Novel alpha-sulfin-and alpha-sulfonamino acid amides

Abstract

The invention relates to novel pesticidally active α-sulfin- and α-sulfonamino acid amides of the general formula (I) including the optical isomers thereof and mixtures of such isomers, wherein n is a number zero or one; R1-R9 have the meanings given in the specification R10 is either hydrogen, (a), (b), (c), (d) or (e) wherein R13, R14, R16, R17 and R19 are each independently hydrogen or C1-C4 alkyl, R15 is C4-C12 alkyl; C1-C12 halogenalkyl; C3-C8 cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl, R18 is optionally substituted aryl or optionally substituted heteroaryl; and Z is oxygen, sulfur —CR20R21— or —NR22—, wherein R20, R21 and R22 independently of each other are hydrogen of C1-C4 alkyl; provided that when R8 is hydrogen, R9 is not C1-C6-alkoxy, C3-C6 alkenyloxy or C3-C6-alkynyloxy in position 3 of the phenyl ring carrying these radicals. The novel compounds possess plant-protecting properties and are suitable for protecting plants against infestation by phytopathogenic microorganisms.

Description

[0001] The present invention relates to novel α-sulfin- and α-sulfonamino acid amides of formula I below. It relates to the preparation of those substances and to agrochemical compositions comprising at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or of the compositions in controlling or preventing the infestation of plants by phytopathogenic microorganisms, especially fungi.

[0002] The invention relates to α-sulfin- and α-sulfonamino acid amides of the general formula I 1

[0003] including the optical isomers thereof and mixtures of such isomers,

[0004] wherein

[0005] n is a number zero or one;

[0006] R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfonyl, C3-C8cycloalkyl, cyano, C1-C6alkoxycarbonyl, C3-C6alkenyloxycarbonyl or C3-C6alkynyloxycarbonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other C1-C6alkyl, or together are tetra- or penta-methylene;

[0007] R2 and R3 are each independently hydrogen; C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl; or the two groups R2 and R3 together with the carbon atom to which they are bonded form a three- to eight-membered hydrocarbon ring;

[0008] R4, R5, R6 and R7 are each independently hydrogen or C1-C4alkyl;

[0009] R8 is hydrogen or an organic radical;

[0010] R9 is an organic radical;

[0011] R10 is either hydrogen, 2

[0012] wherein

[0013] R13, R14, R16, R17 and R19 are each independently hydrogen or C1-C4alkyl,

[0014] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl,

[0015] R18 is optionally substituted aryl or optionally substituted heteroaryl; and

[0016] Z is oxygen, sulfur —CR20R21— or —NR22—, wherein R20, R21 and R22 independently of each other are hydrogen or C1-C4alkyl;

[0017] provided that when R8 is hydrogen, R9 is not C1-C6-alkoxy, C3-C6alkenyloxy or C3-C6-alkynyloxy in position 3 of the phenyl ring carrying these radicals.

[0018] In the above definition aryl includes aromatic hydrocarbon rings like phenyl, naphthyl, anthracenyl, phenanthrenyl, with phenyl being preferred.

[0019] Heteroaryl stands for aromatic ring systems comprising mono-, bi- or tricyclic systems wherein at least one oxygen, nitrogen or sulfur atom is present as a ring member. Examples are furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, indazolyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, phthalazinyl, quinoxalinyl, quinazolinyl, cinnolinyl and naphthyridinyl.

[0020] The above aryl and heteroaryl groups may carry one or more identical or different substituents. Normally not more than three substituents are present at the same time. Examples of substituents of aryl or heteroaryl groups are: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl and phenyl-alkyl, it being possible in turn for all of the preceding groups to carry one or more identical or different halogen atoms; alkoxy; alkenyloxy; alkynyloxy; alkoxyalkyl; halogenalkoxy, alkylthio; halogenalkylthio; alkylsulfonyl; formyl; alkanoyl; hydroxy; halogen; cyano; nitro; amino; alkylamino; dialkylamino; carboxy; alkoxycarbonyl; alkenyloxycarbonyl; alkynyloxycarbonyl.

[0021] In the above definitions “halogen” or the prefix “halo” includes fluorine, chlorine, bromine and iodine.

[0022] The alkyl, alkenyl and alkynyl radicals may be straight-chain or branched. This applies also to the alkyl, alkenyl or alkynyl parts of other alkyl-, alkenyl- or alkynyl-containing groups.

[0023] The organic radical in R8 and R9 indicates that practically every substituent used in the art of organic chemistry may be placed in the indicated position at the phenylene bridge member. Preferred are however the more frequently used radicals like C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino.

[0024] Depending upon the number of carbon atoms mentioned, alkyl on its own or as part of another substituent is to be understood as being, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the isomers thereof, for example isopropyl, isobutyl, tert-butyl or sec-butyl, isopentyl or tert-pentyl.

[0025] Cycloalkyl is, depending upon the number of carbon atoms mentioned, cyclopropyl, cyclo-butyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

[0026] Depending upon the number of carbon atoms mentioned, alkenyl as a group or as a structural element of other groups is to be understood as being, for example, ethenyl, allyl, 1-propenyl, buten-2-yl, buten-3-yl, penten-1-yl, penten-3-yl, hexen-1-yl, 4-methyl-3-pentenyl or 4-methyl-3-hexenyl.

[0027] Alkynyl as a group or as a structural element of other groups is, for example, ethynyl, propyn-1-yl, propyn-2-yl, butyn-1-yl, butyn-2-yl, 1-methyl-2-butynyl, hexyn-1-yl, 1-ethyl-2-butynyl or octyn-1-yl.

[0028] A halogenalkyl group may contain one or more (identical or different) halogen atoms, and for example may stand for CHCl2, CH2F, CCl3, CH2Cl, CHF2, CF3, CH2CH2Br, C2Cl5, CH2Br, CHClBr, CF3CH2, etc.

[0029] Where R2 and R3 together with the carbon atom to which they are attached form a hydrocarbon ring the ring corresponds to cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane or cyclooctane

[0030] The presence of at least one asymmetric carbon atom and/or at least one asymmetric oxidized sulfur atom in the compounds of formula I means that the compounds may occur in optically isomeric forms. As a result of the presence of a possible aliphatic C═C double bond, geometric isomerism may also occur. Formula I is intended to include all those possible isomeric forms and mixtures thereof.

[0031] Preferred subgroups of compounds of formula I are those wherein

[0032] n is one; or

[0033] R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene; or

[0034] R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12halogenalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl; or

[0035] R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4halogenalkyl; or C1-C2dialkylamino; or

[0036] R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino; or

[0037] R2 is hydrogen and R3 is C1-C8alkyl, C1-C8alkyl optionally substituted by hydroxy, C1-C4alkoxy, mercapto or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl or C3-C8cycloalkyl-C1-C4alkyl; or

[0038] R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl; or

[0039] R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl; or

[0040] R2 is hydrogen and R3 is isopropyl; or

[0041] R4 is hydrogen, methyl or ethyl; or

[0042] R4 is hydrogen or methyl; or

[0043] R4 is hydrogen; or

[0044] R5, R6 and R7 are each independently hydrogen or methyl; or

[0045] R5, R6 and R7 are each hydrogen; or

[0046] R8 is hydrogen, C1-C8-alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino; or

[0047] R8 is hydrogen, C1-C8alkyl, C1-C8halogenalkyl, C2-C8alkenyl, C2-C8alkynyl, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C1-C8alkanoyl, formyl, halogen, nitro, cyano or hydroxy; or

[0048] R8 is hydrogen, C1-C4alkyl, C1-C4halogenalkyl, C1-C4alkoxy, C1-C4alkoxycarbonyl, C1-C4alkanoyl, formyl, halogen, cyano or hydroxy; or

[0049] R8 is hydrogen, C1-C4alkyl, halogen or cyano; or

[0050] R9 is C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino, provided that when R8 is hydrogen, R9 is not C1-C6alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy in position 3 of the phenyl ring carrying these radicals ; or

[0051] R9 is C1-C4alkyl, C1-C4halogenalkyl, C1-C4alkoxy, C1-C4alkoxycarbonyl, C1-C4alkanoyl, formyl, halogen, cyano or hydroxy, provided that when R8 is hydrogen, R9 is not C1-C6alkoxy in position 3 of the phenyl ring carrying these radicals; or

[0052] R9 is C1-C4alkyl, halogen or cyano; or

[0053] R13, R14, R16, R17 and R19 are each independently hydrogen or methyl; or

[0054] R13, R14, R16, R17 and R19 are each hydrogen; or

[0055] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or

[0056] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C-alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8-alkanoyl, hydroxy, halogen, cyano, nitro, amino and C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; or

[0057] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or

[0058] R15 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or

[0059] R18 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or

[0060] R18 is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino, C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; or

[0061] R18 is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; or

[0062] R18 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8-alkoxycarbonyl; or

[0063] Z is oxygen, sulfur or —CH2—; or

[0064] Z is oxygen.

[0065] Further preferred subgroups of the compounds of formula I are those wherein

[0066] 1) R1 is C1-C12alkyl, C1-C12alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C3-C8cycloalkyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene;

[0067] R2 is hydrogen and R3 is C1-C8alkyl; C1-C8alkyl substituted with hydroxy, mercapto, C1-C4alkoxy or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl; C3-C8cycloalkyl-C1-C4alkyl;

[0068] R8 is hydrogen, C1-C8-alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino;

[0069] R9 is C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino, provided that when R8 is hydrogen, R9 is not C1-C6alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy in position 3 of the phenyl ring carrying these radicals

[0070] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; and

[0071] R18 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur; or

[0072] 2) n is one;

[0073] R1 is C1-C12alkyl, C2-C12alkenyl; C1-C12halogenalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl;

[0074] R2 is hydrogen and R3 is C1-C4alkyl; C3-C4alkenyl or cyclopropyl;

[0075] R4 is hydrogen, methyl or ethyl;

[0076] R5, R6 and R7 are each independently hydrogen or methyl; or

[0077] R8 is hydrogen, C1-C8alkyl, C1-C8halogenalkyl, C2-C8alkenyl, C2-C8alkynyl, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C1-C8alkanoyl, formyl, halogen, nitro, cyano or hydroxy;

[0078] R9 is C1-C4alkyl, C1-C4halogenalkyl, C1-C4alkoxy, C1-C4alkoxycarbonyl, C1-C4alkanoyl, formyl, halogen, cyano or hydroxy, provided that when R8 is hydrogen, R9 is not C1-C6alkoxy in position 3 of the phenyl ring carrying these radicals;

[0079] R13, R14, R16, R17 and R19 are each independently hydrogen or methyl; or

[0080] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C-alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8-alkanoyl, hydroxy, halogen, cyano, nitro, amino, C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl;

[0081] R18 is phenyl, naphthyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl, isoxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzothiophenyl, benzofuranyl, benzimidazolyl, benzthiazolyl, benzoxazolyl or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, phenyl, phenyl-C1-C4alkyl wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C1-C8alkoxy-C1-C4alkyl, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, C1-C8alkylsulfonyl, formyl, C2-C8alkanoyl, hydroxy, halogen, cyano, nitro, amino, C1-C8alkylamino, C1-C8dialkylamino, carboxy, C1-C8alkoxycarbonyl, C1-C8alkenyloxycarbonyl and C1-C8alkynyloxycarbonyl; and

[0082] Z is oxygen, sulfur or —CH2—; or

[0083] 3) n is one;

[0084] R1 is C1-C4alkyl, C2-C4alkenyl; C1-C4halogenalkyl; or C1-C2dialkylamino;

[0085] R2 is hydrogen and R3 is C3-C4alkyl; allyl or cyclopropyl;

[0086] R4 is hydrogen or methyl;

[0087] R5, R6, R7, R13, R14, R16, R17 and R19 are each hydrogen;

[0088] R8 is hydrogen, C1-C4alkyl, C1-C4halogenalkyl, C1-C4alkoxy, C1-C4alkoxycarbonyl, C1-C4alkanoyl, formyl, halogen, cyano or hydroxy;

[0089] R9 is C1-C4alkyl, halogen or cyano;

[0090] R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8cycloalkyl; phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;

[0091] R18 is phenyl, naphthyl, thienyl, pyridyl, pyrimidinyl, triazinyl, or quinolyl with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8-alkyl, C2-C8alkenyl, wherein the hydrogens of all these substituents may be optionally substituted by one or more identical or different halogen atoms; C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8alogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and

[0092] Z is oxygen, sulfur or —CH2—; or

[0093] 4) n is one;

[0094] R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino;

[0095] R2 is hydrogen and R3 is isopropyl;

[0096] R4, R5, R7, R11, R12, R14, R15 and R17 are each hydrogen;

[0097] R8 is hydrogen;

[0098] R9 is C1-C4alkyl, halogen or cyano;

[0099] R15 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl;

[0100] R18 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8-alkoxycarbonyl; and

[0101] Z is oxygen.

[0102] Preferred individual compounds are:

[0103] N-(2-{3-bromo-4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,

[0104] N-(2-{3-bromo-4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-ethanesullonylamino-3-methyl-butyramide,

[0105] N-(2-{3-bromo-4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,

[0106] N-{2-[3-bromo-4-(3-cyclopropyl-prop-2-ynyloxy)-5-methoxy-phenyl]-ethyl}-2-ethanesulfonylamino-3-methyl-butyramide,

[0107] N-(2-{3-bromo-4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-methanesultonylamino-3-methyl-butyramide,

[0108] N-(2-{3-bromo-4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,

[0109] N-(2-{3-bromo-4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,

[0110] N-(2-[3-bromo-4-(3-cyclopropyl-prop-2-ynyloxy)-5-methoxy-phenyl]-ethyl}-2-methanesulfonylamino-3-methyl-butyramide,

[0111] N-(2-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3,5-dimethoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,

[0112] N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-3,5-dimethoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,

[0113] N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-3,5-dimethoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide,

[0114] N-(2-{4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-3,5-dimethoxy-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,

[0115] N-(2-{4-[3-(4-bromo-phenyl)-prop-2-ynyloxy]-3,5-dimethoxy-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,

[0116] N-(2-{4-[3-(4-fluoro-phenyl)-prop-2-ynyloxy]-3,5-dimethoxy-phenyl}-ethyl)-2-methanesulfonylamino-3-methyl-butyramide,

[0117] N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-3,5-dimethoxy-phenyl]-ethyl}-2-ethanesulfonylamino-3-methyl-butyramide, and

[0118] N-{2-[4-(3-cyclopropyl-prop-2-ynyloxy)-3,5-dimethoxy-phenyl]-ethyl}-2-methanesulfonylamino-3-methyl-butyramide.

[0119] Certain α-sulfin- and α-sulfonamino acid derivatives having a different kind of structure have already been proposed for controlling plant-destructive fungi (for example in WO 95/030651, WO 97/14677, WO 98/38160 and WO 98/38161). The action of those preparations is not, however, satisfactory in all aspects of agricultural needs. Surprisingly, with the compound structure of formula I, new kinds of microbicides having a high level of activity have been found.

[0120] The α-sulfin- and α-sulfonamino acid amides of formula I may be obtained according to one of the following processes: 3

[0121] An amino acid of formula II or a carboxy-activated derivative of an amino acid of formula II wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III wherein R4, R5, R6, R7, R8, R9 and R10 are as defined above optionally in the presence of a base and optionally in the presence of a diluting agent (step B).

[0122] Carboxy-activated derivatives of the amino acid of formula II encompasses all compounds having an activated carboxyl group like an acid halide, such as an acid chloride, like symmetrical or mixed anhydrides, such as mixed anhydrides with O-alkylcarbonates, like activated esters, such as p-nitrophenylesters or N-hydroxysuccinimidesters, as well as in situ produced activated forms of the amino acid of formula II by condensating agents, such as dicyclohexylcarbodiimide, carbonyldiimidazol, benzotriazol-1-yloxy-tris(dimethylamino)-phosphonium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(pentamethylene)-uronium hexafluorophosphate, O-benzotriazol-1-yl N,N,N′,N′-bis(tetramethylene)uronium hexafluorophosphate, O-benzotriazol-1 -yl N,N,N′,N′-tetramethyluronium hexafluoro-phosphate or benzotriazol-1-yloxy-tripyrrolidinophosphonium hexafluorophosphate. The mixed anhydrides of the amino acids of the formula II may be prepared by reaction of an amino acid of formula II with chloroformic acid esters like chloroformic acid alkylesters, such as ethyl chloroformate or isobutyl chloroformate, optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine.

[0123] The present reaction is preferably performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; amides, e.g. N,N-dimethyl-formamide; nitrites e.g. acetonitrile; or ethers e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is preformed optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C.

[0124] The compounds of formula II may be prepared by reaction of an amino acid of formula IV where R2 and R3 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V where R1 and n have the same meanings as defined above and where X is halide, preferentially chlorine or bromine (step A).

[0125] The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons, e.g. dichloromethane or toluene; ketones, e.g. acetone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide or a metal carbonate, preferentially an alkali hydroxide or an alkali carbonate, such as lithium hydroxide, sodium hydroxide or potassium hydroxide at temperatures ranging from −80° C. to +150° C., preferentially at temperatures ranging from −40° C. to +40° C. 4

[0126] The compounds of formula I may also be prepared by reaction of an amino acid derivative of formula VI wherein R2, R3, R4, R5 R6, R7, R8, R9 and R10 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V wherein R. and n are as defined for formula I and X is halide, preferentially chlorine or bromine (step C). The reaction is performed in the same manner as described for step A. 5

[0127] The compounds of formula I may also be prepared by reaction of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7, R8 and R9 are as defined for formula I with a compound of formula VIII wherein R10 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step D).

[0128] The reaction may be performed in an inert solvent like aromatic, non-aromatic or halogenated hydrocarbons, such as chlorohydrocarbons e.g. dichloromethane or toluene; ketones e.g. acetone or 2-butanone; esters, e.g. ethyl acetate; ethers, e.g. diethylether, tert-butyl-methylether, dioxane or tetrahydrofurane, amides, e.g. dimethylformamide, nitriles, e.g. acetonitrile, alcohols, e.g. methanol, ethanol, isopropanol, n-butanol or tert-butanol, sulfoxides e.g. dimethylsulfoxide or water. It is also possible to use mixtures of these solvents. The reaction is performed optionally in the presence of an organic or inorganic base like a tertiary amine, such as triethylamine, N,N-diisopropyl-ethylamine, pyridine, N-methyl-piperidine or N-methyl-morpholine, like a metal hydroxide, a metal carbonate or a metal alkoxide, preferentially an alkali hydroxide, an alkali carbonate or an alkali alkoxide, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide or potassium tert-butoxide at temperatures ranging from −80° C. to +200° C., preferentially at temperatures ranging from 0° C. to +120° C. 6

[0129] The compounds of formula Ia may also be prepared via formula IX wherein R1, n, R2, R3, R4, R5, R6, R7, R8, R9, R13, R14 and R15 are defined for formula I by reacting of a phenol of formula VII wherein R1, n, R2, R3, R4, R5, R6, R7, R8 and R9 are as defined for formula I with a compound of formula VIIIa wherein R13, R14 and R15 are as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate (step E).

[0130] The reaction is performed in the same manner as described for step D.

[0131] The compounds of formula Ia R13, R14 and R15 is as defined for formula I may be prepared by reaction of compounds of formula IX with hydrogen.

[0132] The reaction is performed in a solvent like ethers, e.g. diethylether, dioxane or tetrahydrofuran, or like alcohols, e.g. methanol or ethanol, or water in the presence of transition metals or transition metal salts, e.g. nickel, cobalt, palladium, platinium or rhodium, optionally in the presence of bases, e.g. ammonia, or in the presence of salts, e.g. barium sulfate, at temperatures ranging from −20° C. to +160° C. and at pressures ranging from 1 to 200 bar.

[0133] aa) The intermediate amines of formula III may be obtained by one of the following processes: 789

[0134] Step 1 is the alkylation of a phenol with a compound of formula VIII. The reaction is performed in the same manner as described for procedure c).

[0135] Step 2 is the reaction of an aromatic aldehyde with nitromethane. This reaction is performed in a solvent like an organic carboxylic acids, e.g. acetic acid optionally in the presence of the ammonium salt of this carboxylic acid, e.g. ammonium acetate at temperatures ranging from 0° C. to +200° C.

[0136] Step 3 is the reduction of an unsaturated nitrogen-compound. This reaction is performed in a solvent like an ether, e.g. diethylether, dioxane or tetrahydrofuran, or an alcohol, e.g. methanol, ethanol or isopropanol, with borohydride, with a boron-complex, e.g. the complex of borohydride with tetrahyrofuran, with an alkaliborohydride, with an alkalialuminiumhydride, e.g. lithiumaluminiumhydride, with aluminiumhydride, with an aluminiumalkoxyhydride or with hydrogen optionally in the presence of a transition metal, a transition metal salt or a transition metal complex, e.g. nickel, cobalt, palladium, platinium or rhodium at temperatures ranging from −50° C. to +200° C.

[0137] Step 4 is the reaction of an aldehyde or a ketone of formula with hydroxylamine or with a salt of hydroxylamine. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like an amide, e.g. dimethylformamide, or in water or in a mixture of these solvents optionally in the presence of an organic or inorganic base like a tertiary amine, e.g. triethylamine, like a heterocyclic compound containing nitrogen, e.g. pyridine, or like an alkalicarbonate, e.g. sodium carbonate or potassium carbonate, at temperatures ranging from −20° C. to +150° C.

[0138] Step 5 is the exchange of hydroxy by cyanide. This reaction is performed in an organic solvent like an amide, e.g. dimethylformamide using a metal cyanide like an alkali cyanide, e.g. sodium cyanide or potassium cyanide, at temperatures ranging from 0° C. to +200° C.

[0139] Step 6 is the hydrolysis of an alkyl ester. This reaction is performed in a solvent like an alcohol, e.g. methanol, ethanol or isopropanol, like an ether, e.g. diethylether, dioxane or tetrahydrofuran, like a halogenated hydrocarbon, e.g. dichloromethane, or water or in a mixture of these solvents optionally in the presence of an alkali hydroxide, e.g. lithium hydroxide, sodium hydroxide or potassium hydroxide, or optionally in the presence of an acid, e.g. hydrogen chloride, sulfuric acid or trifluoroacetic acid at temperatures ranging from −20° C. to +160° C.

[0140] Step 7 is the reaction of a carboxylic acid or the activated form of this carboxylic acid with hydrogen azide or an azide-salt. An activated form of a carboxylic acid can be the acid halogenide, e.g. acid chloride, a symmetric or a mixed anhydride. Azide-salts can be alkali azides, e.g. sodium azide. The reaction is performed in a solvent like a hydrocarbon, e.g. toluene or xylene, like a halogenated hydrocarbon, e.g. chloroform, like an ether, e.g. dioxane, like a ketone, e.g. acetone or 2-butanone, like an alcohol, e.g. methanol, ethanol or tert-butanol, or water or in a mixture of these solvents optionally in the presence of an acid like an inorganic acid, e.g. sulfuric acid or hydrogen chloride at temperatures ranging from −40° C. to +200° C.

[0141] In a preferred form the compounds of formula XXVI are prepared starting from compounds of the formula XXV by applying step 5 and step 1 in the same pot.

[0142] bb) Amines of formula VI can be obtained by the following process: 10

[0143] wherein R is lower alkyl or optionally substituted benzyl.

[0144] Step 8 is the amidation of an carbamate-protected amino acid of formula XXXIII with an amine of formula XXXIV. The reaction is performed in the same manner as described for step A.

[0145] Step 9 is the alkylation of a phenol of formula XXXV with an compound of formula VIII. The reaction is performed in the same manner as described for step D.

[0146] Step 10 is the hydrolysis of a carbamate of formula XXXVI. The reaction is performed in a solvent like hydrocarbons, e.g. toluene, like halogenated hydrocarbons, e.g. dichloromethane, like ketones, e.g. acetone, like esters, e.g. ethyl acetate, like ethers, e.g. dioxane or tetrahydrofuran, or like water or in mixtures of these solvents optionally in the presence of an organic acid like carboxylic acid, e.g. trifluoroacetic acid, or like a sulfonic acid, e.g. methanesulfonic acid or toluenesulfonic acid, or in the presence of an inorganic acid, e.g. hydrogen chloride or sulfuric acid, at temperatures ranging from −40° C. to +160° C.

[0147] The compounds of formula I are oils or solids at room temperature and are distinguished by valuable microbiocidal properties. They can be used in the agricultural sector or related fields preventively and curatively in the control of plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished at low rates of concentration not only by outstanding microbiocidal, especially fungicidal, activity but also by being especially well tolerated by plants.

[0148] Surprisingly, it has now been found that the compounds of formula I have for practical purposes a very advantageous biocidal spectrum in the control of phytopathogenic micro-organisms, especially fungi. They possess very advantageous curative and preventive properties and are used in the protection of numerous crop plants. With the compounds of formula I it is possible to inhibit or destroy phytopathogenic microorganisms that occur on various crops of useful plants or on parts of such plants (fruit, blossom, leaves, stems, tubers, roots), while parts of the plants which grow later also remain protected, for example, against phytopathogenic fungi.

[0149] The novel compounds of formula I prove to be effective against specific genera of the fungus class Fungi imperfecti (e.g. Cercospora), Basidiomycetes (e.g. Puccinia) and Ascomycetes (e.g. Erysiphe and Venturia) and especially against Oomycetes (e.g. Plasmopara, Peronospora, Pythium and Phytophthora). They therefore represent in plant protection a valuable addition to the compositions for controlling phytopathogenic fungi. The compounds of formula I can also be used as dressings for protecting seed (fruit, tubers, grains) and plant cuttings from fungal infections and against phytopathogenic fungi that occur in the soil.

[0150] The invention relates also to compositions comprising compounds of formula I as active ingredient, especially plant-protecting compositions, and to the use thereof in the agricultural sector or related fields.

[0151] In addition, the present invention includes the preparation of those compositions, wherein the active ingredient is homogeneously mixed with one or more of the substances or groups of substances described herein. Also included is a method of treating plants which is distinguished by the application of the novel compounds of formula I or of the novel compositions.

[0152] Target crops to be protected within the scope of this invention comprise, for example, the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucurbitaceae (marrows, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamon, camphor) and plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, and also ornamentals.

[0153] The compounds of formula I are normally used in the form of compositions and can be applied to the area or plant to be treated simultaneously or in succession with other active ingredients. Those other active ingredients may be fertilisers, micronutrient donors or other preparations that influence plant growth. It is also possible to use selective herbicides or insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of those preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.

[0154] The compounds of formula I can be mixed with other fungicides, resulting in some cases in unexpected synergistic activities.

[0155] Mixing components which are particularly preferred are azoles such as azoles, such as

[0156] azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, myclobutanil, pefurazoate, penconazole, pyrifenox, prochloraz, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole; pyrimidinyl carbinols, such as ancymidol, fenarimol, nuarimol; 2-amino-pyrimidines, such as bupirimate, dimethirimol, ethirimol; morpholines, such as dodemorph, fenpropidine, fenpropimorph, spiroxamine, tridemorph; anilinopyrimidines, such as cyprodinil, mepanipyrim, pyrimethanil;

[0157] pyrroles, such as fenpiclonil, fludioxonil; phenylamides, such as benalaxyl, furalaxyl, metalaxyl, R-metalaxyl, ofurace, oxadixyl; benzimidazoles, such as benomyl, carbendazim, debacarb, fuberidazole, thiabendazole; dicarboximides, such as chlozolinate, dichlozoline, iprodione, myclozoline, procymidone, vinclozolin; carboxamides, such as carboxin, fenfuram, flutolanil, mepronil, oxycarboxin, thifluzamide; guanidines, such as guazatine, dodine, iminoctadine;

[0158] strobilurines, such as azoxystrobin, kresoxim-methyl, metominostrobin, SSF-129, CGA 279202 (trifloxystrobin), picoxystrobin; dithiocarbamates, such as ferbam, mancozeb, maneb, metiram, propineb, thiram, zineb, ziram; N-halogenmethylthiophthalimides, such as captafol, captan, dichlofluanid, fluoromide, folpet, tolyfluanid; Cu compounds, such as Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper, oxine-copper; nitrophenol derivatives, such as dinocap, nitrothal-isopropyl;

[0159] organo-P derivatives, such as edifenphos, iprobenphos, isoprothiolane, phosdiphen, pyrazophos, tolclofos-methyl; various, such as AC 382042, acibenzolar-S-methyl, anilazine, blasticidin-S, quinomethionat, chloroneb, chlorothalonil, cymoxanil, dichlone, diclomezine, dicloran, diethofencarb, dimethomorph, dithianon, etridiazole, famoxadone, tenamidone, fenhexamid, fentin, ferimzone, fluazinam, flusulfamide, fosetyl-aluminium, hymexazol, IKF-916, iprovalicarb, kasugamycin, methasulfocarb, MON65500, pencycuron, phthalide, polyoxins, probenazole, propamocarb, pyroquilon, quinoxyfen, quintozene, RH-7281, RPA 407213, BAS 50001 F, sulfur, SYP-Z071, triazoxide, tricyclazole, triforine, validamycin.

[0160] Suitable carriers and surfactants may be solid or liquid and correspond to the substances ordinarily employed in formulation technology, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. Such carriers and additives are described, for example, in WO 95/30651.

[0161] A preferred method of applying a compound of formula I, or an agrochemical composition comprising at least one of those compounds, is application to the foliage (foliar application), the frequency and the rate of application depending upon the risk of infestation by the pathogen in question. The compounds of formula I may also be applied to seed grains (coating) either by impregnating the grains with a liquid formulation of the active ingredient or by coating them with a solid formulation.

[0162] The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for that purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

[0163] Advantageous rates of application are normally from 1 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg a.i./ha, especially from 25 g to 750 g a.i./ha. When used as seed dressings, rates of from 0.001 g to 1.0 g of active ingredient per kg of seed are advantageously used.

[0164] The formulations, i.e. the compositions, preparations or mixtures comprising the compound(s) (active ingredient(s)) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

[0165] Further surfactants customarily used in formulation technology will be known to the person skilled in the art or can be found in the relevant technical literature.

[0166] The agrochemical compositions usually comprise 0.01 to 99% by weight, preferably 0.1 to 95% by weight, of a compound of formula I, 99.99 to 1% by weight, preferably 99.9 to 5% by weight, of a solid or liquid adjuvant, and 0 to 25% by weight, preferably 0.1 to 25% by weight, of a surfactant.

[0167] Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

[0168] The compositions may also comprise further ingredients, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.

[0169] The Examples which follow illustrate the invention described above, without limiting the scope thereof in any way. Temperatures are given in degrees Celsius.

PREPARATION EXAMPLES FOR COMPOUNDS OF FORMULA I

Example A1.1

(S)-N-(2-{3-Bromo-4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide

[0170] 11

[0171] A mixture of (S)-N-[2-(3-bromo-4-hydroxy-5-methoxy-phenyl)-ethyl]-2-ethanesuifonylamino-3-methyl-butyramide (1.5 g), toluene-4-sulfonic acid 3-(4-chloro-phenyl)-prop-2-ynyl ester (1.7 g) and sodium methoxide (6.5 ml, 1 M solution in methanol) in methanol (40 ml) is heated to reflux for 2 hours. After cooling water (500 ml) is added. The mixture is extracted with ethyl acetate (2×500 ml). The organic layers are washed with brine (2×100 ml), combined, dried (MgSO4) and the solvent is evaporated. (S)-N-(2-{3-Bromo-4-[3-(4-chloro-phenyl)-prop-2-ynyloxy]-5-methoxy-phenyl}-ethyl)-2-ethanesulfonylamino-3-methyl-butyramide is obtained and is purified by flash-column chromatography on silica gel (ethyl acetate/hexane) and recrystallization (ethyl acetate/hexane), m.p. 109-111° C.

[0172] Analogously to example A1.1 the compounds listed in table A1 are obtained.

[0173] *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl

TABLE A1
12
No	R1	*)	R3	R4	R8	R9	R10	m.p. (° C.)
A1.1	CH3—CH2—	(S)	(CH3)2CH—	H	3-OCH3	5-Br	(4-Cl—Ph)—C≡C—CH2—	109-111
A1.2	CH3—CH2—	(S)	(CH3)2CH—	H	3-OCH3	5-Br	(3,4-di-Cl—Ph)—CH2—	148-150
A1.3	CH3—	(S)	(CH3)2CH—	H	2-OCH3	H	(4-Cl—Ph)—C≡C—CH2—	129-130
A1.4	CH3—	(S)	(CH3)2CH—	H	2-OCH3	H	(4-Br—Ph)—C≡C—CH2—	133-135
A1.5	CH3—	(S)	(CH3)2CH—	H	3-Cl	H	(4-Cl—Ph)—C≡C—CH2—	156-157
A1.6	CH3—	(S)	(CH3)2CH—	H	3-Cl	H	(4-Br—Ph)—C≡C—CH2—	155-156
A1.7	CH3—CH2—	(S)	(CH3)2CH—	H	3-Br	H	(4-Cl—Ph)—C≡C—CH2—	147-149
A1.8	CH3—CH2—	(S)	(CH3)2CH—	H	3-Br	H	(4-CH3—Ph)—C≡C—CH2—	124-126
*) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl

Example A2.1

(S)-N-[2-(3-Bromo-4-hydroxy-5-methoxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide

[0174] 13

[0175] (S)-N-[2-(4-Benzyloxy-3-bromo-5-methoxy-phenyl)-ethyl]-2-ethanesulfonylarnino-3-methyl-butyramide (11.7 g) and palladium (3.6 g, 5% on charcoal) in tetrahydrofuran (200 ml) are shaken under a hydrogen atmosphere at +20 to +22° C. and at normal pressure for 30 hours. The reaction mixture is filtered and evaporated. (S)-N-[2-(3-Bromo-4-hydroxy-5-methoxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide is obtained, and is purified by flash-column chromatography on silica gel (ethyl acetate/hexane) and recrystallization (ethyl acetate/hexane), m.p. 145-147° C.

[0176] Analogously to example A2.1 the compounds listed in table A2 are obtained.

[0177] *) Configuration on the α-C-atom in the amino acid moiety

TABLE A2
14
							m.p.
No	R1	*)	R3	R4	R8	R9	(° C.)
A2.1	CH3—CH2—	(S)	(CH3)2CH—	H	3-OCH3	Br	145-147
A2.2	CH3—	(S)	(CH3)2CH—	H	2-OCH3	H	123-125
A2.3	CH3—	(S)	(CH3)2CH—	H	3-Cl	H	146-151
*) Configuration on the α-C-atom in the amino acid moiety

Example A3.1

(S)-N-[2-(4-Benzyloxy-3-bromo-5-methoxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide

[0178] 15

[0179] To (S)-2-Ethanesulfonylamino-3-methyl-butyric acid (15.6 g), 2-(4-benzyloxy-3-bromo-5-methoxy-phenyl)-ethylamine (25 g) and N,N-diisopropylethylamine (27 ml) in N,N-Dimethyl-formamide (300 ml) is added benzotriazol-1-yloxytris(dimethylamino)phosphonium hexafluorophosphate (36.2 g) in one portion. The reaction mixture is stirred at room temperature for 4 hours. Water (1 l) is then added. The mixture is extracted with ethyl acetate (2×500 ml). The organic layers are washed with brine (2×100 ml), combined, dried (MgSO4) and the solvent is evaporated. (S)-N-[2-(4-Benzyloxy-3-bromo-5-methoxy-phenyl)-ethyl]-2-ethanesulfonylamino-3-methyl-butyramide is obtained, and is purified by flash-column chromatography on silica gel (ethyl acetate/hexane) and recrystallization (ethyl acetate/hexane), m.p. 128-130° C.

[0180] Analogously to example A3.1 the compounds listed in table A3 are obtained.

[0181] *) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl

TABLE A3
16
							m.p.
No	R1	*)	R3	R4	R8	R9	(° C.)
3.1.	CH3—CH2—	(S)	(CH3)2CH—	H	3-OCH3	5-	141-
						Br	152
3.2.	CH3—CH2—	(S)	(CH3)2CH—	H	Ph—CH2—	H	165-
							167
3.3.	(CH3)2N—	(S)	(CH3)2CH—	H	Ph—CH2—	H	108-
							109
3.4.	CH3—	(S)	(CH3)2CH—	H	2-OCH3	H	168-
							169
3.5.	CH3—	(S)	(CH3)2CH—	H	3-Cl	H	178-
							179
*) Configuration on the α-C-atom in the amino acid moiety; Ph means phenyl

[0182] Analogously to the above Examples the following compounds of Tables 1 to 16 may be prepared. In the tables Ph means phenyl.

[0183] Table 1: Compounds represented by the Formula I.1 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 17

[0184] Table 2: Compounds represented by the Formula I.2 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 18

[0185] Table 3: Compounds represented by the Formula I.3 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 19

[0186] Table 4: Compounds represented by the Formula I.4 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 20

[0187] Table 5: Compounds represented by the Formula I.5 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 21

[0188] Table 6: Compounds represented by the Formula I.6 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 22

[0189] Table 7: Compounds represented by the Formula I.7 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 23

[0190] Table 8: Compounds represented by the Formula I.8 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 24

[0191] Table 9: Compounds represented by the Formula I.9 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 25

[0192] Table 10: Compounds represented by the Formula I.10 wherein the combination of the groups R1, R3 and R10 corresponds to each row in table A. 26

[0193] Table 11: Compounds represented by the Formula I.11 wherein the combination of the R1, R3 and R10 corresponds to each row in table A. 27

TABLE A
No.	R1	R3	R10
001	CH3—	CH3—CH2—	CH3—(CH2)3—C≡C—CH2—
002	CH3—CH2—	CH3—CH2—	CH3—(CH2)3—C≡C—CH2—
003	(CH3)2pk N—	CH3—CH2—	CH3—(CH2)3—C≡C—CH2—
004	CH3—CH2—CH2—	CH3—CH2—	CH3—(CH2)3—C≡C—CH2—
005	(CH3)2CH—	CH3—CH2—	CH3—(CH2)3—C≡C—CH2—
006	Cl—CH2—CH2—CH2—	CH3—CH2—	CH3—(CH2)3—C≡C—CH2—
007	CH3—	(CH3)2CH—	CH3—(CH2)3—C≡C—CH2—
008	CH3—CH2—	(CH3)2CH—	CH3—(CH2)3—C≡C—CH2—
009	(CH3)2N—	(CH3)2CH—	CH3—(CH2)3—C≡C—CH2—
010	CH3—CH2—CH2—	(CH3)2CH—	CH3—(CH2)3—C≡C—CH2—
011	(CH3)2CH—	(CH3)2CH—	CH3—(CH2)3—C≡C—CH2—
012	Cl—CH2—CH2—CH2—	(CH3)2CH—	CH3—(CH2)3—C≡C—CH2—
013	CH3—	CH3—CH2—CH2—	CH3—(CH2)3—C≡C—CH2—
014	CH3—CH2—	CH3—CH2—CH2—	CH3—(CH2)3—C≡C—CH2—
015	(CH3)2N—	CH3—CH2—CH2—	CH3—(CH2)3—C≡C—CH2—
016	CH3—CH2—CH2—	CH3—CH2—CH2—	CH3—(CH2)3—C≡C—CH2—
017	(CH3)2CH—	CH3—CH2—CH2—	CH3—(CH2)3—C≡C—CH2—
018	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	CH3—(CH2)3—C≡C—CH2—
019	CH3—	28	CH3—(CH2)3—C≡C—CH2—
020	CH3—CH2—	29	CH3—(CH2)3—C≡C—CH2—
021	(CH3)2N—	30	CH3—(CH2)3—C≡C—CH2—
022	CH3—CH2—CH2—	31	CH3—(CH2)3—C≡C—CH2—
023	(CH3)2CH—	32	CH3—(CH2)3—C≡C—CH2—
024	Cl—CH2—CH2—CH2—	33	CH3—(CH2)3—C≡C—CH2—
025	CH3—	CH2═CH—CH2—	CH3—(CH2)3—C≡C—CH2—
026	CH3—CH2—	CH2═CH—CH2—	CH3—(CH2)3—C≡C—CH2—
027	(CH3)2N—	CH2═CH—CH2—	CH3—(CH2)3—C≡C—CH2—
028	CH3—CH2—CH2—	CH2═CH—CH2—	CH3—(CH2)3—C≡C—CH2—
029	(CH3)2CH—	CH2═CH—CH2—	CH3—(CH2)3—C≡C—CH2—
030	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	CH3—(CH2)3—C≡C—CH2—
031	CH3—	CH≡C—CH2—	CH3—(CH2)3—C≡C—CH2—
032	CH3—CH2—	CH≡C—CH2—	CH3—(CH2)3—C≡C—CH2—
033	(CH3)2N—	CH≡C—CH2—	CH3—(CH2)3—C≡C—CH2—
034	CH3—CH2—CH2—	CH≡C—CH2—	CH3—(CH2)3—C≡C—CH2—
035	(CH3)2CH—	CH≡C—CH2—	CH3—(CH2)3—C≡C—CH2—
036	Cl—CH2—CH2—CH2—	CH≡C—CH2—	CH3—(CH2)3—C≡C—CH2—
037	CH3—	CH3—CH2—CH(CH3)—	CH3—(CH2)3—C≡C—CH2—
038	CH3—CH2—	CH3—CH2—CH(CH3)—	CH3—(CH2)3—C≡C—CH2—
039	(CH3)2N—	CH3—CH2—CH(CH3)—	CH3—(CH2)3—C≡C—CH2—
040	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	CH3—(CH2)3—C≡C—CH2—
041	(CH3)2CH—	CH3—CH2—CH(CH3)—	CH3—(CH2)3—C≡C—CH2—
042	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	CH3—(CH2)3—C≡C—CH2—
045	CH3—	CH3—CH2—	34
046	CH3—CH2—	CH3—CH2—	35
047	(CH3)2N—	CH3—CH2—	36
048	CH3—CH2—CH2—	CH3—CH2—	37
049	(CH3)2CH—	CH3—CH2—	38
050	Cl—CH2—CH2—CH2—	CH3—CH2—	39
51	CH3—	(CH3)2CH—	40
052	CH3—CH2—	(CH3)2CH—	41
053	(CH3)2N—	(CH3)2CH—	42
054	CH3—CH2—CH2—	(CH3)2CH—	43
055	(CH3)2CH—	(CH3)2CH—	44
056	Cl—CH2—CH2—CH2—	(CH3)2CH—	45
057	CH—	CH3—CH2—CH2—	46
058	CH3—CH2—	CH3—CH2—CH2—	47
059	(CH3)2N—	CH3—CH2—CH2—	48
060	CH3—CH2—CH2—	CH3—CH2—CH2—	49
061	(CH3)2CH—	CH3—CH2—CH2—	50
062	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	51
063	CH3—	52	53
064	CH3—CH2—	54	55
065	(CH3)2N—	56	57
066	CH3—CH2—CH2—	58	59
067	(CH3)2CH—	60	61
068	Cl—CH2—CH2—CH2—	62	63
069	CH3—	CH2═CH—CH2—	64
070	CH3—CH2—	CH2═CH—CH2—	65
071	(CH3)2N—	CH2═CH—CH2—	66
072	CH3—CH2—CH2—	CH2═CH—CH2—	67
073	(CH3)2CH—	CH2═CH—CH2—	68
074	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	69
075	CH3—	CH≡C—CH2—	70
076	CH3—CH2—	CH≡C—CH2—	71
077	(CH3)2N—	CH≡C—CH2—	72
078	CH3—CH2—CH2—	CH≡C—CH2—	73
079	(CH3)2CH—	CH≡C—CH2—	74
080	Cl—CH2—CH2—CH2—	CH≡C—CH2—	75
081	CH3—	CH3—CH2—CH(CH3)—	76
082	CH3—CH2—	CH3—CH2—CH(CH3)—	77
083	(CH3)2N—	CH3—CH2—CH(CH3)—	78
084	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	79
085	(CH3)2CH—	CH3—CH2—CH(CH3)—	80
086	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	81
087	CH3—	CH3—CH2—	Ph—C≡C—CH2—
088	CH3—CH2—	CH3—CH2—	Ph—C≡C—CH2—
089	(CH3)2N—	CH3—CH2—	Ph—C≡C—CH2—
090	CH3—CH2—CH2—	CH3—CH2—	Ph—C≡C—CH2—
091	(CH3)2CH—	CH3—CH2—	Ph—C≡C—CH2—
092	Cl—CH2—CH2—CH2—	CH3—CH2—	Ph—C≡C—CH2—
093	CH3—	(CH3)2CH—	Ph—C≡C—CH2—
094	CH3—CH2—	(CH3)2CH—	Ph—C≡C—CH2—
095	(CH3)2N—	(CH3)2CH—	Ph—C≡C—CH2—
096	CH3—CH2—CH2—	(CH3)2CH—	Ph—C≡C—CH2—
097	(CH3)2CH—	(CH3)2CH—	Ph—C≡C—CH2—
098	Cl—CH2—CH2—CH2—	(CH3)2CH—	Ph—C≡C—CH2—
099	CH3—	CH3—CH2—CH2—	Ph—C≡C—CH2—
100	CH3—CH2—	CH3—CH2—CH2—	Ph—C≡C—CH2—
101	(CH3)2N—	CH3—CH2—CH2—	Ph—C≡C—CH2—
102	CH3—CH2—CH2—	CH3—CH2—CH2—	Ph—C≡C—CH2—
103	(CH3)2CH—	CH3—CH2—CH2—	Ph—C≡C—CH2—
104	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	Ph—C≡C—CH2—
105	CH3—	82	Ph—C≡C—CH2—
106	CH3—CH2—	83	Ph—C≡C—CH2—
107	(CH3)2N—	84	Ph—C≡C—CH2—
108	CH3—CH2—CH2—	85	Ph—C≡C—CH2—
109	(CH3)2CH—	86	Ph—C≡C—CH2—
110	Cl—CH2—CH2—CH2—	87	Ph—C≡C—CH2—
111	CH3—	CH2═CH—CH2—	Ph—C≡C—CH2—
112	CH3—CH2—	CH2═CH—CH2—	Ph—C≡C—CH2—
113	(CH3)2N—	CH2═CH—CH2—	Ph—C≡C—CH2—
114	CH3—CH2—CH2—	CH2═CH—CH2—	Ph—C≡C—CH2—
115	(CH3)2CH—	CH2═CH—CH2—	Ph—C≡C—CH2—
116	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	Ph—C≡C—CH2—
117	CH3—	CH≡C—CH2—	Ph—C≡C—CH2—
118	CH3—CH2—	CH≡O—CH2—	Ph—C≡C—CH2—
119	(CH3)2N—	CH≡C—CH2—	Ph—C≡C—CH2—
120	CH3—CH2—CH2—	CH≡C—CH2—	Ph—C≡C—CH2—
121	(CH3)2CH—	CH≡C—CH2—	Ph—C≡C—CH2—
122	Cl—CH2—CH2—CH2—	CH≡C—CH2—	Ph—C≡C—CH2—
123	CH3—	CH3—CH2—CH(CH3)—	Ph—C≡C—CH2—
124	CH3—CH2—	CH3—CH2—CH(CH3)—	Ph—C≡C—CH2—
125	(CH3)2N—	CH3—CH2—CH(CH3)—	Ph—C≡C—CH2—
126	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	Ph—C≡C—CH2—
127	(CH3)2CH—	CH3—CH2—CH(CH3)—	Ph—C≡C—CH2—
128	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	Ph—C≡C—CH2—
129	CH3—	CH3—CH2—	(4-F—Ph)—C≡C—CH2—
130	CH3—CH2—	CH3—CH2—	(4-F—Ph)—C≡C—CH2—
131	(CH3)2N—	CH3—CH2—	(4-F—Ph)—C≡C—CH2—
132	CH3—CH2—CH2—	CH3—CH2—	(4-F—Ph)—C≡C—CH2—
133	(CH3)2CH—	CH3—CH2—	(4-F—Ph)—C≡C—CH2—
134	Cl—CH2—CH2—CH2—	CH3—CH2—	(4-F—Ph)—C≡C—CH2—
135	CH3—	(CH3)2CH—	(4-F—Ph)—C≡C—CH2—
136	CH3—CH2—	(CH3)2CH—	(4-F—Ph)—C≡C—CH2—
137	(CH3)2N—	(CH3)2CH—	(4-F—Ph)—C≡C—CH2—
138	CH3—CH2—CH2—	(CH3)2CH—	(4-F—Ph)—C≡C—CH2—
139	(CH3)2CH—	(CH3)2CH—	(4-F—Ph)—C≡C—CH2—
140	Cl—CH2—CH2—CH2—	(CH3)2CH—	(4-F—Ph)—C≡C—CH2—
141	CH3—	CH3—CH2—CH2—	(4-F—Ph)—C≡C—CH2—
142	CH3—CH2—	CH3—CH2—CH2—	(4-F—Ph)—C≡C—CH2—
143	(CH3)2N—	CH3—CH2—CH2—	(4-F—Ph)—C≡C—CH2—
144	CH3—CH2—CH2—	CH3—CH2—CH2—	(4-F—Ph)—C≡C—CH2—
145	(CH3)2CH—	CH3—CH2—CH2—	(4-F—Ph)—C≡C—CH2—
146	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	(4-F—Ph)—C≡C—CH2—
147	CH3—	88	(4-F—Ph)—C≡C—CH2—
148	CH3—CH2—	89	(4-F—Ph)—C≡C—CH2—
149	(CH3)2N—	90	(4-F—Ph)—C≡C—CH2—
150	CH3—CH2—CH2—	91	(4-F—Ph)—C≡C—CH2—
151	(CH3)2CH—	92	(4-F—Ph)—C≡C—CH2—
152	Cl—CH2—CH2—CH2—	93	(4-F—Ph)—C≡C—CH2—
153	CH3—	CH2═CH—CH2—	(4-F—Ph)—C≡C—CH2—
154	CH3—CH2—	CH2═CH—CH2—	(4-F—Ph)—C≡C—CH2—
155	(CH3)2N—	CH2═CH—CH2—	(4-F—Ph)—C≡C—CH2—
156	CH3—CH2—CH2—	CH2═CH—CH2—	(4-F—Ph)—C≡C—CH2—
157	(CH3)2CH—	CH2═CH—CH2—	(4-F—Ph)—C≡C—CH2—
158	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	(4-F—Ph)—C≡C—CH2—
159	CH3—	CH≡C—CH2—	(4-F—Ph)—C≡C—CH2—
160	CH3—CH2—	CH≡C—CH2—	(4-F—Ph)—C≡C—CH2—
161	(CH3)2N—	CH≡C—CH2—	(4-F—Ph)—C≡C—CH2—
162	CH3—CH2—CH2—	CH≡C—CH2—	(4-F—Ph)—C≡C—CH2—
163	(CH3)2CH—	CH≡C—CH2—	(4-F—Ph)—C≡C—CH2—
164	Cl—CH2—CH2—CH2—	CH≡C—CH2—	(4-F—Ph)—C≡C—CH2—
165	CH3—	CH3—CH2—CH(CH3)—	(4-F—Ph)—C≡C—CH2—
166	CH3—CH2—	CH3—CH2—CH(CH3)—	(4-F—Ph)—C≡C—CH2—
167	(CH3)2N—	CH3—CH2—CH(CH3)—	(4-F—Ph)—C≡C—CH2—
168	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-F—Ph)—C≡C—CH2—
169	(CH3)2CH—	CH3—CH2—CH(CH3)—	(4-F—Ph)—C≡C—CH2—
170	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-F—Ph)—C≡C—CH2—
171	CH3—	CH3—CH2—	(4-Cl—Ph)—C≡C—CH2—
172	CH3—CH2—	CH3—CH2—	(4-Cl—Ph)—C≡C—CH2—
173	(CH3)2N—	CH3—CH2—	(4-Cl—Ph)—C≡C—CH2—
174	CH3—CH2—CH2—	CH3—CH2—	(4-Cl—Ph)—C≡C—CH2—
175	(CH3)2CH—	CH3—CH2—	(4-Cl—Ph)—C≡C—CH2—
176	Cl—CH2—CH2—CH2—	CH3—CH2—	(4-Cl—Ph)—C≡C—CH2—
177	CH3—	(CH3)2CH—	(4-Cl—Ph)—C≡C—CH2—
178	CH3—CH2—	(CH3)2CH—	(4-Cl—Ph)—C≡C—CH2—
179	(CH3)2N—	(CH3)2CH—	(4-Cl—Ph)—C≡C—CH2—
180	CH3—CH2—CH2—	(CH3)2CH—	(4-Cl—Ph)—C≡C—CH2—
181	(CH3)2CH—	(CH3)2CH—	(4-Cl—Ph)—C≡C—CH2—
182	Cl—CH2—CH2—CH2—	(CH3)2CH—	(4-Cl—Ph)—C≡C—CH2—
183	CH3—	CH3—CH2—CH2—	(4-Cl—Ph)—C≡C—CH2—
184	CH3—CH2—	CH3—CH2—CH2—	(4-Cl—Ph)—C≡C—CH2—
185	(CH3)2N—	CH3—CH2—CH2—	(4-Cl—Ph)—C≡C—CH2—
186	CH3—CH2—CH2—	CH3—CH2—CH2—	(4-Cl—Ph)—C≡C—CH2—
187	(CH3)2CH—	CH3—CH2—CH2—	(4-Cl—Ph)—C≡C—CH2—
188	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	(4-Cl—Ph)—C≡C—CH2—
189	CH3—	94	(4-Cl—Ph)—C≡C—CH2—
190	CH3—CH2—	95	(4-Cl—Ph)—C≡C—CH2—
191	(CH3)2N—	96	(4-Cl—Ph)—C≡C—CH2—
192	CH3—CH2—CH2—	97	(4-Cl—Ph)—C≡C—CH2—
193	(CH3)2CH—	98	(4-Cl—Ph)—C≡C—CH2—
194	Cl—CH2—CH2—CH2—	99	(4-Cl—Ph)—C≡C—CH2—
195	CH3—	CH2═CH—CH2—	(4-Cl—Ph)—C≡C—CH2—
196	CH3—CH2—	CH2═CH—CH2—	(4-Cl—Ph)—C≡C—CH2—
197	(CH3)2N—	CH2═CH—CH2—	(4-Cl—Ph)—C≡C—CH2—
198	CH3—CH2—CH2—	CH2═CH—CH2—	(4-Cl—Ph)—C≡C—CH2—
199	(CH3)2CH—	CH2═CH—CH2—	(4-Cl—Ph)—C≡C—CH2—
200	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	(4-Cl—Ph)—C≡C—CH2—
201	CH3—	CH≡C—CH2—	(4-Cl—Ph)—C≡C—CH2—
202	CH3—CH2—	CH≡C—CH2—	(4-Cl—Ph)—C≡C—CH2—
203	(CH3)2N—	CH≡C—CH2—	(4-Cl—Ph)—C≡C—CH2—
204	CH3—CH2—CH2—	CH≡C—CH2—	(4-Cl—Ph)—C≡C—CH2—
205	(CH3)2CH—	CH≡C—CH2—	(4-Cl—Ph)—C≡C—CH2—
206	Cl—CH2—CH2—CH2—	CH≡C—CH2—	(4-Cl—Ph)—C≡C—CH2—
207	CH3—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—C≡C—CH2—
208	CH3—CH2—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—C≡C—CH2—
209	(CH3)2N—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—C≡C—CH2—
210	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—C≡C—CH2—
211	(CH3)2CH—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—C≡C—CH2—
212	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—C≡C—CH2—
213	CH3—	CH3—CH2—	(4-Br—Ph)—C≡C—CH2—
214	CH3—CH2—	CH3—CH2—	(4-Br—Ph)—C≡C—CH2—
215	(CH3)2N—	CH3—CH2—	(4-Br—Ph)—C≡C—CH2—
216	CH3—CH2—CH2—	CH3—CH2—	(4-Br—Ph)—C≡C—CH2—
217	(CH3)2CH—	CH3—CH2—	(4-Br—Ph)—C≡C—CH2—
218	Cl—CH2—CH2—CH2—	CH3—CH2—	(4-Br—Ph)—C≡C—CH2—
219	CH3—	(CH3)2CH—	(4-Br—Ph)—C≡C—CH2—
220	CH3—CH2—	(CH3)2CH—	(4-Br—Ph)—C≡C—CH2—
221	(CH3)2N—	(CH3)2CH—	(4-Br—Ph)—C≡C—CH2—
222	CH3—CH2—CH2—	(CH3)2CH—	(4-Br—Ph)—C≡C—CH2—
223	(CH3)2CH—	(CH3)2CH—	(4-Br—Ph)—C≡C—CH2—
224	Cl—CH2—CH2—CH2—	(CH3)2CH—	(4-Br—Ph)—C≡C—CH2—
225	CH3—	CH3—CH2—CH2—	(4-Br—Ph)—C≡C—CH2—
226	CH3—CH2—	CH3—CH2—CH2—	(4-Br—Ph)—C≡C—CH2—
227	(CH3)2N—	CH3—CH2—CH2—	(4-Br—Ph)—C≡C—CH2—
228	CH3—CH2—CH2—	CH3—CH2—CH2—	(4-Br—Ph)—C≡C—CH2—
229	(CH3)2CH—	CH3—CH2—CH2—	(4-Br—Ph)—C≡C—CH2—
230	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	(4-Br—Ph)—C≡C—CH2—
231	CH3—	100	(4-Br—Ph)—C≡C—CH2—
232	CH3—CH2—	101	(4-Br—Ph)—C≡C—CH2—
233	(CH3)2N—	102	(4-Br—Ph)—C≡C—CH2—
234	CH3—CH2—CH2—	103	(4-Br—Ph)—C≡C—CH2—
235	(CH3)2CH—	104	(4-Br—Ph)—C≡C—CH2—
236	Cl—CH2—CH2—CH2—	105	(4-Br—Ph)—C≡C—CH2—
237	CH3—	CH2═CH—CH2—	(4-Br—Ph)—C≡C—CH2—
238	CH3—CH2—	CH2═CH—CH2—	(4-Br—Ph)—C≡C—CH2—
239	(CH3)2N—	CH2═CH—CH2—	(4-Br—Ph)—C≡C—CH2—
240	CH3—CH2—CH2—	CH2═CH—CH2—	(4-Br—Ph)—C≡C—CH2—
241	(CH3)2CH—	CH2═CH—CH2—	(4-Br—Ph)—C≡C—CH2—
242	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	(4-Br—Ph)—C≡C—CH2—
243	CH3—	CH≡C—CH2—	(4-Br—Ph)—C≡C—CH2—
244	CH3—CH2—	CH≡C—CH2—	(4-Br—Ph)—C≡C—CH2—
245	(CH3)2N—	CH≡C—CH2—	(4-Br—Ph)—C≡C—CH2—
246	CH3—CH2—CH2—	CH≡C—CH2—	(4-Br—Ph)—C≡C—CH2—
247	(CH3)2CH—	CH≡C—CH2—	(4-Br—Ph)—C≡C—CH2—
248	Cl—CH2—CH2—CH2—	CH≡C—CH2—	(4-Br—Ph)—C≡C—CH2—
249	CH3—	CH3—CH2—CH(CH3)—	(4-Br—Ph)—C≡C—CH2—
250	CH3—CH2—	CH3—CH2—CH(CH3)—	(4-Br—Ph)—C≡C—CH2—
251	(CH3)2N—	CH3—CH2—CH(CH3)—	(4-Br—Ph)—C≡C—CH2—
252	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-Br—Ph)—C≡C—CH2—
253	(CH3)2CH—	CH3—CH2—CH(CH3)—	(4-Br—Ph)—C≡C—CH2—
254	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-Br—Ph)—C≡C—CH2—
255	CH3—	CH3—CH2—	H
256	CH3—CH2—	CH3—CH2—	H
257	(CH3)2N—	CH3—CH2—	H
258	CH3—CH2—CH2—	CH3—CH2—	H
259	(CH3)2CH—	CH3—CH2—	H
260	Cl—CH2—CH2—CH2—	CH3—CH2—	H
261	CH3—	(CH3)2CH—	H
262	CH3—CH2—	(CH3)2CH—	H
263	(CH3)2N—	(CH3)2CH—	H
264	CH3—CH2—CH2—	(CH3)2CH—	H
265	(CH3)2CH—	(CH3)2CH—	H
266	Cl—CH2—CH2—CH2—	(CH3)2CH—	H
267	CH3—	CH3—CH2—CH2—	H
268	CH3—CH2—	CH3—CH2—CH2—	H
269	(CH3)2N—	CH3—CH2—CH2—	H
270	CH3—CH2—CH2—	CH3—CH2—CH2—	H
271	(CH3)2CH—	CH3—CH2—CH2—	H
272	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	H
273	CH3—	106	H
274	CH3—CH2—	107	H
275	(CH3)2N—	108	H
276	CH3—CH2—CH2—	109	H
277	(CH3)2CH—	110	H
278	Cl—CH2—CH2—CH2—	111	H
279	CH3—	CH2═CH—CH2—	H
280	CH3—CH2—	CH2═CH—CH2—	H
281	(CH3)2N—	CH2═CH—CH2—	H
282	CH3—CH2—CH2—	CH2═CH—CH2—	H
283	(CH3)2CH—	CH2═CH—CH2—	H
284	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	H
285	CH3—	CH≡C—CH2—	H
286	CH3—CH2—	CH≡C—CH2—	H
287	(CH3)2N—	CH≡C—CH2—	H
288	CH3—CH2—CH2—	CH≡C—CH2—	H
289	(CH3)2CH—	CH≡C—CH2—	H
290	Cl—CH2—CH2—CH2—	CH≡C—CH2—	H
291	CH3—	CH3—CH2—CH(CH3)—	H
292	CH3—CH2—	CH3—CH2—CH(CH3)—	H
293	(CH3)2N—	CH3—CH2—CH(CH3)—	H
294	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	H
295	(CH3)2CH—	CH3—CH2—CH(CH3)—	H
296	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	H
297	CH3—	CH3—CH2—	Ph—CH2—
298	CH3—CH2—	CH3—CH2—	Ph—CH2—
299	(CH3)2N—	CH3—CH2—	Ph—CH2—
300	CH3—CH2—CH2—	CH3—CH2—	Ph—CH2—
301	(CH3)2CH—	CH3—CH2—	Ph—CH2—
302	Cl—CH2—CH2—CH2—	CH3—CH2—	Ph—CH2—
303	CH3—	(CH3)2CH—	Ph—CH2—
304	CH3—CH2—	(CH3)2CH—	Ph—CH2—
305	(CH3)2N—	(CH3)2CH—	Ph—CH2—
306	CH3—CH2—CH2—	(CH3)2CH—	Ph—CH2—
307	(CH3)2CH—	(CH3)2CH—	Ph—CH2—
308	Cl—CH2—CH2—CH2—	(CH3)2CH—	Ph—CH2—
309	CH3—	CH3—CH2—CH2—	Ph—CH2—
310	CH3—CH2—	CH3—CH2—CH2—	Ph—CH2—
311	(CH3)2N—	CH3—CH2—CH2—	Ph—CH2—
312	CH3—CH2—CH2—	CH3—CH2—CH2—	Ph—CH2—
313	(CH3)2CH—	CH3—CH2—CH2—	Ph—CH2—
314	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	Ph—CH2—
315	CH3—	112	Ph—CH2—
316	CH3—CH2—	113	Ph—CH2—
317	(CH3)2N—	114	Ph—CH2—
318	CH3—CH2—CH2—	115	Ph—CH2—
319	(CH3)2CH—	116	Ph—CH2—
320	Cl—CH2—CH2—CH2—	117	Ph—CH2—
321	CH3—	CH2═CH—CH2—	Ph—CH2—
322	CH3—CH2—	CH2═CH—CH2—	Ph—CH2—
323	(CH3)2N—	CH2═CH—CH2—	Ph—CH2—
324	CH3—CH2—CH2—	CH2═CH—CH2—	Ph—CH2—
325	(CH3)2CH—	CH2═CH—CH2—	Ph—CH2—
326	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	Ph—CH2—
327	CH3—	CH≡C—CH2—	Ph—CH2—
328	CH3—CH2—	CH≡C—CH2—	Ph—CH2—
329	(CH3)2N—	CH≡C—CH2—	Ph—CH2—
330	CH3—CH2—CH2—	CH≡C—CH2—	Ph—CH2—
331	(CH3)2CH—	CH≡C—CH2—	Ph—CH2—
332	Cl—CH2—CH2—CH2—	CH≡C—CH2—	Ph—CH2—
333	CH3—	CH3—CH2—CH(CH3)—	Ph—CH2—
334	CH3—CH2—	CH3—CH2—CH(CH3)—	Ph—CH2—
335	(CH3)2N—	CH3—CH2—CH(CH3)—	Ph—CH2—
336	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	Ph—CH2—
337	(CH3)2CH—	CH3—CH2—CH(CH3)—	Ph—CH2—
338	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	Ph—CH2—
339	CH3—	CH3—CH2—	(4-Cl—Ph)—CH2—
340	CH3—CH2—	CH3—CH2—	(4-Cl—Ph)—CH2—
341	(CH3)2N—	CH3—CH2—	(4-Cl—Ph)—CH2—
342	CH3—CH2—CH2—	CH3—CH2—	(4-Cl—Ph)—CH2—
343	(CH3)2CH—	CH3—CH2—	(4-Cl—Ph)—CH2—
344	Cl—CH2—CH2—CH2—	CH3—CH2—	(4-Cl—Ph)—CH2—
345	CH3—	(CH3)2CH—	(4-Cl—Ph)—CH2—
346	CH3—CH2—	(CH3)2CH—	(4-Cl—Ph)—CH2—
347	(CH3)2N—	(CH3)2CH—	(4-Cl—Ph)—CH2—
348	CH3—CH2—CH2—	(CH3)2CH—	(4-Cl—Ph)—CH2—
349	(CH3)2CH—	(CH3)2CH—	(4-Cl—Ph)—CH2—
350	Cl—CH2—CH2—CH2—	(CH3)2CH—	(4-Cl—Ph)—CH2—
351	CH3—	CH3—CH2—CH2—	(4-Cl—Ph)—CH2—
352	CH3—CH2—	CH3—CH2—CH2—	(4-Cl—Ph)—CH2—
353	(CH3)2N—	CH3—CH2—CH2—	(4-Cl—Ph)—CH2—
354	CH3—CH2—CH2—	CH3—CH2—CH2—	(4-Cl—Ph)—CH2—
355	(CH3)2CH—	CH3—CH2—CH2—	(4-Cl—Ph)—CH2—
356	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	(4-Cl—Ph)—CH2—
357	CH3—	118	(4-Cl—Ph)—CH2—
358	CH3—CH2—	119	(4-Cl—Ph)—CH2—
359	(CH3)2N—	120	(4-Cl—Ph)—CH2—
360	CH3—CH2—CH2—	121	(4-Cl—Ph)—CH2—
361	(CH3)2CH—	122	(4-Cl—Ph)—CH2—
362	Cl—CH2—CH2—CH2—	123	(4-Cl—Ph)—CH2—
363	CH3—	CH2═CH—CH2—	(4-Cl—Ph)—CH2—
364	CH3—CH2—	CH2═CH—CH2—	(4-Cl—Ph)—CH2—
365	(CH3)2N—	CH2═CH—CH2—	(4-Cl—Ph)—CH2—
366	CH3—CH2—CH2—	CH2═CH—CH2—	(4-Cl—Ph)—CH2—
367	(CH3)2CH—	CH2═CH—CH2—	(4-Cl—Ph)—CH2—
368	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	(4-Cl—Ph)—CH2—
369	CH3—	CH≡C—CH2—	(4-Cl—Ph)—CH2—
370	CH3—CH2—	CH≡C—CH2—	(4-Cl—Ph)—CH2—
371	(CH3)2N—	CH≡C—CH2—	(4-Cl—Ph)—CH2—
372	CH3—CH2—CH2—	CH≡C—CH2—	(4-Cl—Ph)—CH2—
373	(CH3)2CH—	CH≡C—CH2—	(4-Cl—Ph)—CH2—
374	Cl—CH2—CH2—CH2—	CH≡C—CH2—	(4-Cl—Ph)—CH2—
375	CH3—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—CH2—
376	CH3—CH2—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—CH2—
378	(CH3)2N—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—CH2—
379	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—CH2—
380	(CH3)2CH—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—CH2—
381	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	(4-Cl—Ph)—CH2—
382	CH3—	CH3—CH2—	(3-Cl—Ph)—CH2—
383	CH3—CH2—	CH3—CH2—	(3-Cl—Ph)—CH2—
384	(CH3)2N—	CH3—CH2—	(3-Cl—Ph)—CH2—
385	CH3—CH2—CH2—	CH3—CH2—	(3-Cl—Ph)—CH2—
386	(CH3)2CH—	CH3—CH2—	(3-Cl—Ph)—CH2—
387	Cl—CH2—CH2—CH2—	CH3—CH2—	(3-Cl—Ph)—CH2—
388	CH3—	(CH3)2CH—	(3-Cl—Ph)—CH2—
389	CH3—CH2—	(CH3)2CH—	(3-Cl—Ph)—CH2—
390	(CH3)2N—	(CH3)2CH—	(3-Cl—Ph)—CH2—
391	CH3—CH2—CH2—	(CH3)2CH—	(3-Cl—Ph)—CH2—
392	(CH3)2CH—	(CH3)2CH—	(3-Cl—Ph)—CH2—
393	Cl—CH2—CH2—CH2—	(CH3)2CH—	(3-Cl—Ph)—CH2—
394	CH3—	CH3—CH2—CH2—	(3-Cl—Ph)—CH2—
395	CH3—CH2—	CH3—CH2—CH2—	(3-Cl—Ph)—CH2—
396	(CH3)2N—	CH3—CH2—CH2—	(3-Cl—Ph)—CH2—
397	CH3—CH2—CH2—	CH3—CH2—CH2—	(3-Cl—Ph)—CH2—
398	(CH3)2CH—	CH3—CH2—CH2—	(3-Cl—Ph)—CH2—
399	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	(3-Cl—Ph)—CH2—
400	CH3—	124	(3-Cl—Ph)—CH2—
401	CH3—CH2—	125	(3-Cl—Ph)—CH2—
402	(CH3)2N—	126	(3-Cl—Ph)—CH2—
403	CH3—CH2—CH2—	127	(3-Cl—Ph)—CH2—
404	(CH3)2CH—	128	(3-Cl—Ph)—CH2—
405	Cl—CH2—CH2—CH2—	129	(3-Cl—Ph)—CH2—
406	CH3—	CH2═CH—CH2—	(3-Cl—Ph)—CH2—
407	CH3—CH2—	CH2═CH—CH2—	(3-Cl—Ph)—CH2—
408	(CH3)2N—	CH2═CH—CH2—	(3-Cl—Ph)—CH2—
409	CH3—CH2—CH2—	CH2═CH—CH2—	(3-Cl—Ph)—CH2—
410	(CH3)2CH—	CH2═CH—CH2—	(3-Cl—Ph)—CH2—
411	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	(3-Cl—Ph)—CH2—
412	CH3—	CH≡C—CH2—	(3-Cl—Ph)—CH2—
413	CH3—CH2—	CH≡C—CH2—	(3-Cl—Ph)—CH2—
414	(CH3)2N—	CH≡C—CH2—	(3-Cl—Ph)—CH2—
415	CH3—CH2—CH2—	CH≡C—CH2—	(3-Cl—Ph)—CH2—
416	(CH3)2CH—	CH≡C—CH2—	(3-Cl—Ph)—CH2—
417	Cl—CH2—CH2—CH2—	CH≡C—CH2—	(3-Cl—Ph)—CH2—
418	CH3—	CH3—CH2—CH(CH3)—	(3-Cl—Ph)—CH2—
419	CH3—CH2—	CH3—CH2—CH(CH3)—	(3-Cl—Ph)—CH2—
420	(CH3)2N—	CH3—CH2—CH(CH3)—	(3-Cl—Ph)—CH2—
421	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	(3-Cl—Ph)—CH2—
422	(CH3)2CH—	CH3—CH2—CH(CH3)—	(3-Cl—Ph)—CH2—
423	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	(3-Cl—Ph)—CH2—
424	CH3—	CH3—CH2—	(3-CF3—Ph)—CH2—
425	CH3—CH2—	CH3—CH2—	(3-CF3—Ph)—CH2—
426	(CH3)2N—	CH3—CH2—	(3-CF3—Ph)—CH2—
427	CH3—CH2—CH2—	CH3—CH2—	(3-CF3—Ph)—CH2—
428	(CH3)2CH—	CH3—CH2—	(3-CF3—Ph)—CH2—
429	Cl—CH2—CH2—CH2—	CH3—CH2—	(3-CF3—Ph)—CH2—
430	CH3—	(CH3)2CH—	(3-CF3—Ph)—CH2—
431	CH3—CH2—	(CH3)2CH—	(3-CF3—Ph)—CH2—
432	(CH3)2N—	(CH3)2CH—	(3-CF3—Ph)—CH2—
433	CH3—CH2—CH2—	(CH3)2CH—	(3-CF3—Ph)—CH2—
434	(CH3)2CH—	(CH3)2CH—	(3-CF3—Ph)—CH2—
435	Cl—CH2—CH2—CH2—	(CH3)2CH—	(3-CF3—Ph)—CH2—
436	CH3—	CH3—CH2—CH2—	(3-CF3—Ph)—CH2—
437	CH3—CH2—	CH3—CH2—CH2—	(3-CF3—Ph)—CH2—
438	(CH3)2N—	CH3—CH2—CH2—	(3-CF3—Ph)—CH2—
439	CH3—CH2—CH2—	CH3—CH2—CH2—	(3-CF3—Ph)—CH2—
440	(CH3)2CH—	CH3—CH2—CH2—	(3-CF3—Ph)—CH2—
441	Cl—CH2—CH2—CH2—	CH3—CH2—CH2—	(3-CF3—Ph)—CH2—
442	CH3—	130	(3-CF3—Ph)—CH2—
443	CH3—CH2—	131	(3-CF3—Ph)—CH2—
444	(CH3)2N—	132	(3-CF3—Ph)—CH2—
445	CH3—CH2—CH2—	133	(3-CF3—Ph)—CH2—
446	(CH3)2CH—	134	(3-CF3—Ph)—CH2—
447	Cl—CH2—CH2—CH2—	135	(3-CF3—Ph)—CH2—
448	CH3—	CH2═CH—CH2—	(3-CF3—Ph)—CH2—
449	CH3—CH2—	CH2═CH—CH2—	(3-CF3—Ph)—CH2—
450	(CH3)2N—	CH2═CH—CH2—	(3-CF3—Ph)—CH2—
451	CH3—CH2—CH2—	CH2═CH—CH2—	(3-CF3—Ph)—CH2—
452	(CH3)2CH—	CH2═CH—CH2—	(3-CF3—Ph)—CH2—
453	Cl—CH2—CH2—CH2—	CH2═CH—CH2—	(3-CF3—Ph)—CH2—
454	CH3—	CH≡C—CH2—	(3-CF3—Ph)—CH2—
455	CH3—CH2—	CH≡C—CH2—	(3-CF3—Ph)—CH2—
456	(CH3)2N—	CH≡C—CH2—	(3-CF3—Ph)—CH2—
457	CH3—CH2—CH2—	CH≡C—CH2—	(3-CF3—Ph)—CH2—
458	(CH3)2CH—	CH≡C—CH2—	(3-CF3—Ph)—CH2—
459	Cl—CH2—CH2—CH2—	CH≡C—CH2—	(3-CF3—Ph)—CH2—
460	CH3—	CH3—CH2—CH(CH3)—	(3-CF3—Ph)—CH2—
461	CH3—CH2—	CH3—CH2—CH(CH3)—	(3-CF3—Ph)—CH2—
462	(CH3)2N—	CH3—CH2—CH(CH3)—	(3-CF3—Ph)—CH2—
463	CH3—CH2—CH2—	CH3—CH2—CH(CH3)—	(3-CF3—Ph)—CH2—
464	(CH3)2CH—	CH3—CH2—CH(CH3)—	(3-CF3—Ph)—CH2—
465	Cl—CH2—CH2—CH2—	CH3—CH2—CH(CH3)—	(3-CF3—Ph)—CH2—

[0194] Table 12: Compounds represented by the Formula I.12 where the combination of the R1 and R3 corresponds to each row in table B. 136

[0195] Table 13: Compounds represented by the Formula I.13 where the combination of the R1 and R3 corresponds to each row in table B. 137

[0196] Table 4: Compounds represented by the Formula I.14 where the combination of the R1 and R3 corresponds to each row in table B. 138

	TABLE B
	No.	R1	R3
	001	(CH3—CH2)2N—	CH3—CH2—
	002	CH3—CH2—(CH3)N—	CH3—CH2—
	003	139	CH3—CH2—
	004	CH3—(CH2)2—CH2—	CH3—CH2—
	005	(CH3)2CH—CH2—	CH3—CH2—
	006	CH3—CH2—(CH3)CH—	CH3—CH2—
	007	(CH3)3C—	CH3—CH2—
	008	CH2═CH—	CH3—CH2—
	009	140	CH3—CH2—
	010	(CH3—CH2)2N—	(CH3)2CH—
	011	CH3—CH2—(CH3)N—	(CH3)2CH—
	012	141	(CH3)2CH—
	013	CH3—(CH2)2—CH2—	(CH3)2CH—
	014	(CH3)2CH—CH2—	(CH3)2CH—
	015	CH3—CH2—(CH3)CH—	(CH3)2CH—
	016	(CH3)3C—	(CH3)2CH—
	017	CH2═CH—	(CH3)2CH—
	018	142	(CH3)2CH—
	019	(CH3—CH2)2N—	CH3—CH2—CH2
	020	CH3—CH2—(CH3)N—	CH3—CH2—CH2
	021	143	CH3—CH2—CH2
	022	CH3—(CH2)2—CH2—	CH3—CH2—CH2
	023	(CH3)2CH—CH2—	CH3—CH2—CH2
	024	CH3—CH2—(CH3)CH—	CH3—CH2—CH2
	025	(CH3)3C—	CH3—CH2—CH2
	026	CH2═CH—	CH3—CH2—CH2
	027	144	CH3—CH2—CH2
	028	(CH3—CH2)2N—	CH3—CH2—(CH3)CH—
	029	CH3—CH2—(CH3)N—	CH3—CH2—(CH3)CH—
	030	145	CH3—CH2—(CH3)CH—
	031	CH3—(CH2)2—CH2—	CH3—CH2—(CH3)CH—
	032	(CH3)2CH—CH2—	CH3—CH2—(CH3)CH—
	033	CH3—CH2—(CH3)CH—	CH3—CH2—(CH3)CH—
	034	(CH3)3C—	CH3—CH2—(CH3)CH—
	035	CH2═CH—	CH3—CH2—(CH3)CH—
	036	146	CH3—CH2—(CH3)CH—
	037	(CH3—CH2)2N—	147
	038	CH3—CH2—(CH3)N—	148
	039	149	150
	040	CH3—(CH2)2—CH2—	151
	041	(CH3)2CH—CH2—	152
	042	CH3—CH2—(CH3)CH—	153
	043	(CH3)3C—	154
	044	CH2═CH—	155
	045	156	157
	046	CH3—	HO—CH2—
	047	CH3—CH2—	HO—CH2—
	048	(CH3)2N—	HO—CH2—
	049	CH3—CH2—CH2—	HO—CH2—
	050	(CH3)2CH—	HO—CH2—
	051	CH3—CH2—(CH3)CH—	HO—CH2—
	052	CH3—	HO—(CH3)CH—
	053	CH3—CH2—	HO—(CH3)CH—
	054	(CH3)2N—	HO—(CH3)CH—
	055	CH3—CH2—CH2—	HO—(CH3)CH—
	056	(CH3)2CH—	HO—(CH3)CH—
	057	CH3—CH2—(CH3)CH—	HO—(CH3)CH—
	058	CH3—	(CH3)3C—O—(CH3)CH—
	059	CH3—CH2—	(CH3)3C—O—(CH3)CH—
	060	(CH3)2N—	(CH3)3C—O—(CH3)CH—
	061	CH3—CH2—CH2—	(CH3)3C—O—(CH3)CH—
	062	(CH3)2CH—	(CH3)3C—O—(CH3)CH—
	063	CH3—CH2—(CH3)CH—	(CH3)3C—O—(CH3)CH—
	064	CH3—	CH3—S—CH2—CH2—
	065	CH3—CH2—	CH3—S—CH2—CH2—
	066	(CH3)2N—	CH3—S—CH2—CH2—
	067	CH3—CH2—CH2—	CH3—S—CH2—CH2—
	068	(CH3)2CH—	CH3—S—CH2—CH2—
	069	CH3—CH2—(CH3)CH—	CH3—S—CH2—CH2—
	070	CH3—	HS—CH2—CH2—
	071	CH3—CH2—	HS—CH2—CH2—
	072	(CH3)2N—	HS—CH2—CH2—
	073	CH3—CH2—CH2—	HS—CH2—CH2—
	074	(CH3)2CH—	HS—CH2—CH2—
	075	CH3—CH2—(CH3)CH—	HS—CH2—CH2—
	076	CH3—	(CH3)3C—
	077	CH3—CH2—	(CH3)3C—
	078	(CH3)2N—	(CH3)3C—
	079	CH3—CH2—CH2—	(CH3)3C—
	080	(CH3)2CH—	(CH3)3C—
	081	CH3—CH2—(CH3)CH—	(CH3)3C—

[0197] Table 15: Compounds represented by the Formula I.15 where the combination of the group R10 corresponds to each row in table C. 158

[0198] Table 16: Compounds represented by the Formula I.16 where the combination of the group responds to each row in table C. 159

TABLE C
No. R10
001 CH3—CH2—C(CH3)H—C≡C—CH2—
002 (CH3)3C—C≡C—CH2—
003 (CH3)2CH—CH2—C≡C—CH2—
004 CH3—(CH2)4—C≡C—CH2—
005 160
006 161
007 (4-CH3—Ph)—C≡C—CH2—
008 (2-Cl—Ph)—C≡C—CH2—
009 (3-Cl—Ph)—C≡C—CH2—
010 (3-Br—Ph)—C≡C—CH2—
011 (3-F—Ph)—C≡C—CH2—
012 (3-CH3—Ph)—C≡C—CH2—
013 (2,4-di-Cl—Ph)—C≡C—CH2—
014 (3,4-di-Cl—Ph)—C≡C—CH2—
015 (3,4-di-F—Ph)—C≡C—CH2—
016 (3-CH3-4-Cl—Ph)—C≡C—CH2—
017 (3-CH3-4-Br—Ph)—C≡C—CH2—
018 (3-CF3—Ph)—C≡C—CH2—
019 (4-CF3O—Ph)—C≡C—CH2—
020 (4-Et—Ph)—C≡C—CH2—
021 [4-(CH3)3C—Ph]—C≡C—CH2—
022 (4-CH2═CH—Ph)—C≡C—CH2—
023 (4-CH≡C—Ph)—C≡C—CH2—
024 (4-CH3—CO—Ph)—C≡C—CH2—
025 (4-CH3OOC—Ph)—C≡C—CH2—
026 (4-CH3O—Ph)—C≡C—CH2—
027 162
028 163
029 164
030 165
031 Ph—(CH3)CH—
032 Ph—(CH3)2C—
033 (3-F—Ph)—CH2—
034 (4-Br—Ph)—CH2—
035 (4-J-Ph)—CH2—
036 (4-CH3—Ph)—CH2—
037 (4-CH3O—Ph)—CH2—
038 (4-CF3O—Ph)—CH2—
039 (4-F—Ph)—CH2—
040 (2,4-di-F—Ph)—CH2—
041 (3,4-di-F—Ph)—CH2—
042 (3,4-di-Br—Ph)—CH2—
043 (3,4-di-Cl—Ph)—CH2—
044 (3-Cl-4-CH3—Ph)—CH2—
045 (3-CH3-4-Cl—Ph)—CH2—
046 (2,4,5-tri-Cl—Ph)—CH2—
047 166
048 167
049 168
050 169
051 170
052 171
053 172
054 173
055 174
056 175
057 Ph—CH═CH—CH2—
058 (4-Cl—Ph)—CH═CH—CH2—
059 (4-F—Ph)—CH═CH—CH2—
060 (4-Br—Ph)—CH═CH—CH2—
061 (3-CF3-Ph)—CH═CH-2-
062 Ph—CH2—CH2—
063 Ph—(CH2)2—CH2—
064 (4-Cl—Ph)—(CH2)2—CH2—
065 (4-Br—Ph)—(CH2)2—CH2—
066 Ph—O—CH2—CH2—
067 (4-Cl—Ph)—O—CH2—CH2—
068 (4-F—Ph)—O—CH2—CH2—
069 (4-Br—Ph)—O—CH2—CH2—
070 (3-F—Ph)—O—CH2—CH2—
071 (3,4-di-Cl—Ph)—O—CH2—CH2—
072 (4-Cl—Ph)—O—(CH3)CH—CH2—
073 (3,4-di-Cl—Ph)—O—(CH3)CH—CH2—
074 Ph—N(CH3)—CH2—CH2—
075 Ph—N(CH2—CH3)—CH2—CH2—
076 Ph—S—CH2—CH2—
077 (4-Cl—Ph)—S—CH2—CH2—

[0199] Formulations may be prepared analogously to those described in, for example, WO 95/30651.

Biological Examples

[0200] D-1: Action Against Plasmopara viticola (Downy Mildew) on Vines

[0201] 5 week old grape seedlings cv. Gutedel are treated with the formulated test compound in a spray chamber. One day after application grape plants are inoculated by spraying a sporangia suspension (4×104 sporangia/ml) on the lower leaf side of the test plants. After an incubation period of 6 days at +21° C. and 95% r. h. in a greenhouse the disease incidence is assessed.

[0202] Compounds of Tables 1 to 16 exhibit a good fungicidal action against Plasmopara viticola on vines. Compounds A1.3 and A1.4 at 200 ppm inhibit fungal infestation in this test to a 80%, while under the same conditions untreated control plants are infected by the pathogenic fungi to over 80%.

[0203] D-2: Action Against Phytophthora (Late Blight) on Tomato Plants

[0204] 3 week old tomato plants cv. Roter Gnom are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (2×104 sporangia/ml) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Compounds of Tables 1 to 16 exhibit a long-lasting effect against fungus infestation. Compounds A1.3 and A1.4 at 200 ppm inhibit fungal infestation in this test to a least 80%, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80%.

[0205] D-3: Action Against Phytophthora (Late Blight) on Potato Plants

[0206] 5 week old potato plants cv. Bintje are treated with the formulated test compound in a spray chamber. Two day after application the plants are inoculated by spraying a sporangia suspension (14×104 sporangia/ml) on the test plants. After an incubation period of 4 days at +18° C. and 95% r. h. in a growth chamber the disease incidence is assessed. Fungal infestation is effectively controlled with compounds of Tables 1 to 16.

Claims

1. α-Sulfin- and α-sulfonamino acid amides of formula I

2. A compound according to claim 1 wherein n is one.

3. A compound of formula I according to claim 1 wherein R1 is C1-C12alkyl, C1-C2alkyl substituted with C1-C4alkoxy, C1-C4alkylthio, or C1-C4alkylsulfonyl; C2-C12alkenyl; C2-C12alkynyl; C1-C12halogenalkyl; or a group NR11R12 wherein R11 and R12 are each independently of the other hydrogen or C1-C6alkyl, or together are tetra- or penta-methylene.

4. A compound of formula I according to claim 1 wherein R2 is hydrogen and R3 is C1-C8alkyl, C1-C8alkyl optionally substituted by hydroxy, C1-C4alkoxy, mercapto or C1-C4alkylthio; C3-C8alkenyl; C3-C8alkynyl; C3-C8cycloalkyl or C3-C8cycloalkyl-C1-C4alkyl.

5. A compound of formula I according to claim 1 wherein R4 is hydrogen, methyl or ethyl.

6. A compound of formula I according to claim 1 wherein R5, R6 and R7 are each independently hydrogen or methyl.

7. A compound of formula I according to claim 1 wherein R8 is hydrogen, C1-C8-alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, C1-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino.

8. A compound of formula I according to claim 1 wherein R9 is C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C1-C4alkyl, C1-C8alkylthio, C1-C8alkylsulfonyl, C1-C8alkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, C3-C8cycloalkoxy, Cl-C8alkoxy-C1-C4alkyl, C1-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkanoyl, C1-C8dialkylamino, C1-C8alkylamino wherein in each of the above radicals the alkyl, alkenyl, alkynyl or cycloalkyl groups may be partially or fully halogenated; carboxy, formyl, halogen, nitro, cyano, hydroxy or amino, provided that when R8 is hydrogen, R9 is not C1-C6alkoxy, C3-C6alkenyloxy or C3-C6alkynyloxy in position 3 of the phenyl ring carrying these radicals.

9. A compound of formula I according to claim 1 wherein R13, R14, R16, R17 and R19 are each independently hydrogen or methyl.

10. A compound of formula I according to claim 1 wherein R15 is C4-C12alkyl; C1-C12halogenalkyl; C3-C8Cycloalkyl; optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.

11. A compound of formula I according to claim 1 wherein R18 is optionally substituted aryl or optionally substituted heteroaryl consisting of one or two condensed five or six membered rings with 1 to 4 identical or different heteroatoms selected from oxygen, nitrogen or sulfur.

12. A compound of formula I according to claim 1 wherein Z is oxygen, sulfur or —CH2—.

13. A compound of formula I according to claim 1 wherein n is one; R1 is C1-C4alkyl, vinyl; C1-C4halogenalkyl; or dimethylamino; R2 is hydrogen and R3 is isopropyl; R4, R5, R7, R11, R12, R14, R15 and R17 are each hydrogen; R8 is hydrogen; R9 is C1-C4alkyl, halogen or cyano; R15 is C4-C8alkyl; C1-C6halogenalkyl; C3-C8cycloalkyl; phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8alkyl, C1-C8halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; R18 is phenyl, pyridyl, with each of the aromatic ring being optionally substituted by 1 to 3 substituents selected from the group consisting of C1-C8-alkyl, C1-C8-halogenalkyl, C1-C8alkoxy, C1-C8halogenalkoxy, C1-C8alkylthio, C1-C8halogenalkylthio, halogen, cyano, nitro and C1-C8alkoxycarbonyl; and Z is oxygen.

14. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting a) an amino acid of formula II or a carboxy-activated derivative thereof 178wherein R1, n, R2 and R3 are as defined for formula I is reacted with an amine of formula III 179wherein R4, R5 R6, R7, R8, R9 and R10 are as defined for formula I optionally in the presence of a base and optionally in the presence of a diluting agent, or b) an amino acid derivative of formula VI 180wherein R2, R3, R4, R5, R6, R7, R8, R9and R10 are as defined for formula I with a sulfonyl halide or a sulfinyl halide of formula V 181wherein R1 and n are as defined for formula I and X is halide, preferentially chlorine or bromine, or c) a phenol of formula VII 182wherein R1, n, R2, R3, R4, R5, R6, R7, R8 and R9 are as defined for formula I with a compound of formula VIII Y—R10  (VIII) wherein R10 is as defined for formula I and Y is a leaving group like a halide such as a chloride or bromide or a sulfonic ester such as a tosylate, mesylate or triflate.

15. A process for the preparation of a compound of formula Ia

16. A composition for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I according to claim 1 as active ingredient together with a suitable carrier.

17. The use of a compound of formula I according to claim 1 in protecting plants against infestation by phytopathogenic microorganisms.

18. A method of controlling and preventing an infestation of crop plants by phytopathogenic microorganisms, preferably fungal organisms, which comprises the application of a compound of formula I according to claim 1 as active ingredient to the plant, to parts of plants or to the locus thereof.