
397 (M + 1)


292
3-(n-PrOC(═O))
CH2
O
H
CH2CH3
*
399 (M + 1)


293
3-(CH3C≡CCH2OC(═O))
CH2
O
H
CH2CH3
*
409 (M + 1)


299
3-(HOC(═O))
CH2
O
H
CH2CH3
*



325
3-(HC≡CCH2OC(═O))
CH2
O
H
CH2CH3
*
395 (M + 1)


326
3-(CH3CH2C≡CCH2OC(═O))
CH2
O
H
CH2CH3
*
423 (M + 1)


327
3-(i-PrOC(═O))
CH2
O
H
CH2CH3
*
399 (M + 1)


356
3-(n-BuOC(═O))
CH2
O
H
CH2CH3
*
413 (M + 1)


357
3-(i-BuOC(═O))
CH2
O
H
CH2CH3
*
413 (M + 1)


358
3-(CH2═C(Me)CH2OC(═O))
CH2
O
H
CH2CH3
*
411 (M + 1)


359
3-(CH3C(═O)CH2OC(═O))
CH2
O
H
CH2CH3
*
413 (M + 1)


360
3-(MeOCH2CH2OC(═O))
CH2
O
H
CH2CH3
*
415 (M + 1)


361
3-(c-BuCH2OC(═O))
CH2
O
H
CH2CH3
*
425 (M + 1)


362
3-(ClCH2CH2CH2OC(═O))
CH2
O
H
CH2CH3
*
433 (M + 1)





*See Index Table M for 19F NMR data.













INDEX TABLE 1









embedded image







A dash “—” in the R13 column means no R13 substituent is present and the remaining carbon valences are


occupied by the hydrogen atoms. Unless otherwise indicated, the configuration of substituents


about the double bond in the above structure is as shown in the structure














Cmpd. No.
R13
L
A
R2d
R2c
NMR
MS





81
5-CN
CH2
O
H
CH2CH3
*
337 (M − 1)


82
3-CN
CH2
O
H
CH2CH3
*
337 (M − 1)


122
5-(MeOC(═O))
CH2
O
H
CH2CH3
*
370 (M − 1)


123
3-(MeOC(═O))
CH2
O
H
CH2CH3
*
370 (M − 1)


157
—
CH2
O
H
CH2CH3
*
312 (M − 1)


260
5-MeS
CH2
O
H
CH2CH3
*
358 (M − 1)


261
3-MeS
CH2
O
H
CH2CH3
*
360 (M + 1)





*See Index Table M for 19F NMR data.













INDEX TABLE J









embedded image







Unless otherwise indicated, the configuration of substituents about the double bond in the above


structure is as shown in the structure.















Cmpd. No.
R13
M
L
A
R2d
R2c
NMR
MS





129
4-(CF3CH2NHC(═O))
S
CH2
O
H
CH2CH3
*



130
4-(c-PrCH2NH(═O))
S
CH2
O
H
CH2CH3
*



254
5-(c-PrCH2NHC(═O))
S
CH2
O
H
CH2CH3

427 (M + 1)


255
5-(CHF2CH2NHC(═O))
O
CH2
O
H
CH2CH3

421 (M + 1)


258
5-(c-PrCH2NHC(═O))
O
CH2
O
H
CH2CH3

411 (M + 1)


276
5-(CHF2CH2NHC(═O))
S
CH2
O
H
CH2CH3

437 (M + 1)





*See Index Table M for 19F NMR data.













INDEX TABLE K









embedded image







A dash “—” in the L columna means that L is a direct bond. Unless otherwise indicated, the configuration of


substituents about the double bond in the above structure is as shown in the structure.













Cmpd. No.
R13
L
R2d
R2c
NMR
MS





265
EtOC(═O)
CH2
H
CH2CH3
*
385 (M + 1)


(Ex. 7)








300
CH3C≡CCH2OC(═O)
CH2
H
CH2CH3
*
409 (M + 1)


304
EtOC(═O)
CH(Me)
H
CH2CH3

399 (M + 1)


317
EtOC(═O)
—
H
CH2CH3

371 (M + 1)


323
HOC(═O)
CH2
H
CH2CH3
*
357 (M + 1)


324
EtOC(═O)
CH2
H
n-Pr

399 (M + 1)


330
MeOC(═O)
CH2
H
CH2CH3
*
371 (M + 1)


331
n-PrOC(═O)
CH2
H
CH2CH3
*
399 (M + 1)


332
i-PrOC(═O)
CH2
H
CH2CH3
*
399 (M + 1)


333
CH2═CHCH2OC(═O)
CH2
H
CH2CH3
*
397 (M + 1)


334
i-BuOC(═O)
CH2
H
CH2CH3
*
413 (M + 1)


335
CH2═C(Me)CH2OC(═O)
CH2
H
CH2CH3
*
411 (M + 1)


336
CH≡CCH2OC(═O)
CH2
H
CH2CH3
*
395 (M + 1)


337
CH3C(═O)CH2OC(═O)
CH2
H
CH2CH3
*
413 (M + 1)


338
Cl(CH2)3OC(═O)
CH2
H
CH2CH3
*
433 (M + 1)


339
n-BuOC(═O)
CH2
H
CH2CH3
*
413 (M + 1)


340
CH3O(CH2)2OC(═O)
CH2
H
CH2CH3
*
415 (M + 1)


341
c-PrCH2OC(═O)
CH2
H
CH2CH3
*
411 (M + 1)


342
c-BuCH2OC(═O)
CH2
H
CH2CH3
*
425 (M + 1)


343
EtNHC(═O)
CH2
H
CH2CH3
*
382 (M − 1)


345
EtOC(═O)
CH2CH3
H
CH2CH3
*
399 (M + 1)


347
CHF2CH2OC(═O)
CH2
H
CH2CH3
*
421 (M + 1)


348
CF3CH2CH2OC(═O)
CH2
H
CH2CH3
*
453 (M + 1)


349
CF2═CFCH2CH2OC(═O)
CH2
H
CH2CH3
*
465 (M + 1)


350
(Me)2CH(CH2)2OC(═O)
CH2
H
CH2CH3
*



351
CH3O(CH2)3OC(═O)
CH2
H
CH2CH3
*
429 (M + 1)


352
CF3O(CH2)2OC(═O)
CH2
H
CH2CH3
*
469 (M + 1)


355
CF3(CH2)3OC(═O)
CH2
H
CH2CH3
*
467 (M + 1)


365
EtOC(═O)
CH2
H
CH3
*



390
c-pentyl-NHC(═O)
CH2
H
CH2CH3

424 (M + 1)


391
c-propyl-NHC(═O)
CH2
H
CH2CH3

396 (M + 1)


393
c-propyl-CH2NHC(═O)
CH2
H
CH2CH3

410 (M + 1)


394
CF2HCH2NHC(═O)
CH2
H
CH2CH3

420 (M + 1)


401
CF3CH2NHC(═O)
CH2
H
CH2CH3

438 (M + 1)


402
2-pyrimidinyl-CH2NHC(═O)
CH2
H
CH2CH3

448 (M + 1)


403
CH3NHC(═O)
CH2
H
CH2CH3

370 (M + 1)


404
(CH3CH2)2NC(═O)
CH2
H
CH2CH3

412 (M + 1)


415
i-PrNHC(═O)
CH2
H
CH2CH3

398 (M + 1)


421
EtOC(═O)
(CH2)3
H
CH2CH3

413 (M + 1)





*See Index Table M for 19F NMR data.













INDEX TABLE K1









embedded image







A dash “—” in the R8 column means no R8 substituent is present and the remaining carbon


valence is occupied by a hydrogen atom. Unless otherwise indicated, the configuration of substituents


about the double bond in the above structure is as shown in the structure.












Cmpd. No.
R13
L
R8
R2c
MS





301
4-(EtOC(═O))
CH2
2-F
CH2CH3
403 (M + 1)


302
4-(EtOC(═O))
CH2
6-F
CH2CH3
403 (M + 1)


303
4-(EtOC(═O))
CH2
2-Me
CH2CH3
399 (M + 1)


378
3-(EtOC(═O))
CH2
5-MeO
CH2CH3
415 (M + 1)


405
3-(EtOC(═O))
CH2
5-Me
CH2CH3
399 (M + 1)


406
4-(EtOC(═O))
CH2
5-Me
CH2CH3
399 (M + 1)


407
3-(EtOC(═O))
CH2
4-MeO
CH2CH3
415 (M + 1)


408
4-(EtOC(═O))
CH2
4-MeO
CH2CH3
415 (M + 1)


418
4-(EtOC(═O))
CH2
4-F
CH2CH3
403 (M + 1)


419
5-(EtOC(═O))
CH2
4-F
CH2CH3
403 (M + 1)


420
3-(EtOC(═O))
CH2
4-F
CH2CH3
403 (M + 1)


448
5-(EtOC(═O))
CH2
—
CH2CH3
386 (M + 1)


449
3-(EtOC(═O))
CH2
—
CH2CH3
386 (M + 1)


451
4-(EtOC(═O))
CH2
6-Me
CH2CH3
399 (M + 1)


462
5-(EtOC(═O))
CH2
5-Me
CH2CH3
399 (M + 1)


463
5-(EtOC(═O))
CH2
4-MeO
CH2CH3
415 (M + 1)




















INDEX TABLE L









m.p.


Cmpd. No.
Structure
NMR
MS
(° C.)







 63 [Note 6]


embedded image


*







124


embedded image



402 (M + 1)






146


embedded image


*
401 (M + 1)






147


embedded image


*
274 (M + 1)






165


embedded image


*







166


embedded image



402 (M + 1)






263


embedded image


*







266 (Ex. 6)


embedded image


*







273


embedded image


**







305


embedded image


*







320


embedded image



391 (M + 1)






321


embedded image


*







346


embedded image


*
389 (M + 1)






353


embedded image


*
417 (M + 1)






367


embedded image


*







368


embedded image



349 (M + 1)
81-84





370


embedded image



403 (M + 1)






377


embedded image



455 (M + 1)






385


embedded image


*







386


embedded image


*

83.7-86.5





392


embedded image



473 (M + 1)
59-62





395


embedded image


*







398


embedded image



437 (M + 1)






399


embedded image



385 (M + 1)






417


embedded image



403 (M + 1)






423


embedded image


*







424


embedded image



409 (M + 1)






425


embedded image



419 (M + 1)






439


embedded image



289 (M − 1)






440


embedded image



339 (M − 1)






441


embedded image



272 (M − 1)






442


embedded image



279 (M − 1)






446


embedded image


*







447


embedded image


*







450


embedded image



373 (M + 1)






452


embedded image



369 (M − 1)






453


embedded image



365 (M + 1)






454


embedded image



419 (M + 1)






457


embedded image



417 (M + 1)






460


embedded image



275 (M − 1)





Note 6: 3:2 mixture of geometric isomers.


*See Index Table M for 19F NMR data.


**See Index Table N for 1H NMR data.
















INDEX TABLE M








Cmpd.



No.

19F NMR Dataa











1
δ −84.92 (s).


2
δ (DMSO-d6) −81.80 (s).


3
δ −81.39 (s).


4
δ (DMSO-d6) −81.50 (s).


5
δ −82.61 (s), −75.48 (s).


6
δ −79.03 (s).


7
δ −81.50 (s), −81.71 (s).


8
δ −81.50 (s), −81.71 (s).


9
δ −81.27 (s).


10
δ −79.64 (s).


12
δ −81.01 (s).


13
δ −81.38 (s).


14
δ −81.39 (s).


15
δ −81.38 (s).


16
δ −81.39 (s).


17
δ −81.38 (s).


18
δ −81.38 (s).


20
δ −78.49 (s).


21
δ −80.99 (s).


22
δ −81.39 (s).


23
δ −81.37 (s).


24
δ −81.37 (s).


25
δ −81.37 (s).


26
δ −81.39 (s).


27
δ −81.41 (s).


28
δ −81.38 (s).


29
δ −84.92 (s).


31
δ (DMSO-d6) −81.91 (s).


32
δ −81.39 (s).


33
δ (DMSO-d6) −81.83 (s).


34
δ (DMSO-d6) −81.89 (s).


35
δ −84.94 (s).


36
δ (DMSO-d6) −81.37 (s).


37
δ (DMSO-d6) −81.82 (s).


39
δ −84.93 (s).


40
δ (acetone-d6) −83.12 (s).


41
δ −84.81 (s).


42
δ (DMSO-d6) −81.82 (s).


43
δ (DMSO-d6) −81.82 (s).


44
δ −84.21 (s).


45
δ (DMSO-d6) −81.82 (s), −72.33 (t).


46
δ (DMSO-d6) −81.83 (s), −82.96 (s),



−122.29 (t).


47
δ (DMSO-d6) −81.82 (s).


48
δ (DMSO-d6) −81.82 (s).


49
δ (DMSO-d6) −81.82 (s).


50
δ (DMSO-d6) −81.82 (s), −138.53 (m),



−139.66 (m).


51
δ −87.93 (s).


52
δ −76.89 (s).


53
δ −70.09 (s).


54
δ −69.99 (s).


55
δ −69.95 (s).


56
δ −69.73 (s).


57
δ −69.75 (s).


58
δ −70.10 (s).


60
δ −70.30 (s).


61
δ −70.26 (s).


62
δ −70.15 (s).


63
δ −63.30 (s), −63.67 (s).


64
δ −70.13 (s).


65
δ −70.03 (s).


66
δ −85.74 (s).


67
δ −82.36 (s).


72
δ −70.24 (s).


73
δ −70.20 (s).


74
δ −70.22 (s).


75
δ −70.22 (s).


79
δ −70.22 (s).


80
δ −84.87 (s).


81
δ −70.17 (s).


82
δ −70.14 (s).


83
δ −70.17 (s).


84
δ −70.16 (s).


85
δ −70.14 (s).


86
δ −70.12 (s).


87
δ −70.11 (s).


88
δ −70.19 (s).


89
δ −70.13 (s).


90
δ −70.16 (s).


91
δ −70.12 (s).


92
δ −70.13 (s).


93
δ −81.42 (s).


94
δ −70.21 (s).


95
δ −70.21 (s).


96
δ −69.98 (s).


97
δ −84.95 (s).


98
δ −81.40 (s).


99
δ −70.19 (s).


100
δ −70.16 (s).


101
δ −70.15 (s).


102
δ −70.18 (s).


103
δ −70.16 (s).


104
δ −70.16 (s).


105
δ −70.16 (s).


111
δ −70.08 (s).


112
δ −81.43 (s).


113
δ −63.01 (s), −70.10 (s).


114
δ −70.09 (s).


116
δ −70.14 (s).


119
δ −70.16 (s).


120
δ −70.15 (s).


121
δ −70.16 (s).


122
δ −70.14 (s).


123
δ −70.15 (s).


126
δ −81.38 (s).


127
δ −81.38 (s).


129
δ −70.06 (s), −72.25 (s).


130
δ 70.06 (s).


131
δ −84.93 (s).


132
δ −70.05 (s).


133
δ −81.40 (s).


134
δ −81.40 (s), −73.70 (s).


140
δ −69.16 (s).


164
δ −81.33 (s).


165
δ −81.34 (s).


166
δ −81.38 (s).


167
δ −69.60 (s).


141
δ −81.28 (s).


142
δ −84.83 (s).


143
δ −60.46(s), −70.25 (s).


144
δ −70.30 (s).


145
δ −69.79 (s).


146
δ −81.37 (s).


147
δ −81.36 (s).


149
δ −70.07 (s).


150
δ −70.07 (s).


151
δ −70.09 (s).


152
δ −70.09 (s).


153
δ −70.12 (s).


154
δ −70.10 (s).


155
δ −70.05 (s).


156
δ −70.05 (s).


157
δ −70.19 (s).


158
δ −70.10 (s).


160
δ −81.44 (s).


161
δ −81.38 (s).


162
δ (DMSO-d6) −80.02 (s).


163
δ −81.38 (s).


169
δ −81.38 (s).


170
δ −81.38 (s).


171
δ −81.37 (s).


172
δ −81.37 (s).


174
δ −80.00 (s).


176
δ −81.40 (s).


177
δ −84.85 (s).


179
δ −62.79 (s), −81.40 (s).


180
δ −70.10 (s).


181
δ −61.85 (s).


182
δ −56.40 (s).


183
δ −70.09 (s).


184
δ −70.11 (s).


189
δ −81.42 (s).


190
δ −81.38 (s).


191
δ −81.42 (s).


192
δ −81.39 (s).


193
δ −70.01 (s).


195
δ −70.04 (s).


196
δ −70.08 (s)..


197
δ −72.38 (s), −81.38 (s).


198
δ −81.38 (s).


199
δ −81.38 (s).


200
δ −81.38 (s).


201
δ −81.38 (s).


202
δ −81.39 (s).


203
δ −81.39 (s).


204
δ −81.38 (s).


205
δ −70.14 (s).


206
δ −84.95 (s).


209
δ −81.36 (s).


210
δ −70.08 (s).


214
δ −81.43 (s).


224
δ −70.09 (s).


225
δ −70.08 (s).


226
δ −70.10 (s).


227
δ −81.57 (s), −84.95 (s).


228
δ −81.39 (s).


230
δ −70.21 (s).


231
δ −70.12 (s).


232
δ −81.39 (s).


233
δ −84.87 (s).


234
δ −84.95 (s).


235
δ −81.45 (s).


236
δ −81.46 (s).


237
δ −81.44 (s).


239
δ −81.42 (s).


240
δ −81.39 (s)


241
δ −70.11 (s).


245
δ −68.61 (s).


249
δ −81.39 (s).


250
δ −70.11 (s).


251
δ −70.13 (s).


252
δ −70.09 (s).


253
δ −70.11 (s).


260
δ −70.12 (s).


261
δ −70.12 (s).


262
δ −70.33 (s).


263
δ −81.60 (s), −132.13 (s).


264
δ −84.92 (s).


265
δ −70.09 (s).


266
δ −84.88 (s).


267
δ −70.13 (s).


268
δ −70.03 (s).


269
δ −70.03 (s).


270
δ −70.12 (s).


271
δ −70.12 (s).


272
δ −69.99 (s).


278
δ −70.11 (s).


279
δ −70.31 (s).


280
δ −84.80 (s).


284
δ −81.38 (s).


285
δ −81.39 (s).


286
δ −84.94 (s).


287
δ −70.05 (s).


288
δ −70.04 (s).


289
δ −81.39 (s).


290
δ −81.37 (s).


291
δ −70.12 (s).


292
δ −70.13 (s).


293
δ −70.13 (s).


294
δ −70.01 (s).


296
δ −81.38 (s).


297
δ −70.01 (s).


298
δ −70.05 (s), −74.96 (s).


299
δ −70.12 (s).


300
δ −70.10 (s).


305
δ −84.85 (s).


309
δ −70.02 (s).


310
δ −70.04 (s).


311
δ −70.01 (s).


312
δ −70.03 (s).


318
δ −81.38 (s).


319
δ −79.29 (s), 82.67 (s).


321
δ −68.60 (s).


322
δ −81.70 (s).


323
δ −70.10 (s).


325
δ −70.11 (s).


326
δ −70.13 (s).


327
δ −70.13 (s).


328
δ −68.54 (s).


329
δ −77.08 (s).


330
δ −70.09 (s).


331
δ −70.10 (s).


332
δ −70.08 (s).


333
δ −70.09 (s).


334
δ −70.09 (s).


335
δ −70.09 (s).


336
δ −70.08 (s).


337
δ −70.08 (s).


338
δ −70.06 (s).


339
δ −70.10 (s).


340
δ −70.09 (s).


341
δ −70.09 (s).


342
δ −70.11 (s).


343
δ −70.11 (s).


344
δ −70.50 (s).


345
δ −68.59 (s).


346
δ −81.82 (s).


347
δ −70.09 (s), −125.54 (s).


348
δ −64.93 (s), −70.09 (s).


349
δ −70.13 (s), −103.21 (s),



−123.98 (s), −175.15 (s).


350
δ −70.09 (s).


351
δ −70.09 (s).


352
δ −60.95 (s), −70.12 (s).


353
δ −81.41 (s).


354
δ −70.03 (s).


355
δ −66.44 (s), −70.09 (s).


356
δ −70.14 (s).


357
6 −70.13 (s).


358
δ −70.12 (s).


359
δ −70.11 (s).


360
δ −70.12 (s).


361
δ −70.13 (s).


362
δ −70.11 (s).


365
δ −70.05 (s).


367
δ −70.08 (s).


369
δ −83.07 (s).


385
δ −80.30 (s).


386
δ −84.80 (s).


395
δ −80.30 (s).


396
δ −84.90 (s).


423
δ −84.80 (s).


432
δ −84.80 (s).


433
δ −70.00 (s).


443
δ −81.72 (s).


445
δ −70.10 (s).


446
δ −70.10 (s).


447
δ −70.08 (s).






a19F NMR spectra are reported in ppm relative to CF3CCl3, in CDCl3 solution unless indicated otherwise.


Couplings are designated by (s)—singlet, (t)—triplet and (m)—multiplet.
















INDEX TABLE N








Compound



No.

1H NMR Dataa





273
(CDCl3): δ 1.36-1.32 (t, 3H), 4.21 (s, 6H), 4.32-4.25 (q, 2H), 5.32 (s, 2H), 6.20 (s, 1H),



6.70 (s, 1H), 7.89 (s, 1H), 7.95 (s, 1H).


366
(DMSO-d6): δ 1.26 (t, 3H), 3.98 (s, 2H), 4.21 (q, 2H), 6.03 (s, 2H), 6.86-6.94 (m, 2H),



6.95-7.06 (m, 2H), 7.27 (s, 2H), 7.94 (s, 1H), 8.53 (s, 1H).


434
(CDCl3): δ 1.34 (t, 3H), 4.18 (s, 2H), 4.57 (q, 2H), 6.78 (s, 1H), 7.05 (s, 2H), 7.36 (s, 2H).






a1H NMR data are reported in ppm downfield from tetramethylsilane.


Couplings are designated by (s)—singlet, (t)—triplet, (q)—quartet.






Biological Examples of the Invention

General protocol for preparing test suspensions for Tests A-E: the test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at the desired concentration (in ppm) in acetone and purified water (50/50 mix by volume) containing 250 ppm of the surfactant PEG400 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests A-E.


Test A

The test solution was sprayed to the point of run-off on soybean seedlings. The following day the seedlings were inoculated with a spore suspension of Phakopsora pachyrhizi (the causal agent of Asian soybean rust) and incubated in a saturated atmosphere at 22° C. for 24 h, and then moved to a growth chamber at 22° C. for 8 days, after which time visual disease ratings were made.


Test B

The test solution was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20° C. for 24 h, and then moved to a growth chamber at 20° C. for 6 days, after which time disease ratings were made.


Test C

The test solution was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Uncinula necator (the causal agent of grape powdery mildew) and incubated in a growth chamber at 20° C. for 12 days, after which time disease ratings were made.


Test D

The test solution was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Zymoseptoria tritici (the causal agent of wheat leaf blotch) and incubated in a saturated atmosphere at 24° C. for 48 h, and then moved to a growth chamber at 20° C. for 17 days, after which time disease ratings were made.


Test E

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Blumeria graminis f. sp. tritici, (also known as Erysiphe graminis f. sp. tritici, the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20° C. for 8 days, after which time visual disease ratings were made.


Results for Tests A-E are given in Table A. In the Table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). An asterisk “*” or a double asterisk “**” or a triple asterisk “***” next to the rating value indicates a 50 ppm, 10 ppm and 250 ppm test suspension was used, respectively. A dash (-) indicates the compound was not tested.















TABLE A





Cmpd. No.
Rate in ppm
Test A
Test B
Test C
Test D
Test E





















1
250
100
91
—
97
81


2
10
77
32
—
—
—


3
10
100
0
—
—
—


4
10
100
89
100*
—
—


5
10
0
0
—
—
—


6
10
0
0
—
—
—


7
10
94
0
—
—
—


8
10
96
9
—
—
—


9
10
98
86
—
—
—


10
10
100
86
—
—
—


12
10
13
0
—
—
—


13
10
99
0
—
—
—


14
10
100
0
—
—
—


15
10
100
0
—
—
—


16
10
99
0
—
—
—


17
10
100
0
—
—
—


18
10
100
0
—
—
—


20
10
98
86
—
—
—


21
10
84
23
—
—
—


22
10
38
0
—
—
—


23
10
0
19
—
—
—


24
10
81
91
—
—
—


25
10
0
0
—
—
—


26
10
99
0
—
—
—


27
10
0
0
—
—
—


28
10
0
0
—
—
—


29
10
84
28
—
0***
79***


30
10
0
0
—
—
—


31
10
44
93
—
—
—


32
50
100
68
100**
89***
97***


33
10
96
86
—
—
—


34
10
0
80
—
—
—


35
10
99
32
—
—
—


36
10
70
0
—
—
—


37
10
99
86
—
—
—


38
10
97
89
—
—
—


39
10
91
79
—
—
—


40
10
91
68
—
—
—


41
10
92
23
—
—
—


42
10
99
85
—
—
—


43
10
96
60
—
—
—


44
10
97
85
16***
98***
91***


45
10
87
85
—
—
—


46
10
64
85
—
—
—


47
50
100
95
—
—
—


48
50
100
91
—
—
—


49
10
0
86
—
—
—


50
10
54
91
—
—
—


51
10
0
0
81***
3***
0***


52
10
99
0
—
—
—


53
50
100
67
—
—
—


54
10
0
0
—
—
—


55
10
0
0
—
—
—


56
10
38
0
—
—
—


57
250
100
0
64***
28
95***


58
10
0
0
—
—
—


60
10
0
0
—
—
—


61
10
0
0
—
—
—


62
10
0
0
—
—
—


63
10
0
0
—
—
—


64
250
100
99
100**
73
99


65
10
100
0
—
—
—


66
50
92
89
—
—
—


67
50
65
0
—
—
—


68
10
100
95
—
—
—


69
10
98
96
—
—
—


70
250
100
100
86
91
83


71
10
100
96
—
—
—


72
50
13
0
—
—
—


73
10
0
0
—
—
—


74
10
0
0
—
—
—


75
10
0
0
—
—
—


76
10
0
0
—
—
—


77
10
99
0
—
—
—


78
10
94
0
—
—
—


79
50
0
0
—
—
—


80
50
99
100
0
96***
99***


81
10
0
0
—
—
—


82
10
97
0
—
—
—


83
10
82
0
—
—
—


84
10
0
0
—
—
—


85
10
89
0
—
—
—


86
10
99
0
—
—
—


87
10
0
0
—
—
—


88
10
65
0
—
—
—


89
10
0
0
—
—
—


90
10
100
0
—
—
—


91
10
0
0
—
—
—


92
10
0
0
—
—
—


93
10
96
0
—
—
—


94
10
0
0
—
—
—


95
10
0
0
—
—
—


96
10
13
0
—
—
—


97
50
94
0
—
—
—


98
250
100
100
31
77
0


99
10
0
80
—
—
—


100
10
0
0
—
—
—


101
10
0
0
—
—
—


102
10
0
0
—
—
—


103
10
0
0
—
—
—


104
10
0
80
—
—
—


105
10
0
68
—
—
—


106
10
0
0
—
—
—


107
10
0
0
—
—
—


109
10
0
0
—
—
—


110
50
79
0
—
—
—


111
10
0
0
—
—
—


112
10
0
0
—
—
—


113
10
0
0
—
—
—


114
50
44
0
—
—
—


115
250
0
0
58
19
56


116
10
100
0
—
—
—


117
10
23
0
—
—
—


118
50
100
0
77***
13***
76***


119
10
97
0
—
—
—


120
50
100
0
23
17
98


121
10
100
0
—
—
—


122
10
0
0
—
—
—


123
10
98
0
—
—
—


124
50
100
0
100
92***
98


125
10
100
0
—
—
—


126
10
100
0
100*
—
—


127
10
100
0
100*
—
—


129
10
100
0
—
—
—


130
10
100
0
—
—
—


131
50
99
86
—
—
—


132
10
100
0
98*
—
—


133
10
79
0
—
—
—


134
10
89
32
—
—
—


135
10
86
61
—
—
—


136
10
98
83
—
—
—


137
10
79
0
—
—
—


138
10
100
0
100*
31***
99***


139
10
100
0
—
—
—


140
10
98
23
—
—
—


141
10
0
0
—
—
—


142
10
92
100
19***
100***
99***


143
10
0
0
—
—
—


144
10
78
0
—
—
—


145
10
82
0
—
—
—


146
50
60
0
—
—
—


147
50
77
0
—
—
—


148
10
0
0
—
—
—


149
10
0
0
—
—
—


150
10
33
0
—
—
—


151
10
0
0
—
—
—


152
10
0
0
—
—
—


153
10
100
0
—
—
—


154
10
0
0
—
—
—


155
10
0
0
—
—
—


156
10
0
0
—
—
—


157
10
0
9
—
—
—


158
10
0
0
—
—
—


160
10
13
0
—
—
—


161
10
100
0
—
—
—


162
10
100
0
100*
—
—


163
10
100
0
100*
—
—


164
10
31
0
—
—
—


165
10
0
0
—
—
—


166
10
100
95
—
—
—


167
10
38
0
—
—
—


168
10
0
0
—
—
—


169
10
100
0
—
—
—


170
10
100
0
100*
—
—


171
10
100
0
99*
—
—


172
10
100
0
—
—
—


173
10
0
0
—
—
—


174
10
0
0
—
—
—


175
10
0
0
—
—
—


176
10
0
0
—
—
—


177
50
100
89
—
—
—


178
10
0
0
—
—
—


179
10
0
0
—
—
—


180
10
0
0
—
—
—


181
10
0
0
—
—
—


182
10
0
0
—
—
—


183
10
0
0
70***
66***
0***


184
10
0
0
—
—
—


185
10
100
0
100*
0***
95***


186
10
100
0
100*
9***
84***


187
10
93
74
—
—
—


188
10
100
0
—
—
—


189
10
0
0
—
—
—


190
10
0
0
—
—
—


191
10
0
0
—
—
—


192
10
0
0
—
—
—


193
10
0
86
—
—
—


195
10
0
0
—
—
—


196
10
0
74
—
—
—


197
10
0
0
—
—
—


198
10
0
0
—
—
—


199
10
100
0
—
—
—


200
10
100
0
—
—
—


201
10
100
0
—
—
—


202
10
100
0
—
—
—


203
10
50
0
—
—
—


204
10
100
0
—
—
—


205
10
0
0
—
—
—


206
50
100
98
34***
93***
93***


207
10
0
0
—
—
—


209
10
89
0
—
—
—


210
10
0
0
—
—
—


211
10
0
0
—
—
—


212
10
44
0
—
—
—


214
10
0
0
—
—
—


215
10
80
55
—
—
—


216
10
100
0
20***
37***
87***


217
10
100
0
75***
23***
96***


218
10
100
0
75***
53***
90***


219
10
100
0
92***
0***
83***


220
10
100
0
85***
28***
92***


221
10
100
0
41***
10***
95***


222
10
100
0
38***
17***
90***


223
10
75
0
—
—
—


224
10
0
0
—
—
—


225
10
0
0
—
—
—


226
10
0
0
—
—
—


227
10
99
55
—
—
—


228
10
100
0
—
—
—


229
50
99
100
—
96***
99***


230
10
0
0
—
—
—


231
10
100
0
—
—
—


232
10
98
0
—
—
—


233
50
100
96
—
—
—


234
50
100
92
—
—
—


235
10
97
0
—
—
—


236
10
75
0
—
—
—


237
10
97
0
—
—
—


238
10
73
0
—
—
—


239
10
0
0
—
—
—


240
10
99
0
—
—
—


241
10
0
0
—
—
—


242
10
100
0
87***
27***
69***


243
10
100
0
29***
0***
56***


244
10
100
0
—
0***
0***


245
10
100
0
24***
18***
76***


246
10
100
0
85***
12***
90***


247
10
13
0
21***
79***
21***


248
10
71
0
62***
93***
89***


249
10
100
0
—
—
—


250
10
0
0
—
—
—


251
10
100
9
—
—
—


252
10
0
0
—
—
—


253
10
0
0
—
—
—


254
10
73
0
10***
67***
56***


255
10
89
0
93***
60***
64***


256
10
73
0
15***
95***
82***


257
10
54
0
81***
35***
92***


258
10
96
0
64***
13***
53***


259
10
25
0
31***
88***
83***


260
10
0
0
—
—
—


261
10
0
0
—
—
—


262
10
100
0
99*
—
—


263
10
100
0
100*
—
—


264
10
99
80
—
95***
96***


265
50
100
0
98
—
—


266
50
86
74
—
—
—


267
10
94
0
—
—
—


268
10
99
0
—
—
—


269
10
100
0
—
—
—


270
10
25
0
—
—
—


271
10
0
0
—
—
—


272
10
100
0
—
—
—


273
50
100
0
49***
20***
65***


274
10
48
0
—
—
—


275
10
0
0
—
—
—


276
10
13
0
100*
53***
86***


277
10
50
45
—
—
—


278
50
94
0
—
—
—


279
50
0
0
—
—
—


280
50
100
100
—
99***
99***


281
50
95
98
—
—
—


282
50
0
0
—
—
—


283
50
100
99
—
—
—


284
10
100
0
—
—
—


285
10
100
0
—
—
—


286
10
87
55
—
—
—


287
50
77
0
—
—
—


288
50
96
0
—
—
—


289
10
0
0
—
—
—


290
50
50
19
—
—
—


291
10
100
0
—
—
—


292
10
100
0
—
—
—


293
10
100
0
—
—
—


294
10
100
0
—
—
—


295
50
99
80
—
—
—


296
10
0
0
—
—
—


297
10
100
0
—
—
—


298
10
0
0
—
—
—


299
10
100
0
—
—
—


300
10
100
0
—
—
—


301
50
100
0
100*
—
—


302
50
99
0
—
—
—


303
50
0
0
—
—
—


304
50
96
0
—
—
—


305
10
70
0
—
—
—


306
50
96
68
—
—
—


307
50
0
0
—
—
—


308
50
25
0
—
—
—


309
10
100
0
—
—
—


310
10
100
0
—
—
—


311
10
0
0
—
—
—


312
10
0
0
—
—
—


313
50
0
0
—
—
—


314
50
0
0
—
—
—


316
50
100
9
100
2
73


317
50
0
0
—
—
—


318
10
100
0
—
—
—


319
50
100
41
—
—
—


320
10
89
68
—
81***
91***


321
10
100
0
—
—
—


322
10
99
86
48***
100***
97***


323
50
100
0
—
—
—


324
10
0
0
—
—
—


325
10
100
0
—
—
—


326
10
100
0
—
—
—


327
10
100
0
—
—
—


328
10
100
0
—
—
—


329
50
100
41
—
—
—


330
10
100
0
—
—
—


331
10
100
0
—
—
—


332
10
100
0
—
—
—


333
10
100
0
—
—
—


334
10
100
0
—
—
—


335
10
100
0
—
—
—


336
10
100
0
—
—
—


337
10
100
0
—
—
—


338
10
100
0
—
—
—


339
10
100
0
—
—
—


340
10
100
0
—
—
—


341
10
100
0
—
—
—


342
10
100
0
—
—
—


343
10
0
0
—
—
—


344
50
100
0
—
—
—


345
10
0
0
—
—
—


346
10
0
0
—
—
—


347
50
100
0
—
—
—


348
10
100
0
—
—
—


349
10
100
0
—
—
—


350
10
100
0
—
—
—


351
10
100
0
—
—
—


352
10
100
0
—
—
—


353
50
0
0
—
—
—


354
10
100
0
—
—
—


355
10
100
0
—
—
—


356
10
100
0
—
—
—


357
10
100
9
—
—
—


358
10
100
0
—
—
—


359
10
100
0
—
—
—


360
10
100
0
—
—
—


361
10
100
0
—
—
—


362
10
100
0
—
—
—


364
50
100
0
100
0
56


365
10
100
0
—
—
—


366
10
79
55
—
—
—


367
10
0
0
—
—
—


368
50
0
0
33***
0***
0***


369
—
—
—
—
—
—


370
10
0
0
—
—
—


371
50
0
77
—
—
—


372
50
97
28
—
99***
99***


373
50
81
0
56***
99***
98***


374
50
0
0
—
0***
76***


375
50
100
0
66***
95***
99***


376
50
100
92
36
98***
99***


377
10
44
0
—
—
—


378
10
0
0
—
—
—


379
50
0
0
93***
0***
21***


380
10
0
0
—
0***
56***


381
10
25
28
—
0***
69***


382
50
0
0
22***
4***
56***


383
50
0
0
74***
0***
0***


384
50
99
83
—
48***
87***


385
50
100
68
—
—
—


386
10
84
19
—
—
—


387
—
—
—
—
—
—


388
—
—
—
—
—
—


389
—
—
—
—
—
—


390
50
0
—
—
—
—


391
50
0
—
—
—
—


392
10
97
19
—
—
—


393
50
38
0
63***
69***
0***


394
50
0
0
75***
24***
0***


395
50
100
100
100
—
—


396
50
31
19
—
—
—


398
10
0
0
—
—
—


399
50
97
0
—
—
—


400
50
100
0
—
—
—


401
10
0
0
35***
0***
0***


402
50
97
—
48***
5***
0***


403
50
54
—
74***
17***
0***


404
50
0
0
44***
11***
0***


405
50
0
0
—
—
—


406
50
0
0
—
—
—


407
50
0
0
—
—
—


408
50
44
0
—
—
—


409
—
—
—
—
—
—


410
10
100
0
88***
11***
13***


411
50
87
0
—
—
—


412
50
100
0
—
—
—


413
10
0
0
61***
90***
35***


414
10
45
0
91***
97***
90***


415
10
0
0
9***
0***
0***


416
50
81
0
34***
0***
0***


417
10
0
0
—
—
—


418
10
0
0
—
—
—


419
10
0
0
—
—
—


420
10
0
0
—
—
—


421
10
0
0
—
—
—


422
50
100
84
—
—
—


423
50
87
80
—
—
—


424
10
97
41
—
—
—


425
10
100
0
—
—
—


426
10
0
0
45***
2***
43***


427
10
13
0
5***
53***
29***


428
10
0
0
43***
2***
0***


430
50
100
0
82***
3***
99***


431
250
—
—
36
93
96


432
50
100
98
—
—
—


433
50
0
0
—
—
—


434
50
0
0
—
—
—


435
50
96
0
45***
5***
81***


436
50
99
0
48***
—
0***


437
50
77
0
77***
78***
69***


438
50
73
0
59***
26***
98***


439
—
—
—
—
—
—


440
—
—
—
—
—
—


441
—
—
—
—
—
—


442
50
0
0
—
—
—


443
50
48
0
—
—
—


444
—
—
—
—
—
—


445
50
38
0
—
—
—


446
10
98
0
—
—
—


447
10
0
0
—
—
—


448
10
0
0
—
—
—


449
50
99
0
—
—
—


450
50
97
0
—
—
—


451
50
0
0
—
—
—


452
—
—
—
—
—
—


453
10
0
0
—
—
—


454
10
100
0
100
—
—


455
50
99
86
34
43
0


456
50
99
93
6
80
98***


457
250
89**
0**
73
7
0


458
10
100
0
25***
41***
94***


459
50
100
97
—
37***
0***


460
—
—
—
—
—
—


461
50
0
0
—
53***
69***


462
10
0
0
—
—
—


463
10
0
0
—
—
—


464
50
100
0
73***
4***
99***


465
50
100
100
73***
59***
91***









The test results presented above in Table A for compounds of Formula 1 illustrate the fungicidal activity of component (a) contributing to the plant disease control utility of compositions comprising component (a) in combination with component (b) and optionally at least one additional fungicidal compound according to the present invention.


TEST F below demonstrates the control efficacy of compositions of this invention on Asian soybean rust. The general protocol for preparing test compositions for Test F was as follows: Compound 32, Compound 64, azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole and trifloxystrobin were obtained as unformulated, technical-grade materials. Copper hydroxide and mancozeb was obtained as a formulated product marketed under the trademarks KOCIDE 3000 and MANZATE, respectively. Unformulated materials were first dissolved in acetone and then suspended at the desired concentration (in ppm) in acetone and purified water (50/50 mix by volume) containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). Formulated materials were dispersed in sufficient water to give the desired concentration, and neither organic solvent nor surfactant was added to the suspension. The resulting test mixtures were then used in Test F. The tests were run on four individual plants and the results reported as the mean average of the four plants.


The presence of a synergistic effect between two active ingredients was established with the aid of the Colby equation (see Colby, S. R. “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds, (1967), 15, 20-22):







p
=

A
+
B
-

[


A
×
B


1
⁢
0
⁢
0


]



.




Using the method of Colby, the presence of a synergistic interaction between two active ingredients is established by first calculating the predicted activity, p, of the mixture based on activities of the two components applied alone. If p is lower than the experimentally established effect, synergism has occurred. In the equation above, A is the fungicidal activity in percentage control of one component applied alone at rate x. The B term is the fungicidal activity in percentage control of the second component applied at rate y. The equation estimates p, the expected fungicidal activity of the mixture of A at rate x with B at rate y if their effects are strictly additive and no interaction has occurred.


Test F

The test mixture was sprayed to the point of run-off on soybean seedlings. The following day the seedlings were inoculated with a spore suspension of Phakopsora pachyrhizi (the causal agent of Asian soybean rust) and incubated in a saturated atmosphere at 22° C. for 24 h and then moved to a growth chamber at 22° C. for 8 days, after which time visual disease ratings were made.


Results for Test F are given in Tables B-1 through I-1 for Compound 32 and Tables B-2 through I-2 for Compound 64. Each table corresponds to a set of evaluations performed together at the same time. In each table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). Columns labeled “Obsd” indicate the average of results observed from test run on four individual plants. Columns labeled “Exp” indicate the expected value for each treatment mixture using the Colby equation.









TABLE B-1







Observed and Expected Effects of Compound 32 Alone and Mixtures with Picoxystrobin


in Controlling Asian Soybean Rust











Application Rate (ppm)














of Compound 32 (i.e.

Application Rate (ppm)
Test F











Component (a))
Component (b)
of Component (b)
Obsd
Exp














0
None
0
 0
—


1.422
None
0
55
—


2.276
None
0
64
—


0
picoxystrobin
20.596
73
—


0
picoxystrobin
33.865
75
—


1.422
picoxystrobin
20.596
75
88


1.422
picoxystrobin
33.865
66
89


2.276
picoxystrobin
20.596
66
90


2.276
picoxystrobin
33.865
72
91
















TABLE B-2







Observed and Expected Effects of Compound 64 Alone and Mixtures


with Picoxystrobin in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 64
Component
(ppm) of
Test F











(i.e. Component (a))
(b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
53
—


0.489
None
0
68
—


0
picoxystrobin
20.596
73
—


0
picoxystrobin
33.865
75
—


0.303
picoxystrobin
20.596
59
87


0.303
picoxystrobin
33.865
67
88


0.489
picoxystrobin
20.596
65
91


0.489
picoxystrobin
33.865
72
92
















TABLE C-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Bixafen, Fluxapyroxad


and Fluindapyr in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
39
—


2.276
None
0
44
—


0
bixafen
11.327
54
—


0
bixafen
19.525
55
—


1.422
bixafen
11.327
64
72


1.422
bixafen
19.525
59
72


2.276
bixafen
11.327
56
75


2.276
bixafen
19.525
59
74


0
fluxapyroxad
2.757
19
—


0
fluxapyroxad
4.748
52
—


1.422
fluxapyroxad
2.757
68
50


1.422
fluxapyroxad
4.748
74
70


2.276
fluxapyroxad
2.757
72
54


2.276
fluxapyroxad
4.748
82
73


0
fluindapyr
8.820
61
—


0
fluindapyr
15.230
79
—


1.422
fluindapyr
8.820
50
76


1.422
fluindapyr
15.230
51
87


2.276
fluindapyr
8.820
64
78


2.276
fluindapyr
15.230
71
88
















TABLE C-2







Observed and Expected Effects of Compound 64 Alone


and Mixtures with Bixafen, Fluxapyroxad and


Fluindapyr in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
34
—


0.489
None
0
63
—


0
bixafen
11.327
54
—


0
bixafen
19.525
55
—


0.303
bixafen
11.327
35
70


0.303
bixafen
19.525
66
69


0.489
bixafen
11.327
13
83


0.489
bixafen
19.525
53
83


0
fluxapyroxad
2.757
19
—


0
fluxapyroxad
4.748
52
—


0.303
fluxapyroxad
2.757
27
46


0.303
fluxapyroxad
4.748
54
68


0.489
fluxapyroxad
2.757
53
70


0.489
fluxapyroxad
4.748
48
82


0
fluindapyr
8.820
61
—


0
fluindapyr
15.230
79
—


0.303
fluindapyr
8.820
64
74


0.303
fluindapyr
15.230
72
86


0.489
fluindapyr
8.820
61
86


0.489
fluindapyr
15.230
65
92
















TABLE D-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Mancozeb, Fenpropimorph and


Tebuconazole in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
52
—


2.276
None
0
60
—


0
mancozeb
42.532
70
—


0
mancozeb
74.012
71
—


1.422
mancozeb
42.532
94
86


1.422
mancozeb
74.012
91
86


2.276
mancozeb
42.532
94
88


2.276
mancozeb
74.012
73
88


0
fenpropimorph
242.823
33
—


0
fenpropimorph
458.587
44
—


1.422
fenpropimorph
242.823
73
68


1.422
fenpropimorph
458.587
67
73


2.276
fenpropimorph
242.823
79
73


2.276
fenpropimorph
458.587
91
78


0
tebuconazole
486.921
30
—


0
tebuconazole
841.166
55
—


1.422
tebuconazole
486.921
52
66


1.422
tebuconazole
841.166
76
78


2.276
tebuconazole
486.921
64
72


2.276
tebuconazole
841.166
72
82
















TABLE D-2







Observed and Expected Effects of Compound 64


Alone and Mixtures with Mancozeb, Fenpropimorph and


Tebuconazole in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
49
—


0.489
None
0
63
—


0
mancozeb
42.532
70
—


0
mancozeb
74.012
71
—


0.303
mancozeb
42.532
83
85


0.303
mancozeb
74.012
82
85


0.489
mancozeb
42.532
92
89


0.489
mancozeb
74.012
92
89


0
fenpropimorph
242.823
33
—


0
fenpropimorph
458.587
44
—


0.303
fenpropimorph
242.823
64
66


0.303
fenpropimorph
458.587
94
72


0.489
fenpropimorph
242.823
88
75


0.489
fenpropimorph
458.587
92
79


0
tebuconazole
486.921
30
—


0
tebuconazole
841.166
55
—


0.303
tebuconazole
486.921
48
65


0.303
tebuconazole
841.166
54
77


0.489
tebuconazole
486.921
50
74


0.489
tebuconazole
841.166
66
83
















TABLE E-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Cyproconazole, Azoxystrobin and


Trifloxystrobin in Controlling Asian Soybean Rust











Application

Application




Rate (ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
78
—


2.276
None
0
80
—


0
cyproconazole
37.333
44
—


0
cyproconazole
64.883
68
—


1.422
cyproconazole
37.333
80
87


1.422
cyproconazole
64.883
82
93


2.276
cyproconazole
37.333
87
88


2.276
cyproconazole
64.883
87
93


0
azoxystrobin
95.873
70
—


0
azoxystrobin
169.226
88
—


1.422
azoxystrobin
95.873
85
93


1.422
azoxystrobin
169.226
90
97


2.276
azoxystrobin
95.873
87
94


2.276
azoxystrobin
169.226
86
98


0
trifloxystrobin
20.511
69
—


0
trifloxystrobin
35.310
86
—


1.422
trifloxystrobin
20.511
79
93


1.422
trifloxystrobin
35.310
94
97


2.276
trifloxystrobin
20.511
92
94


2.276
trifloxystrobin
35.310
94
97
















TABLE E-2







Observed and Expected Effects of Compound 64


Alone and Mixtures with Cyproconazole, Azoxystrobin


and Trifloxystrobin in Controlling Asian Soybean Rust











Application

Application




Rate (ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
78
—


0.489
None
0
77
—


0
cyproconazole
37.333
44
—


0
cyproconazole
64.883
68
-—


0.303
cyproconazole
37.333
82
88


0.303
cyproconazole
64.883
80
93


0.489
cyproconazole
37.333
86
87


0.489
cyproconazole
64.883
90
93


0
azoxystrobin
95.873
70
—


0
azoxystrobin
169.226
88
—


0.303
azoxystrobin
95.873
84
93


0.303
azoxystrobin
169.226
85
97


0.489
azoxystrobin
95.873
91
93


0.489
azoxystrobin
169.226
87
97


0
trifloxystrobin
20.511
69
—


0
trifloxystrobin
35.310
86
—


0.303
trifloxystrobin
20.511
90
93


0.303
trifloxystrobin
35.310
87
97


0.489
trifloxystrobin
20.511
86
93


0.489
trifloxystrobin
35.310
82
97
















TABLE F-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Epoxiconazole and


Pydiflumetofen in Controlling Asian Soybean Rust











Application

Application




Rate (ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
75
—


2.276
None
0
77
—


0
epoxiconazole
46.795
23
—


0
epoxiconazole
89.631
70
—


1.422
epoxiconazole
46.795
76
81


1.422
epoxiconazole
89.631
79
92


2.276
epoxiconazole
46.795
81
82


2.276
epoxiconazole
89.631
88
93


0
pydiflumetofen
70.950
0
—


0
pydiflumetofen
135.850
73
—


1.422
pydiflumetofen
70.950
61
75


1.422
pydiflumetofen
135.850
81
93


2.276
pydiflumetofen
70.950
84
77


2.276
pydiflumetofen
135.850
76
94
















TABLE F-2







Observed and Expected Effects of Compound 64


Alone and Mixtures with Epoxiconazole and


Pydiflumetofen in Controlling Asian Soybean Rust











Application

Application




Rate (ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
37
—


0.489
None
0
68
—


0
epoxiconazole
46.795
23
—


0
epoxiconazole
89.631
70
—


0.303
epoxiconazole
46.795
58
52


0.303
epoxiconazole
89.631
68
81


0.489
epoxiconazole
46.795
69
76


0.489
epoxiconazole
89.631
73
90


0
pydiflumetofen
70.950
0
—


0
pydiflumetofen
135.850
73
—


0.303
pydiflumetofen
70.950
47
37


0.303
pydiflumetofen
135.850
66
83


0.489
pydiflumetofen
70.950
63
68


0.489
pydiflumetofen
135.850
63
92
















TABLE G-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Benzovindiflupyr, Prothioconazole


and Chlorothalonil in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
39
—


2.276
None
0
61
—


0
benzovindiflupyr
0.606
67
—


0
benzovindiflupyr
0.980
67
—


1.422
benzovindiflupyr
0.606
70
80


1.422
benzovindiflupyr
0.980
80
80


2.276
benzovindiflupyr
0.606
76
87


2.276
benzovindiflupyr
0.980
80
87


0
prothioconazole
10.165
7
—


0
prothioconazole
16.339
65
—


1.422
prothioconazole
10.165
72
43


1.422
prothioconazole
16.339
47
79


2.276
prothioconazole
10.165
71
64


2.276
prothioconazole
16.339
87
86


0
chlorothalonil
138.129
59
—


0
chlorothalonil
222.081
85
—


1.422
chlorothalonil
138.129
50
75


1.422
chlorothalonil
222.081
88
91


2.276
chlorothalonil
138.129
57
84


2.276
chlorothalonil
222.081
88
94
















TABLE G-2







Observed and Expected Effects of Compound 64


Alone and Mixtures with Benzovindiflupyr, Prothioconazole


and Chlorothalonil in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
52
—


0.489
None
0
50
—


0
benzovindiflupyr
0.606
67
—


0
benzovindiflupyr
0.980
67
—


0.303
benzovindiflupyr
0.606
83
84


0.303
benzovindiflupyr
0.980
79
84


0.489
benzovindiflupyr
0.606
73
83


0.489
benzovindiflupyr
0.980
86
84


0
prothioconazole
10.165
7
—


0
prothioconazole
16.339
65
—


0.303
prothioconazole
10.165
61
55


0.303
prothioconazole
16.339
69
83


0.489
prothioconazole
10.165
60
53


0.489
prothioconazole
16.339
73
82


0
chlorothalonil
138.129
59
—


0
chlorothalonil
222.081
85
—


0.303
chlorothalonil
138.129
34
81


0.303
chlorothalonil
222.081
89
93


0.489
chlorothalonil
138.129
65
79


0.489
chlorothalonil
222.081
91
92
















TABLE H-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Pydiflumetofen, Pyraclostrobin


and Metominostrobin in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
69
—


2.276
None
0
63
—


0
pydiflumetofen
41.364
49
—


0
pydiflumetofen
128.793
36
—


1.422
pydiflumetofen
41.364
67
84


1.422
pydiflumetofen
128.793
72
80


2.276
pydiflumetofen
41.364
76
81


2.276
pydiflumetofen
128.793
83
76


0
pyraclostrobin
45.860
35
—


0
pyraclostrobin
137.503
45
—


1.422
pyraclostrobin
45.860
43
80


1.422
pyraclostrobin
137.503
65
83


2.276
pyraclostrobin
45.860
55
76


2.276
pyraclostrobin
137.503
78
79


0
metominostrobin
29.673
13
—


0
metominostrobin
86.003
37
—


1.422
metominostrobin
29.673
65
73


1.422
metominostrobin
86.003
52
80


2.276
metominostrobin
29.673
63
67


2.276
metominostrobin
86.003
82
76
















TABLE H-2







Observed and Expected Effects of Compound 64


Alone and Mixtures with Pydiflumetofen, Pyraclostrobin


and Metominostrobin in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
50
—


0.489
None
0
70
—


0
pydiflumetofen
41.364
49
—


0
pydiflumetofen
128.793
36
—


0.303
pydiflumetofen
41.364
64
75


0.303
pydiflumetofen
128.793
78
68


0.489
pydiflumetofen
41.364
71
84


0.489
pydiflumetofen
128.793
67
81


0
pyraclostrobin
45.860
35
—


0
pyraclostrobin
137.503
45
—


0.303
pyraclostrobin
45.860
70
68


0.303
pyraclostrobin
137.503
80
73


0.489
pyraclostrobin
45.860
68
80


0.489
pyraclostrobin
137.503
59
83


0
metominostrobin
29.673
13
—


0
metominostrobin
86.003
37
—


0.303
metominostrobin
29.673
52
57


0.303
metominostrobin
86.003
69
69


0.489
metominostrobin
29.673
46
74


0.489
metominostrobin
86.003
66
81
















TABLE I-1







Observed and Expected Effects of Compound 32


Alone and Mixtures with Copper hydroxide, Flutriafol


and Fenpropidin in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 32 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


1.422
None
0
63
—


2.276
None
0
71
—


0
copper hydroxide
3610.778
87
—


0
copper hydroxide
7371.507
65
—


1.422
copper hydroxide
3610.778
84
95


1.422
copper hydroxide
7371.507
81
87


2.276
copper hydroxide
3610.778
93
96


2.276
copper hydroxide
7371.507
87
90


0
flutriafol
544.265
13
—


0
flutriafol
1124.021
52
—


1.422
flutriafol
544.265
82
68


1.422
flutriafol
1124.021
87
82


2.276
flutriafol
544.265
75
75


2.276
flutriafol
1124.021
88
86


0
fenpropidin
78.393
45
—


0
fenpropidin
161.740
68
—


1.422
fenpropidin
78.393
48
80


1.422
fenpropidin
161.740
80
88


2.276
fenpropidin
78.393
83
84


2.276
fenpropidin
161.740
87
91
















TABLE I-2







Observed and Expected Effects of Compound 64


Alone and Mixtures with Copper Hydroxide, Flutriafol


and Fenpropidin in Controlling Asian Soybean Rust











Application Rate

Application




(ppm) of

Rate












Compound 64 (i.e.

(ppm) of
Test F











Component (a))
Component (b)
Component (b)
Obsd
Exp














0
None
0
0
—


0.303
None
0
50
—


0.489
None
0
81
—


0
Copper Hydroxide
3610.778
87
—


0
Copper Hydroxide
7371.507
65
—


0.303
Copper Hydroxide
3610.778
79
93


0.303
Copper Hydroxide
7371.507
82
83


0.489
Copper Hydroxide
3610.778
86
97


0.489
Copper Hydroxide
7371.507
84
93


0
flutriafol
544.265
13
—


0
flutriafol
1124.021
52
—


0.303
flutriafol
544.265
65
56


0.303
flutriafol
1124.021
74
76


0.489
flutriafol
544.265
75
83


0.489
flutriafol
1124.021
75
91


0
fenpropidin
78.393
45
—


0
fenpropidin
161.740
68
—


0.303
fenpropidin
78.393
37
72


0.303
fenpropidin
161.740
77
84


0.489
fenpropidin
78.393
75
90


0.489
fenpropidin
161.740
82
94








Claims
  • 1. A fungicidal composition comprising: (a) at least one compound selected from the compounds of Formula 1, N-oxides, and salts thereof:
  • 2. The composition of claim 1 wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein R1 is CF3, CCl3 or CF2Cl;W is O;R5a and R5b are each independently H, hydroxy or methyl;R2a and R2b are each independently H or methyl; orR2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is selected from C(═O), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members;R2c is C1-C2 alkyl, C2-C3 alkenyl or C2-C3 alkynyl;R2d is H or methyl;A1 is CR6cR6d or O;A2 is a direct bond, CR6eR6f or O;R6a, R6b, R6c, R6d, R6e and R6f are each independently H, cyano, hydroxy, Br, Cl, F or methyl;J is J-1, J-6 or J-14;each R8 is independently F, Cl or methyl;each R9a and R9b is independently H, halogen or methyl;n is 0, 1 or 2;E1 is C1-C6 alkoxy, C1-C6 alkylsulfonyl, C2-C6 alkylcarbonyl or C2-C6 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b;R10a is phenyl optionally substituted with up to 2 substituents independently selected from R11a; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members and R11b on nitrogen atom ring members;each R10b is independently halogen, hydroxy, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylsulfonyl, C2-C4 alkylcarbonyl or C2-C5 alkoxycarbonyl;each R11a is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C3 alkoxycarbonyl;each R11b is independently methyl, methoxy, methylcarbonyl or methoxycarbonyl;G is selected from the group consisting of:
  • 3. The composition of claim 2 wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein T is T-2 or T-3;R1 is CF3;X is O;Y is O;R2a and R2b are each independently H or methyl; orR2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member;R2c is methyl or ethyl;R2d is H;A1 is O;A2 is a direct bond or CH2;R6a and R6b are each independently H, cyano hydroxy or methyl;J is J-1 or J-6;q is 0 or 1;each R9a and R9b is independently H or methyl;E1 is C1-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a and up to 3 substituents independently selected from R10b;R10a is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members;each R10b is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C4 alkoxycarbonyl;G is G-1, G-3, G-12 or G-22;x is 1 or 2;each R13 is independently C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkenyloxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R19;each R14a is independently H or C1-C2 alkyl;each R14b is independently H, C1-C3 alkyl, C1-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl;each R19 is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl;each U is independently a direct bond or C(═O)O;each V is independently a direct bond or CH2;each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R27;each R27 is independently halogen, methyl or methoxy; andZ is a direct bond, O, NH, C(═O), C(═O)NH or NHC(═O).
  • 4. The composition of claim 3 wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein R2a and R2b are each H; orR2a and R2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms;A2 is a direct bond;R6a and R6b are each H;R8 is F or C1;L is a direct bond, CH2 or CH2CH2;E1 is C1-C2 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R10a;R10a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R11a on carbon atom ring members;each R11a is independently methoxycarbonyl or ethoxycarbonyl;G is G-1 and the 2-position of G-1 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13;x is 1;R13 is C(═O)NR14aR14b or —U—V-Q; or C2-C5 alkoxycarbonyl, C3-C5 alkynyloxycarbonyl or C4-C6 cycloalkoxycarbonyl, each optionally substituted with up to 1 substituent selected from R19;R14a is H;R14b is H, methyl or cyclopropylmethyl;R19 is cyano, halogen, cyclopropyl or methoxy;U is C(═O)O;V is CH2;Q is phenyl optionally substituted with up to 2 substituents independently selected from R27; andZ is a direct bond, O, NH or C(═O).
  • 5. The composition of claim 4 wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein R8 is F;L is a direct bond or CH2;E1 is methoxy substituted with 1 substituent selected from R10a;R10a is pyrazolyl optionally substituted with up to 1 substituent selected from R11a on a carbon atom ring member;G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R13; andR13 is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from R19;R19 is cyano, Cl, F, cyclopropyl or methoxy; andZ is a direct bond.
  • 6. The composition of claim 5 wherein component (a) comprises a compound of Formula 1 or salt thereof, wherein J is J-1;q is 0;L is CH2;E is E2;G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R13; andR13 is methoxycarbonyl or ethoxycarbonyl.
  • 7. The composition of claim 1 wherein component (a) comprises a compound selected from the group consisting of ethyl 1-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-3-carboxylate;ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]-3-fluorophenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[[3-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenoxy]methyl]-1H-pyrazole-4-carboxylate;N-(cyclopropylmethyl)-2-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]-methyl]thiazole-4-carboxamide;2-methylpropyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;cyclopropylmethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[2-[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]ethyl]-1H-pyrazole-4-carboxylate;2-methoxyethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;2-butyn-1-yl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;3-cyanopropyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;phenylmethyl 1-[[4-1[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;butyl 1-[[4-1[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;3-chloropropyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;methyl 4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenylcarboxylate;ethyl 1-[[3-fluoro-4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]methyl]-1H-pyrazole-4-carboxylate;ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenylmethoxy]methyl]-1H-pyrazole-4-carboxylate;methyl 1-[[3-1[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate; andpropyl 1-[[3-1[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-carboxylate.
  • 8. The composition of any one of claims 1 through 7 wherein component (b) includes at least one fungicidal compound selected from the group consisting of: (b1) methyl benzimidazole carbamate (MBC) fungicides;(b2) dicarboximide fungicides;(b3) demethylation inhibitor (DMI) fungicides;(b4) phenylamide (PA) fungicides;(b5) amine/morpholine fungicides;(b6) phospholipid biosynthesis inhibitor fungicides;(b7) succinate dehydrogenase inhibitor (SDHI) fungicides;(b8) hydroxy(2-amino-)pyrimidine fungicides;(b9) anilinopyrimidine (AP) fungicides;(b10) N-phenyl carbamate fungicides;(b11) quinone outside inhibitor (QoI) fungicides;(b12) phenylpyrrole (PP) fungicides;(b13) azanaphthalene fungicides;(b14) cell peroxidation inhibitor fungicides;(b15) melanin biosynthesis inhibitor-reductase (MBI-R) fungicides;(b16a) melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides;(b16b) melanin biosynthesis inhibitor-polyketide synthase (MBI-P) fungicides;(b17) keto reductase inhibitor (KRI) fungicides;(b18) squalene-epoxidase inhibitor fungicides;(b19) polyoxin fungicides;(b20) phenylurea fungicides;(b21) quinone inside inhibitor (QiI) fungicides;(b22) benzamide and thiazole carboxamide fungicides;(b23) enopyranuronic acid antibiotic fungicides;(b24) hexopyranosyl antibiotic fungicides;(b25) glucopyranosyl antibiotic: protein synthesis fungicides;(b26) glucopyranosyl antibiotic fungicides;(b27) cyanoacetamideoxime fungicides;(b28) carbamate fungicides;(b29) oxidative phosphorylation uncoupling fungicides;(b30) organo tin fungicides;(b31) carboxylic acid fungicides;(b32) heteroaromatic fungicides;(b33) phosphonate fungicides;(b34) phthalamic acid fungicides;(b35) benzotriazine fungicides;(b36) benzene-sulfonamide fungicides;(b37) pyridazinone fungicides;(b38) thiophene-carboxamide fungicides;(b39) complex I NADH oxido-reductase inhibitor fungicides;(b40) carboxylic acid amide (CAA) fungicides;(b41) tetracycline antibiotic fungicides;(b42) thiocarbamate fungicides;(b43) benzamide fungicides;(b44) microbial fungicides;(b45) quinone outside inhibitor, stigmatellin binding (QoSI) fungicides;(b46) plant extract fungicides;(b47) cyanoacrylate fungicides;(b48) polyene fungicides;(b49) oxysterol binding protein inhibitor (OSBPI) fungicides;(b50) aryl-phenyl-ketone fungicides;(b51) host plant defense induction fungicides;(b52) multi-site activity fungicides;(b53) biologicals with multiple modes of action;(b54) fungicides other than fungicides of component (a) and components (b1) through (b53); and salts of compounds of (b1) through (b54).
  • 9. The composition of claim 8 wherein component (b) comprises at least one fungicidal compound from each of two different groups selected from (b1) through (b54).
  • 10. The composition of any one of claims 1 through 7 wherein component (b) includes at least one compound selected from acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl, benalaxyl-M, benodanil, benomyl, benthiavalicarb, benthiavalicarb-isopropyl, benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, carboxin, carpropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper hydroxide, copper salts, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M, dinocap, dithianon, dodemorph, dodine, edifenphos, enestroburin, epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine, fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluindapyr, flumetover, flumorph, fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-aluminum, fuberidazole, furalaxyl, furametpyr, hexaconazole, hymexazol, guazatine, imazalil, imibenconazole, iminoctadine, iodocarb, ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb, mepronil, meptyldinocap, metalaxyl, metalaxyl-M, metconazole, methasulfocarb, metiram, metominostrobin, mepanipyrim, metrafenone, myclobutanil, naftifine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone, ofurace, orysastrobin, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron, penflufen, penthiopyrad, pefurazoate, phosphorous acid and salts thereof, phthalide, picoxystrobin, piperalin, polyoxin, probenazole, prochloraz, procymidone, propamocarb, propamocarb-hydrochloride, propiconazole, propineb, proquinazid, prothiocarb, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone, pyrisoxazole, pyroquilon, pyrrolnitrin, quinomethionate, quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole, tebufloquin, tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl, tolylfluanid, tolnifanide, triadimefon, triadimenol, triazoxide, tricyclazole, tridemorph, triflumizole, tricyclazole, trifloxystrobin, triforine, trimorphamide, triticonazole, uniconazole, validamycin, valifenalate, vinclozolin, zineb, ziram, zoxamide, N-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, 5-chloro-6-(2,4,6-trifluorophenyl)-7-(4-methylpiperidin-1-yl) [1,2,4]triazolo[1,5a]pyrimidine (DPX-BAS600F), N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxy-phenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide, N-[2-[4-[[3-(4-chloro-phenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]-butanamide, 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]-methyl]propyl]carbamate, N-[[(cyclopropylmethoxy)amino] [6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide, α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]methyl]benzeneacetamide, N-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, 2-[[[[3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide and 1-[(2-propenylthio)carbonyl]-2-(1-methyl-ethyl)-4-(2-methylphenyl)-5-amino-1H-pyrazol-3-one, 5-ethyl-6-octyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-ylamine.
  • 11. The composition of claim 10 wherein component (b) includes at least one compound selected from azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, mancozeb, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole and trifloxystrobin.
  • 12. A composition comprising: (a) at least one compound selected from the compounds of Formula 1 as defined in claim 1, N-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.
  • 13. A composition comprising the composition of any one of claims 1 through 12 and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • 14. A method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of the composition of any one of claims 1 through 13 to the plant or plant seed.
  • 15. A method for protecting a plant from a rust disease comprising applying to the plant a fungicidally effective amount of the composition of any one of claims 1 through 13 wherein component (b) includes at least one fungicidal compound selected from (b11) quinone outside inhibitor fungicides, (b3) demethylation inhibitor fungicides, (b5) amine/morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b11) quinone outside inhibitor (QoI) fungicides, (b13) methyl benzimidazole carbamate fungicides and (b52) multi-site activity fungicides.
PCT Information
Filing Document Filing Date Country Kind
PCT/US2021/021806 3/11/2021 WO
Provisional Applications (1)
Number Date Country
62991306 Mar 2020 US