Certain 2-(2-chloro-3-alkoxy-4-substituted benzoyl)-5-methyl-5-1,3-cyclohexanediones as herbicides

BACKGROUND OF THE INVENTION
Compounds having the structural formula ##STR2## wherein X can be alkyl, n can be 0, 1, or 2, and R.sub.1 can be phenyl or substituted phenyl are described in Japanese Patent Application 84632-1974 as being intermediates for the preparation of herbicidal compounds of the formula ##STR3## wherein R.sub.1, X, and n are as defined above and R.sub.2 is alkyl, alkenyl, or alkynyl. Specifically taught herbicidal compounds of this latter group are those where n is 2, X is 5,5-dimethyl, R.sub.2 is allyl and R.sub.1 is phenyl, 4-chlorophenyl or 4-methoxyphenyl.
The precursor intermediates for these three specifically taught compounds have no or almost no herbicidal activity.
DESCRIPTION OF THE INVENTION
Embodiment A of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of this embodiment have the following structural formula ##STR4## wherein
R and R.sup.1 are hydrogen, C.sub.1 -C.sub.4 alkyl, preferably methyl or isopropyl, R.sup.a OC(O)-, where R.sup.a is C.sub.1 -C.sub.4 alkyl; most preferably R and R.sup.1 are hydrogen;
R.sup.2 is chlorine, bromine, iodine or C.sub.1 -C.sub.4 alkoxy, preferably methoxy; most preferably R.sub.2 is chlorine, bromine or methoxy;
R.sup.3, R.sup.4 and R.sup.5 independently are hydrogen or an aliphatic group, preferably: (1) hydrogen; (2) halogen, preferably chlorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl, C.sub.1 -C.sub.4 haloalkyl, phenyl, benzyl, --NR.sup.d R.sup.e wherein R.sup.d and R.sup.e independently are hydrogen or C.sub.1 -C.sub.4 alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR5## wherein R.sup.c is C.sub.1 -C.sub.4 alkyl and R.sup.j is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl; (11) R.sup.f C(O) wherein R.sup.f is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy; (12) --NR.sup.g R.sup.h wherein R.sup.g and R.sup.h independently are hydrogen or C.sub.1 -C.sub.4 alkyl; or less preferably (13) R.sup.3 and R.sup.4 together can form a ring structure with two adjacent carbon atoms of the phenyl ring.
R.sup.3 and R.sup.4 can also be (14) C.sub.3 -C.sub.5 alkenyloxy (thio) optionally substituted, preferably with halogen or (15) C.sub.3 -C.sub.5 alkynyloxy (thio), optionally substituted, preferably with halogen.
Most preferably, R.sup.3 is chlorine, hydrogen, dimethylamino or methoxy. Preferably, R.sup.4 is hydrogen, chlorine, nitro, SO.sub.2 CH.sub.3, SO.sub.2 N(CH.sub.3).sub.2 or trifluoromethyl. Preferably, R.sup.5 is hydrogen.
Embodiment A' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier threfor. Preferably, the 2-position of the benzoyl moiety is substituted with chlorine, bromine, iodine or C.sub.1 -C.sub.4 alkoxy; more preferably chlorine, bromine or methoxy; most preferably chlorine. The 5-position of the 1,3-cyclohexanedione moiety can be substituted with one or two C.sub.1 -C.sub.4 alkyl groups, preferably methyl, although such a substitution is not preferred.
The compounds of Embodiment A of this invention can have the following four structural formulae because of tautomerism: ##STR6## wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR7## wherein R, R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals, e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
In the above description of the compounds of this invention, alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
Embodiment B of this invention relates to certain novel 2-(2-substituted benzoyl)-cyclohexane-1,3-diones as herbicides. The compounds of this embodiment have the following structural formula ##STR8## wherein
R.sup.10 is C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 -C.sub.4, more preferably methyl;
R.sup.11 is hydrogen or C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 -C.sub.4, more preferably methyl or ##STR9## wherein R.sup.a is C.sub.1 -C.sub.4 alkyl or R.sup.10 and R.sup.11 together are alkylene having 3 to 6 carbon atoms, most preferably R.sup.11 is hydrogen or methyl;
R.sup.12 is chlorine, bromine, iodine, fluorine or C.sub.1 -C.sub.4 alkoxy, preferably methoxy; most preferably R.sup.12 is chlorine, bromine or methoxy;
R.sup.13 and R.sup.14 independently are (1) hydrogen or an aliphatic group, preferably hydrogen; (2) halogen, preferably, fluorine, chlorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 aliphatic alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl, C.sub.1 -C.sub.4 haloalkyl, phenyl, benzyl, --NR.sup.d R.sup.e wherein R.sup.d and R.sup.e independently are hydrogen or C.sub.1 -C.sub.4 alkyl; and n is the integer 0, 1 or 2, preferably 2; ##STR10## wherein R.sup.c is C.sub.1 -C.sub.4 alkyl and R.sup.j is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl; (11) R.sup.f C(O) wherein R.sup.f is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy; (12) --NR.sup.g R.sup.h wherein R.sup.g and R.sup.h independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (13) C.sub.1 -C.sub.4 alkylthio or less preferably (14) R.sup.13 and R.sup.14 together can form a ring structure with two adjacent carbon atoms of the phenyl ring to which they are attached or less preferably (15) R.sup.13 and R.sup.14 are the groups phenoxy or substituted phenoxy wherein the substituent is halogen or halomethyl or both;
R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are independently the same or different and are selected from the group consisting of hydrogen, C.sub.1 -C.sub.6 alkyl, preferably C.sub.1 -C.sub.4 alkyl, more preferably methyl, most preferably hydrogen or methyl, and their salts;
provided, however, that R.sup.15 and R.sup.16 together may form a substituted or unsubstituted alkylene ring of 2-5 carbon atoms, the preferred substituent being 1 or 2 methyl groups.
More preferably, R.sup.13 is chlorine, hydrogen, methyl, alkylthio or methoxy. Preferably R.sup.14 is hydrogen, chlorine, nitro, trifluoromethyl, or R.sup.b SO.sub.n wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl and n is the integer 0, 1 or 2, preferably 2.
The compounds of Embodiment B of this invention can have the following four structural formulae because of tautomerism: ##STR11## wherein R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR12## wherein R.sup.10, R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 and R.sup.18 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, alkaline earth metals, e.g. barium, magnesium, calcium and strontium, or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substitutent is an aliphatic or aromatic group.
The term "aliphatic group" is used form Embodiments A and B herein in a broad sense to cover a large class of organic groups characterized by being derived from (1) an acylic (open-chain structure) of the paraffin, olefin and acetylene hydrocarbon series and their derivatives or (2) alicyclic compounds. The aliphatic group can have from 1 to 10 carbon atoms.
The term "aromatic group" is used for Embodiments A and B herein in a broad sense to distinguish from the aliphatic group and includes a group derived from (1) compounds having 6 to 20 carbon atoms and characterized by the presence of at least one benzene ring, including monocyclic, bicyclic and polycyclic hydrocarbons and their derivatives and (2) heterocyclic compounds having 5 to 19 carbon atoms which are similar in structure and are characterized by having an unsaturated ring structure containing at least one atom other than carbon such as nitrogen, sulfur and oxygen and derivatives of these heterocyclic compounds.
In the above description of the compounds of this invention alkyl and alkoxy include both straight and branched configurations; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl.
Embodiment C of this invention relates to certain novel 2-(2'-cyanobenzoyl)cyclohexane-1,3-diones as herbicides. The compounds of of this embodiment have the following structural formula ##STR13## wherein R.sup.21 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.21 is hydrogen or methyl;
R.sup.22 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl or ##STR14## wherein R.sup.a is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.22 is hydrogen or methyl; or R.sup.21 and R.sup.22 together are alkylene having 3 to 6 carbon atoms;
R.sup.23 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.23 is hydrogen or methyl;
R.sup.24 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.24 is hydrogen or methyl;
R.sup.25 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.25 is hydrogen or methyl;
R.sup.26 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.26 is hydrogen;
R.sup.27 and R.sup.28 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined, with the proviso that R.sup.27 is not attached to the 6-position.
Preferably, R.sup.27 is in the 3-position. Most preferably R.sup.27 is hydrogen and R.sup.28 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this embodiment can have the following four structural formulae because of tautomerism: ##STR15## wherein R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27 and R.sup.28 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR16## wherein R.sup.21, R.sup.22, R.sup.23, R.sup.24, R.sup.25, R.sup.26, R.sup.27 and R.sup.28 are as defined above.
Examples of cations of these bases are inorgaic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substitutent is an aliphatic or aromatic group.
Embodiment D of this invention relates to 2-(2-nitrobenzoyl)-1,3-cyclohexanediones and their use as herbicides.
The compounds have a nitro substitution in the 2-position of the phenyl moiety of their compounds. The nitro substitution imparts exceptional herbicidal activity to the compounds of this invention.
Embodiment D' of this invention is an herbicidal composition comprising an herbicidally active 2-(2-nitrobenzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment D have the following structural formula ##STR17## wherein R.sup.31 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.31 is hydrogen or methyl;
R.sup.32 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl or ##STR18## wherein R.sup.a is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.32 is hydrogen or methyl;
R.sup.31 and R.sup.32 together are alkylene having 3 to 6 carbon atoms;
R.sup.33 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.33 is hydrogen or methyl;
R.sup.34 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.34 is hydrogen or methyl;
R.sup.35 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.35 is hydrogen or methyl;
R.sup.36 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.36 is hydrogen;
R.sup.37 and R.sup.38 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined, with the proviso that R.sup.37 is not attached to the 6-position.
Preferably, R.sup.37 is in the 3-position. Most preferably R.sup.37 is hydrogen or C.sub.1 -C.sub.4 alkoxy and R.sup.38 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chlorine, bromine, iodine or fluorine.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR19## wherein R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37 and R.sup.38 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR20## wherein R.sup.31, R.sup.32, R.sup.33, R.sup.34, R.sup.35, R.sup.36, R.sup.37 and R.sup.38 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium or organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substitutent is an aliphatic or aromatic group.
Embodiment E of this invention relates to 2-(2-benzoyl)-1,3-cyclohexanediones and their use as herbicides.
Embodiment E' of this invention is an herbicidal composition comprising an herbicidally active 2-(2-C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfinyl or C.sub.1 -C.sub.4 alkylsulfonyl benzoyl)-1,3-cyclohexanedione and an inert carrier therefor. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment E have the structural formula ##STR21## wherein n is the interger 0, 1 or 2, preferably 2;
R.sup.40 is C.sub.1 -C.sub.4 alkyl, preferably methyl;
R.sup.41 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.41 is hydrogen or methyl;
R.sup.42 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl or ##STR22## wherein R.sup.a is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.42 is hydrogen or methyl; or
R.sup.41 and R.sup.42 together are alkylene having 3 to 6 carbon atoms;
R.sup.43 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.43 is hydrogen or methyl;
R.sup.44 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.44 is hydrogen or methyl;
R.sup.45 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.45 is hydrogen or methyl;
R.sup.46 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.46 is hydrogen;
R.sup.47 and R.sup.48 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkoxy; or (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined, with the proviso that R.sup.47 is not attached to the 6-position.
Preferably, R.sup.47 is in the 3-position. Most preferably R.sup.47 is hydrogen or 3-chlorine and R.sup.48 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl.
The term "C.sub.1 -C.sub.4 " alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR23## wherein n, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47 and R.sup.48 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR24## wherein n, R.sup.40, R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45, R.sup.46, R.sup.47 and R.sup.48 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium, organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
Embodiment F of this invention relates to 2-(2-alkylbenzoyl)-1,3-cyclohexanediones and their use as herbicides.
Embodiment F' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-1,3-cyclohexanedione and an inert carrier therefor wherein the 2-position of the benzoyl moiety is substituted with C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, optionally substituted with halogen, more preferably methyl or trifluoromethyl and the 4-position preferably is substituted with an electron withdrawing group, such as halogen, cyano, trifluoromethyl or nitro. The 4-, 5- and 6-positions of the 1,3-cyclohexanedione moiety can be substituted, preferably with the groups hereinafter recited. More preferably, the 1,3-cyclohexanedione moiety has no substitution or the 4- or 6-positions are substituted with one or two methyl groups. The 3-, 4- and 5-positions of the benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment F have the following structural formula ##STR25## wherein R.sup.50 is C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, optionally substituted with halogen, more preferably methyl and trifluoromethyl;
R.sup.51 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.51 is hydrogen or methyl;
R.sup.52 is hydrogen; C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl or ##STR26## wherein R.sup.a is C.sub.1 -C.sub.4 alkyl, most preferably R.sup.52 is hydrogen or methyl; or
R.sup.51 and R.sup.52 together are alkylene having 3 to 6 carbon atoms;
R.sup.53 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.53 is hydrogen or methyl;
R.sup.54 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.54 is hydrogen or methyl;
R.sup.55 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl; most preferably R.sup.55 is hydrogen or methyl;
R.sup.56 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably C.sub.1 -C.sub.2 alkyl, more preferably methyl, most preferably R.sup.56 is hydrogen;
R.sup.57 and R.sup.58 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; or (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined, with the proviso that R.sup.57 is not attached to the 6-position.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The term "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "haloalkyl" includes the eight alkyl groups with one or more hydrogens replaced by chloro, bromo, iodo or fluoro.
Preferably, R.sup.57 is in the 3-position. Most preferably R.sup.57 is hydrogen and R.sup.58 is hydrogen, chlorine, bromine, fluorine, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl.
Salts of the above-described compounds (as defined hereinafter) are also the subject of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR27## wherein R.sup.50, R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55, R.sup.56, R.sup.57 and R.sup.58 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by any base to give a salt having an anion of the following four resonance forms: ##STR28## wherein R.sup.50, R.sup.51, R.sup.52, R.sup.53 R.sup.54, R.sup.55, R.sup.56, R.sup.57 and R.sup.58 are as defined above.
Examples of cations of these bases are inorganic cations such as alkali metals e.g. lithium, sodium, and potassium organic cations such as substituted ammonium, sulfonium or phosphonium wherein the substituent is an aliphatic or aromatic group.
Embodiment G of this invention relates to 2-benzoyl-1,3,5-cyclohexanetriones and their use as herbicides.
Embodiment G' of this invention is an herbicidal composition comprising an herbicidally active 2-benzoyl-substituted-1,3,5-cyclohexanetrione and an inert carrier therefor. The 4- and 6-positions of the 1,3,5-cyclohexanetrione moiety are preferably substituted with groups hereinafter defined, most preferably with all methyl groups. The benzoyl moiety can be substituted, preferably with the groups hereinafter recited.
The novel compounds of Embodiment G have the following structural formula ##STR29## wherein R.sup.60 is hydrogen; halogen; C.sub.1 -C.sub.2 alkyl, preferably methyl; C.sub.1 -C.sub.2 alkoxy, preferably methoxy; nitro; cyano; C.sub.1 -C.sub.2 haloalkyl, preferably trifluoromethyl; R.sup.a SO.sub.n -- wherein n is 0 or 2, preferably 2 and R.sup.a is C.sub.1 -C.sub.2 alkyl, preferably methyl, trifluoromethyl or difluoromethyl; or trifluoromethoxy or difluoromethoxy. Preferably, R.sup.60 is chlorine, bromine, C.sub.1 -C.sub.2 alkyl, C.sub.1 -C.sub.2 alkoxy, trifluoromethyl, cyano, nitro, C.sub.1 -C.sub.2 alkylthio or C.sub.1 -C.sub.2 alkylsulfonyl; more preferably chlorine, nitro, methyl, trifluoromethyl or methylsulfonyl; and
R.sup.61 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl;
R.sup.62 is hydrogen or C.sub.1 -C.sub.4 alkyl, preferably methyl; or
R.sup.61 and R.sup.62 together are C.sub.2 -C.sub.5 alkylene;
R.sup.63 is C.sub.1 -C.sub.4 alkyl, preferably methyl;
R.sup.64 is C.sub.1 -C.sub.4 alkyl, preferably methyl; or
R.sup.63 and R.sup.64 together are C.sub.2 -C.sub.5 alkylene;
R.sup.65 and R.sup.66 independently are (1) hydrogen; (2) halogen, preferably chlorine, fluorine or bromine; (3) C.sub.1 -C.sub.4 alkyl, preferably methyl; (4) C.sub.1 -C.sub.4 alkoxy, preferably methoxy; (5) trifluoromethoxy; (6) cyano; (7) nitro; (8) C.sub.1 -C.sub.4 haloalkyl, more preferably trifluoromethyl; (9) R.sup.b SO.sub.n -- wherein n is the integer 0, 1 or 2, preferably 2; and
R.sup.b is
(a) C.sub.1 -C.sub.4 alkyl, preferably methyl;
(b) C.sub.1 -C.sub.4 alkyl substituted with halogen or cyano, preferably chloromethyl, trifluoromethyl or cyanomethyl;
(c) phenyl; or
(d) benzyl;
(10) --NR.sup.c R.sup.d wherein R.sup.c and R.sup.d independently are hydrogen or C.sub.1 -C.sub.4 alkyl; (11) R.sup.e C(O)- wherein R.sup.e is C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy; (12) --SO.sub.2 NR.sup.c R.sup.d wherein R.sup.c and R.sup.d are as defined; or (13) --N(R.sup.c)C(O)R.sup.d wherein R.sup.c and R.sup.d are as defined.
Preferably R.sup.65 is in the 3-position. More preferably R.sup.65 is hydrogen, chlorine, fluorine, trifluoromethyl, cyano, C.sub.1 -C.sub.4 alkoxy or C.sub.1 -C.sub.4 thioalkyl. Most preferably, R.sup.65 is hydrogen. Preferably R.sup.66 is in the 4-position. Most preferably R.sup.66 is halogen, cyano, trifluoromethyl, or R.sup.b SO.sub.2 wherein R.sup.b is C.sub.1 -C.sub.4 alkyl, preferably methyl or C.sub.1 -C.sub.4 haloalkyl, preferably chloromethyl, difluoromethyl or trifluoromethyl.
The term "C.sub.1 -C.sub.4 alkyl" includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and t-butyl. The term "halogen" includes chlorine, bromine, iodine and fluorine. The terms "C.sub.1 -C.sub.4 alkoxy" includes methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy. The term "C.sub.1 -C.sub.4 haloalkyl" includes the alkyl groups defined above under C.sub.1 -C.sub.4 alkyl in which one or more hydrogens is replaced by chlorine, bromine, iodine or fluorine.
Salts of the above-described compounds (as defined hereinafter) are included within the scope of the instant invention.
The compounds of this invention can have the following four structural formulae because of tautomerism: ##STR30## wherein R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 and R.sup.66 are as defined above.
The circled proton on each of the four tautomers is reasonably labile. These protons are acidic and can be removed by reaction with a base to form a salt having an anion of the following four resonance forms: ##STR31## wherein R.sup.60, R.sup.61, R.sup.62, R.sup.63, R.sup.64, R.sup.65 and R.sup.66 are as defined above.
Examples of cations of these bases are inorganic cations such as alkalimetals, e.g., lithium, sodium and potassium; the alkaline earth metals, e.g. calcium and magnesium or ammonium or organic cations such as substituted ammonium, sulfonium, sulfoxonium or phosphonium wherein the substituents are aliphatic or aromatic groups.
Those skilled in the art will recognize in considering the salts of this invention that varying degrees os association between the anion and cation will exist depending upon the nature of the cation. In some instances with a suitable cation, such as copper, the salt can exist in a chelated form.
The compounds of this invention and their salts are active herbicides of a general type. That is, they are herbicidally effective against a wide range of plant species. The method of controlling undesirable vegetation of the present invention comprises applying an herbicidally effective amount of the above-described compounds to the area where control is desired.
The compounds of Embodiments A and A' of the present invention can be prepared by the following general method. ##STR32##
Generally, mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride. The two reactants and the zinc chloride are combined in a solvent such as methylene chloride. A slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.
The reaction product is worked up by conventional techniques.
The above-described substituted benzoyl cyanide can be prepared according to the teaching of T. S. Oakwood and C. A. Weisgerber, Organic Synthesis Collected, Vol. III, pp. 122 (1955).

The following example teaches the synthesis of a representative compound of Embodiments A and A' of this invention.
EXAMPLE 1-A,A'
2- (2,4-Dichlorobenzoyl)-cyclohexane-1,3-dione ##STR33##
1,3-Cyclohexanedione [11.2 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na.sub.2 CO.sub.3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was dissolved in ether and stirred with 250 ml of 5% copper (II) acetate. The resulting copper salt was filtered, washed with ether and stirred with 6N hydrochloric acid to destroy the salt. The extract was washed with ether to yield 22.15 grams of the desired product m.p. 138.degree.-140.degree. C. (77.7% yield). The structure was confirmed by instrumental analysis.
The compounds of Embodiment B of the present invention can be prepared by the following general method. ##STR34##
Generally, mole amounts of the dione and substituted benzoyl cyanide are used, along with a slight mole excess of zinc chloride. The two reactants and the zinc chloride are combined in a solvent such as methylene chloride. A slight mole excess of triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for 5 hours.
The reaction product is worked up by conventional techniques.
The above-described substituted benzoyl cyanide can be prepared according to the teaching of T. S. Oakwood and C. A. Weisgerber, Organic Synthesis Collected, Vol. III, pp. 122 (1955).
The following example teaches the synthesis of a representative compound of Embodiment B of this invention.
EXAMPLE 1-B
4,4-Dimethyl-2-(2,4-dichlorobenzoyl)-cyclohexane-1,3-dione ##STR35##
4,4-Dimethyl-1,3-cyclohexanedione [14.0 grams (g), 0.1 mole], 20.0 g (0.1 mole) 2,4-dichlorobenzoyl cyanide and 13.6 g (0.11 mole) anhydrous, powdered zinc chloride were combined in 100 milliliters (ml) methylene chloride. Triethylamine (10.1 g, 0.12 mole) was slowly added with cooling. The reaction mixture was stirred at room temperature for 5 hours and then poured into 2N hydrochloric acid. The aqueous phase was discarded and the organic phase was washed with 150 ml 5% Na.sub.2 CO.sub.3 four times. The aqueous washings were combined and acidified with HCl, extracted with methylene chloride, dried and concentrated to yield 25.3 g of crude product. The crude product was chromatographed (2% AcOH/CH.sub.2 Cl.sub.2) in 5 g aliquots then reduced on rotavap under reduced pressure at 50.degree. C. for 30 minutes to remove AcOH. This yielded an oil (40% yield). The structure was confirmed by instrumental analysis.
The compounds of Embodiment C of the present invention can be prepared by the following general method. ##STR36##
Generally, in step (1) mole amounts of the dione and substituted benzoyl chloride are used, along with a slight mole excess of triethylamine. The two reactants are combined in a solvent such as methylene chloride. The triethylamine is slowly added to the reaction mixture with cooling. The mixture is stirred at room temperature for several hours.
The reaction product is worked up by conventional techniques. ##STR37##
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the triethylamine, preferably 2 moles of the triethylamine and up to 0.5 mole, preferably 0.1 mole of a cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot for about one hour at room temperature and the desired product is recovered by conventional techniques.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR38## wherein R.sup.27 and R.sup.28 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of the The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are two representative examples of the methods described therein. ##STR39## wherein R.sup.27 and R.sup.28 are as previously defined.
In reaction (a) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR40## wherein R.sup.27 and R.sup.28 are as previously defined.
In reaction (b) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
The following example teaches the synthesis of a representative compound of Embodiment C of this invention.
EXAMPLE 1-C
2-(2'-Cyanobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR41##
2-Cyanobenzoyl chloride (3.9 g, 24 mmol) and 4,4-dimethyl-1,3-cyclohexanedione (3.3 g, 24 mmol) were dissolved in 75 ml methylene chloride. Triethylamine (5.0 ml, 36 mmol) was added dropwise and the resulting solution stirred for one and one-half hours at room temperature. The solution was washed with water, 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K.sub.2 CO.sub.3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (4.4 ml, 32 mmol) and acetone cyanohydrin (5 drops) were added and the solution stirred for two hours. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K.sub.2 CO.sub.3. The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with water and brine, dried (MgSO.sub.4) and concentrated under vacuum. The residue was purified by silica gel chromatography, yielding 1.2 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The compounds of Embodiments D and D' of the present invention can be prepared by the following two-step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR42## wherein R.sup.31 through R.sup.38 and moderate base are as defined and X is halogen, preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1 -C.sub.4 alkoxy-C(O)-O- or ##STR43## wherein R.sup.37 and R.sup.38 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0.degree. C.-50.degree. C. until the reaction is substantially complete. ##STR44## wherein the moderate base and R.sup.31 through R.sup.38 are as defined above.
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50.degree. C., preferably about 20.degree. C. to about 40.degree. C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40.degree. C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangement may be conducted at temperatures up to about 50.degree. C.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR45## wherein R.sup.37 and R.sup.38 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods described therein. ##STR46## wherein R.sup.37 and R.sup.38 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR47## wherein R.sup.37 and R.sup.38 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR48## wherein R.sup.37 and R.sup.38 are as previously defined.
In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
The following examples teach the synthesis of representative compounds of Embodiment D and D' of this invention.
EXAMPLE 1-D,D'
2-(2'-Nitrobenzoyl)-1,3-cyclohexanedione ##STR49##
2-Nitrobenzoyl chloride (5.0 g, 27 mmol) and cyclohexanedione (3.0 g, 27 mmol) were dissolved in methylene chloride. Triethylamine (4.9 ml, 35 mmol) was added dropwise and the resulting solution stirred for one hour. The solution was washed with 2 normal hydrochloric acid (2N HCl), water, 5% potassium carbonate solution and saturated sodium chloride solution, dried over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (1 equivalent) and potassium cyanide (40 mol %) were added and the solution stirred for one hour at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% potassium carbonate solution. The aqueous extract was acidified and ether was added. Filtration of the resulting mixture yielded 3.2 g of the desired compound (m.p. 132.degree.-135.degree. C.) which was identified by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
EXAMPLE 2-D,D'
2-(2'-Nitrobenzoyl)-5,5-dimethyl-1,3-cyclohexanedione ##STR50##
Triethylamine (3.4 ml, 25 mmol) was added dropwise to a methylene chloride solution of 2-nitrobenzoyl chloride (3.5 g, 19 mmol) and 5,5-dimethylcyclohexanedione (2.4 g, 19 mmol). After stirring for one hour at room temperature an additional 3 equivalents of triethylamine and 0.4 ml acetone cyanohydrin were added. The solution was stirred for 2.5 hours, then washed with 2N HCl and extracted with 5% potassium carbonate solution. The basic extracts were acidified with 2N HCl and extracted with ether. The ether portion was washed with saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated under vacuum. The residue was recrytallized from ethyl acetate yielding 2.0 g of the desired compound (m.p. 130.degree.-133.degree. C.) which was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The compounds of Embodiments E and E' of the present invention can be prepared by the following two or three step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR51## wherein moderate base, and R.sup.40 through R.sup.48 are defined herein, and X is halogen, preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1 -C.sub.4 alkoxy-C(O)-O- or ##STR52## wherein R.sup.40, R.sup.47 and R.sup.48 in this portion of the moledule are identical with those in the reactant shown above, and the moderate base is as defined, preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0.degree. C.-50.degree. C. until the reaction is substantially complete. ##STR53##
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetonecyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50.degree. C., preferably about 20.degree. C. to about 40.degree. C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40.degree. C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1, 2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangment may be conducted at temperatures up to about 50.degree. C. ##STR54## wherein n is 1 or 2.
Generally in step (3), a mole of the reaction product of step (2) is reacted with a slight mole or two mole excess of of an oxidizing agent such as m-chloroperbenzoic acid after being dissolved in a solvent such as methylene chloride. After completion of the reaction, the resulting mixture is stripped under vacuum. The residue is purified by silica gel chromatography to yield the desired product.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR55## wherein R.sup.40, R.sup.47 and R.sup.48 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of the The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods described therein. ##STR56## wherein R.sup.40, R.sup.47 and R.sup.48 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR57## wherein R.sup.40, R.sup.47 and R.sup.48 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR58## wherein R.sup.40, R.sup.47 and R.sup.48 are as defined and X is chlorine, bromine or iodine.
In reaction (c) the substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.
The following examples teach the synthesis representative compounds of Embodiments E and E' of this invention.
EXAMPLE 1-E,E'
2-(2'-Methylthiobenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR59##
2-Methylthiobenzoyl chloride (7.2 g, 39 mmol) and 4,4,6-trimethylcyclohexanedione (5.0 g, 39 mmol) were dissolved in methylene chloride. Triethylamine (7.0 ml, 50 mmol) was added dropwise and the resulting solution stirred for one hour at room temperature. The solution was washed with 2 normal hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K.sub.2 CO.sub.3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (2.5 equivalents) and acetone cyanohydrin (0.4 ml) were added and the solution stirred for 45 minutes at room temperature. After dilution with ether, the solution was washed with 2N HCl and extracted with 5% K.sub.2 CO.sub.3. The aqueous extract was acidified with hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO.sub.4) and concentrated under vacuum. The residue was purified by trituration with ether, yielding 5.0 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy (nmr), infrared spectroscopy (ir) and mass spectroscopy (ms).
EXAMPLE 2-E,E'
2-(2'-Methanesulfonylbenzoyl)-4,4,6-trimethyl -1,3-cyclohexanedione ##STR60##
The benzoyl cyclohexanedione prepared in Example 1 (2.5 g, 7.9 mmol) was dissolved in 40 ml methylene chloride. m-Chloroperbenzoic acid (3.5 g, 16 mmol) was added and the resulting solution was stirred for 45 minutes. The solution was concentrated under vacuum. Purification of the residue by silica gel chromatography yielded 1.7 g of a viscous oil which was identified as the desired compound by nmr, ir and ms.
EXAMPLE 3-E,E'
2-(4'-Trifluoromethyl-2'-methanesulfinylbenzoyl)-4,4-dimethyl-1,3-cyclohexanedione ##STR61##
2-(4'-Trifluoromethyl-2'-methylthiobenzoyl)-4,4-dimethyl-1,3-cyclohexanedione (5.0 g, 14 mmol) (which was prepared according to the method of Example 1) was dissolved in 50 ml methylene chloride. A solution of m-chloroperbenzoic acid (2.4 g--80%, 14 mmol) in 50 ml methylene chloride was added dropwise and the resulting solution was stirred for three hours at room temperature. After concentration under vacuum, the residue was dissolved in ether and washed with 1% hydrochloric acid. A 5% copper (II) acetate solution was added to the ether fraction, followed by hexane. The liquid phase was decanted and the remaining gummy solid stirred with 6N HCl and ether. The ether layer was dried (MgSO.sub.4) and concentrated to give 4.7 of a thick yellow solid. Purification on a centrifugally accelerated thin layer chromatograph (4 mm silica gel, 50:50:1 hexane:ethyl acetate:acetic acid-eluent) yielded 2.4 g of a viscous oil which was identified as the desired compound by nmr, ir and ms.
The compounds of Embodiments F and F' of the present invention can be prepared by the following two-step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR62## wherein R.sup.50 through R.sup.58 are as defined and X is halogen, preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1 -C.sub.4 alkoxy-C(O)-O- or ##STR63## wherein R.sup.50, R.sup.57 and R.sup.58 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the dione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably are added to the reaction mixture with cooling. The mixture is stirred at 0.degree. C.-50.degree. C. until the reaction is substantially complete.
The reaction product is worked up by conventional techniques. ##STR64## wherein R.sup.50 through R.sup.58 are as defined.
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably around 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 80.degree. C., preferably about 20.degree. C. to about 40.degree. C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40.degree. C. on a small scale. Larger scale reactions give more reproducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases such as tertiary amines and inorganic bases such as alkali metal carbonates and phosphates. Suitable tertiary amines include trialkylamines such as triethylamine. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the Crown ethers.
A number of different solvents may be usable in this process, depending on the nature of the acid chloride or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangment may be conducted at temperatures up to about 50.degree. C.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR65## wherein R.sup.50, R.sup.57 and R.sup.58 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N.Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are four representative examples of the methods described therein. ##STR66## wherein R.sup.50, R.sup.57 and R.sup.58 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR67## wherein R.sup.50, R.sup.57 and R.sup.58 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR68## wherein R.sup.50, R.sup.57 and R.sup.58 are as defined and X is chlorine, bromine or iodine.
The substituted aromatic halide is allowed to react with magnesium in a solvent such as ether. The solution is then poured over crushed dry ice and the benzoic acid is isolated by conventional techniques.
The following example teachs the synthesis of a representative compound of Embodiments F and F' of this invention.
EXAMPLE 1-F,F'
2-(4'-Bromo-2'-trifluoromethylbenzoyl)-4,4,6-trimethyl-1,3-cyclohexanedione ##STR69##
4-Bromo-2-trifluoromethylbenzoyl chloride (4.3 g, 15 mmol) and 4,4,6-trimethyl-1,3-cyclohexanedione (2.3 g, 15 mmol) were dissolved in 100 ml methylene chloride. The solution was cooled with an ice bath and triethylamine (2.1 ml, 15 mmol) in 10 ml methylene chloride was added dropwise. The ice bath was then removed and the resulting solution stirred for 30 minutes at room temperature. The solution was washed with 2N hydrochloric acid (2N HCl), 5% potassium carbonate solution (5% K.sub.2 CO.sub.3) and saturated sodium chloride solution (brine), dried over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The residue (5.1 g) was dissolved in 20 ml acetonitrile. Triethylamine (3.5 ml, 25 mmol) and 0.4 ml acetone cyanohydrin were added and the solution stirred for two hours at room temperature while protected by a drying tube (calcium sulfate). After dilution with ether, the solution was washed with 2N HCl and extracted with 5 % K.sub.2 CO.sub.3. The aqueous extract was acidified with concentrated hydrochloric acid and extracted with ether. The ether was washed with brine, dried (MgSO.sub.4) and concentrated under vacuum. The resulting oil was purified on a silica gel column (80:20:1 hexane:ethyl acetate: acetic acid-eluent), yielding 1.5 g of a viscous oil which was identified as the desired compound by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The compounds of Embodiment G and G' of the present invention can be prepared by the following two-step general method.
The process proceeds via the production of an enol ester intermediate as shown in reaction (1). The final product is obtained by rearrangement of the enol ester as shown in reaction (2). The two reactions may be conducted as separate steps by isolation and recovery of the enol ester using conventional techniques prior to conducting step (2), or by addition of a cyanide source to the reaction medium after the formation of the enol ester, or in one step by inclusion of the cyanide source at the start of reaction (1). ##STR70## wherein R.sup.60 through R.sup.66 and moderate base are as defined and X is halogen, preferably chlorine, C.sub.1 -C.sub.4 alkyl-C(O)-O-, C.sub.1 -C.sub.4 alkoxy-C(O)-O- or ##STR71## wherein R.sup.60, R.sup.65 and R.sup.66 in this portion of the molecule are identical with those in the reactant shown above and the moderate base is as defined, preferably tri-C.sub.1 -C.sub.6 alkylamine, alkali metal carbonate or alkali metal phosphate.
Generally, in step (1) mole amounts of the trione and substituted benzoyl reactant are used, along with a mole amount or excess of the base. The two reactants are combined in an organic solvent such as methylene chloride, toluene, ethyl acetate or dimethylformamide. The base or benzoyl reactant preferably is added to the reaction mixture with cooling. The mixture is stirred at 0.degree. C.-50.degree. C. until the reaction is substantially complete. ##STR72## wherein the moderate base and R.sup.60 through R.sup.66 are as defined above.
Generally, in step (2) a mole of the enol ester intermediate is reacted with 1 to 4 moles of the moderate base, preferably about 2 moles of moderate base and from 0.01 mole to about 0.5 mole or higher, preferably about 0.1 mole of the cyanide source (e.g., potassium cyanide or acetone cyanohydrin). The mixture is stirred in a reaction pot until the rearrangement is substantially complete at a temperature below 50.degree. C., preferably about 20.degree. C. to about 40.degree. C., and the desired product is recovered by conventional techniques.
The term "cyanide source" refers to a substance or substances which under the rearrangement conditions consists of or generates hydrogen cyanide and/or cyanide anion.
The process is conducted in the presence of a catalytic amount of a source of cyanide anion and/or hydrogen cyanide, together with a molar excess, with respect to the enol ester, of a moderate base.
Preferred cyanide sources are alkali metal cyanides such as sodium and potassium cyanide; cyanohydrins of methyl alkyl ketones having from 1-4 carbon atoms in the alkyl groups, such as acetone or methyl isobutyl ketone cyanohydrins; cyanohydrins of benzaldehyde or of C.sub.2 -C.sub.5 aliphatic aldehydes such as acetaldehyde, propionaldehyde, etc., cyanohydrins; zinc cyanide; tri(lower alkyl) silyl cyanides, notably trimethyl silyl cyanide; and hydrogen cyanide itself. Hydrogen cyanide is considered most advantageous as it produces relatively rapid reaction and is inexpensive. Among cyanohydrins the preferred cyanide source is acetone cyanohydrin.
The cyanide source is used in an amount up to about 50 mole percent based on the enol ester. It may be used in as little as about 1 mole percent to produce an acceptable rate of reaction at about 40.degree. C. on a small scale. Larger scale reactions give more reporducible results with slightly higher catalyst levels of about 2 mole percent. Generally about 1-10 mole % of the cyanide source is preferred.
The process is conducted with a molar excess, with respect to the enol ester, of a moderate base. By the term "moderate base" is meant a substance which acts as a base yet whose strength or activity as a base lies between that of strong bases such as hydroxides (which could cause hydrolysis of the enol ester) and that of weak bases such as bicarbonates (which would not function effectively). Moderate bases suitable for use in this embodiment include both organic bases, e.g., trialkylamines such as triethylamine and inorganic bases such as alkali metal carbonates and phosphates. Suitable inorganic bases include potassium carbonate and trisodium phosphate.
The base is used in an amount of from about 1 to about 4 moles per mole of enol ester, preferably about 2 moles per mole.
When the cyanide source is an alkali metal cyanide, particularly potassium cyanide, a phase transfer catalyst may be included in the reaction. Particularly suitable phase transfer catalysts are the crown ethers.
A number of different solvents are useful in this process, depending on the nature of the acid halide or the acylated product. A preferred solvent for this reaction is 1,2-dichloroethane. Other solvents which may be employed, depending on the reactants or products include toluene, acetonitrile, methylene chloride, ethyl acetate, dimethylformamide, and methyl isobutyl ketone (MIBK).
In general, depending on the nature of the reactants and the cyanide source, the rearrangment may be conducted at temperatures up to about 50.degree. C.
The above described substituted benzoyl chlorides can be prepared from the corresponding substituted benzoic acids according to the teaching of Reagents for Organic Synthesis, Vol. I, L. F. Fieser and M. Fieser, pp. 767-769 (1967). ##STR73## wherein R.sup.60, R.sup.65 and R.sup.66 are as previously defined.
The substituted benzoic acids can be prepared by a wide variety of general methods according to the teaching of The Chemistry of Carboxylic Acids and Esters, S. Patai, editor, J. Wiley and Sons, New York, N. Y. (1969) and Survey of Organic Synthesis, C. A. Buehler and D. F. Pearson, J. Wiley and Sons, (1970).
The following are three representative examples of the methods described therein. ##STR74## wherein R.sup.60, R.sup.65 and R.sup.66 are as previously defined.
In reaction (a) the substituted benzonitrile is heated to reflux in aqueous sulfuric acid for several hours. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR75## wherein R.sup.60, R.sup.65 and R.sup.66 are as previously defined.
In reaction (b) the substituted acetophenone is heated to reflux for several hours in an aqueous hypochlorite solution. The mixture is cooled and the reaction product is isolated by conventional techniques. ##STR76## wherein R.sup.60, R.sup.65 and R.sup.66 are as previously defined.
In reaction (c) the substituted toluene is heated to reflux in an aqueous solution of potassium permanganate for several hours. The solution is then filtered and the reaction product is isolated by conventional techniques.
The following example teaches the synthesis of a representative compound of Embodiment G and G' of this invention.
EXAMPLE 1-G,G'
2-(2'-Nitro-4'-chlorobenzoyl)-4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione ##STR77##
2-Nitro-4-chlorobenzoyl chloride (2.2 g, 10 mmol) and 4,4,6,6-tetramethyl-1,3,5-cyclohexanetrione (1.8 g, 10 mmol) were dissolved in methylene chloride. Triethylamine was added and the resulting solution stirred at room temperature for 30 minutes. The solution was washed with 1 normal hydrochloric acid (1N HCl), and saturated sodium chloride (brine), dried over anhydrous magnesium sulfate (MgSO.sub.4) and concentrated under vacuum. The residue was dissolved in 20 ml acetonitrile. Triethylamine (5 ml, 3.5 equivalents) and acetone cyanohydrin (0.5 g, 0.6 equivalent) were added and the mixture stirred at room temperature for 4 hours. After dilution with ether, the solution was washed with 1N HCl and extracted with 5% K.sub.2 CO.sub.3. The basic extract was acidified with HCl and extracted with ether. The ether extract was washed with brine, dried over MgSO.sub.4 and concentrated under vacuum, yielding 2.2 g of crude product. This was recrystallized from benzene to remove syncarpic acid still present. Concentration of the mother liquor under vacuum gave 1.7 g of the desired product as an oil, which solidified on standing (m.p. 76.degree.-82.degree. C.). It was identified as such by nuclear magnetic resonance spectroscopy, infrared spectroscopy and mass spectroscopy.
The following are tables of certain selected compounds of Embodiments A-G' that are preparable according to the procedures described herein. Compound numbers are assigned to each compound and are used throughout the remainder of the application.
TABLE I-A__________________________________________________________________________ ##STR78##Cmpd. n.sub.D.sup.30 orNo. R R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 m.p. .degree.C.__________________________________________________________________________1A CH.sub.3 CH.sub.3 Cl H H H 1.56132A CH.sub.3 CH.sub.3 Cl H 4-Cl H 1.56553A CH.sub.3 CH.sub.3 Cl H H 6-Cl 103-1084A* H H Cl H 4-Cl H 138-1405A CH.sub.3 CH.sub.3 Br H H H6A CH.sub.3 CH.sub.3 Cl H H 5-Cl 74-777A H H Cl H H 5-Cl 104-1078A H H Br H H H 93-969A H H Cl H H H 79-8710A H H I H H H 66-7011A H H Cl H 4-NO.sub.2 H 118-12212A H H Cl H H 6-Cl 143-14813A H H Cl H H 5-Br 109-11514A H H I 3-I H 5-I 164-16715A H H Cl H H 5-CH.sub.3 60-6516A H H Cl H 4-CH.sub.3 H 79-8617A H H Cl H 4-CH.sub.3 O H 60-6318A H H Cl 3-Cl H 6-Cl19A H H Cl H H 5-CH.sub.3 O 77-8020A H H Cl 3-Cl H H 80-9021A H H Cl H H 5-CF.sub.3 74-7522A H H Cl H H 5-NO.sub.2 140-14323A H H Cl 3-Cl 4-Cl H 152-15424A H H Cl 3-Cl 4-CH.sub.3 O H 169-17025A H H Cl H 4-Br H 104-10726A CH.sub.3 CH.sub.3 CH.sub.3 O H H H 104-10827A H H Cl H ##STR79## H28A H H Br H H (a)29A H H CH.sub.3 O 3-CH.sub.3 O H H 75-7930A H H CH.sub.3 O H H 5-CH.sub.3 O 89-9231A H H Br H 4-CH.sub.3 O 5-CH.sub.3 O 92-9632A H H Br H (4)-OCH.sub.2 O-(5) 63-6833A CH.sub.3 CH.sub.3 Cl 3-Cl 4-Cl H 86-8934A H H Cl 3-Cl H 5-Cl35A CH.sub.3 CH.sub.3 Cl 3-Cl H 5-Cl 105-10936A CH.sub.3 CH.sub.3 Cl 3-Cl 4-Cl 5-Cl 137-13937A H H Cl 3-Cl 4-Cl 5-Cl 106-11038A H H Cl H 4-Cl 5-Cl 108-11139A ##STR80## H Cl H 4-Cl H40A ##STR81## H Cl H 4-Cl H41A CH(CH.sub.3).sub.2 H Cl H 4-Cl H42A CH(CH.sub.3).sub.2 H Cl 3-Cl 4-Cl H43A H H Cl H 4-F H44A sodium salt of Compound No. 23 85-9445A isopropylamine salt of Compound No. 23 160-16546A triethylamine salt of Compound No. 23 82-8547A potassium salt of Compound No. 23 107-10648A triethanolammonium salt of Compound No. 3949A sodium salt of Compound No. 43 60-6350A CH(CH.sub.3).sub.2 H Cl 3-CH.sub.3 O 4-Br H51A H H Cl H 4-CH.sub.3 SO.sub.2 H 140-14152A H CH.sub.3 Cl H 4-Cl H53A i-C.sub.4 H.sub.9 H Cl H 4-Cl H54A i-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 O H H55A CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 SO.sub.2 H56A CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-Cl H57A H H Cl 3-CH.sub.3 4-Cl H 56-6458A H H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H 98-10259A H H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H 98-10960A H H Cl H 4-C.sub.3 H.sub.7 SO.sub.2 H semi-solid61A H H Cl 3-CH.sub.3 O 4-CH.sub.3 SO.sub.2 H 48-5962A CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO.sub.2 H semi-solid63A H H Cl 3-Cl 4-n-C.sub.3 H.sub.7 SO.sub.2 H 145-148.564A H H Cl 3-C.sub.2 H.sub.5 S 4-C.sub.2 H.sub.5 SO.sub.2 H oil65A CH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H 103-10866A CH.sub.3 CH.sub.3 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H 108-11467A i-C.sub.3 H.sub.7 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H brown gum68A H H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H 145-15469A i-C.sub.3 H.sub.7 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H70A H H Br H 4-CH.sub.3 SO.sub.2 H brown gum71A H H Cl H 4-i-C.sub.3 H.sub.7 SO.sub.2 H semi-solid72A H H Cl H 4-CH.sub.3 S H 74-7773A H H Cl 3-Cl 4-CH.sub.3 S H74A CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.3 H.sub.7 SO.sub.2 H 120-12375A H H Cl H 4-n-C.sub.4 H.sub.9 SO.sub.2 H semi-solid76A CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.4 H.sub.9 SO.sub.2 H77A H H Cl 3-C.sub.2 H.sub.5 O 4-CH.sub.3 SO.sub.2 H semi-solid78A H H Cl 3-CH.sub.3 O 4-n-C.sub.3 H.sub.7 SO.sub.2 H golden gum79A CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.3 H.sub.7 SO.sub.2 H 125-12880A CH(CH.sub.3).sub.2 H CH.sub.3 O 3-Cl 5-Cl H81A H H Cl 3-CH.sub.3 O 4-Br H 110-11182A H H Cl 3-CH.sub.3 4-Cl H 56-6483A H H Cl H 4-Cl 5-CH.sub.3 O softens >7084A CH(CH.sub.3).sub.2 H Cl 3-n-C.sub.3 H.sub.7 O 4-Br H85A H H Cl 3-C.sub.2 H.sub.5 O 4-Br H 101-10486A H H Cl H 4-i-C.sub.4 H.sub.9 SO.sub.2 H 136-14087A CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.4 H.sub.9 SO.sub.2 H88A H H Cl 3-Cl 4-i-C.sub.3 H.sub.7 SO.sub.2 H 173-17689A H H Cl 3-Cl 4-n-C.sub.4 H.sub.9 SO.sub.2 H 135-13890A H H Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2 H.sub.5 SO.sub.2 H gum91A H H Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 SO.sub.2 H gum92A H H Cl 3-Cl 4-C.sub.2 H.sub.5 S H 91-9493A H H Cl 3-C.sub.2 H.sub.5 S 4-n-C.sub.3 H.sub.7 SO.sub.2 H oil94A H H Cl 3-C.sub.2 H.sub.5 S 4-C.sub.2 H.sub.5 S H oil95A H H Cl H 4-(CH.sub.3).sub.2 NSO.sub.2 H oil96A H H Cl 3-C.sub.2 H.sub.5 O 4-n-C.sub.3 H.sub.7 SO.sub.2 H97A H H Cl 3-n-C.sub.3 H.sub.7 O 4-C.sub.2 H.sub.5 SO.sub.2 H oil98A CH.sub.3 CH.sub.3 Cl H 4-(CH.sub.3).sub.2 NSO.sub.2 H oil99A H H Cl H 4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2 H 90-92100A CH.sub.3 CH.sub.3 Cl H 4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2 H101A H H Cl H 4-C.sub.2 H.sub.5 S H102A H H Cl H 4-n-C.sub.3 H.sub.7 S H103A H H Cl H 4-i-C.sub.3 H.sub.7 S H104A H H Cl H 4-C.sub.2 H.sub.5 SO H105A H H CH.sub.3 O H 4-NO.sub.2 H semi-solid106A H H Cl 3-n-C.sub.3 H.sub.7 O 4-Br H107A H H Cl 3-n-C.sub.3 H.sub.7 O 4-CH.sub.3 SO.sub.2 H 96-100108A H H Cl 3-allyloxy 4-CH.sub.3 SO.sub.2 H semi-solid109A H H Cl 3-CH.sub.3 C(O)NH 4-Cl H 155-160110A H H Cl 3-Cl 4-n-C.sub.3 H.sub.7 S H111A H H Cl 3-CH.sub.3 O 4-NO.sub.2 H 150-153112A H H Cl 3-allyloxy 4-C.sub.2 H.sub.5 SO.sub.2 H113A H H Cl 3-CH.sub.2 BrCHBrCH.sub.2 O 4-C.sub.2 H.sub.5 SO.sub.2 H114A H H Cl 3-n-C.sub.4 H.sub.9 O 4-C.sub.2 H.sub.5 SO.sub.2 H gum115A H H Cl 3-i-C.sub.4 H.sub.9 O 4-C.sub.2 H.sub.5 SO.sub.2 H116A H H Cl H 4-allylthio H117A CH.sub.3 CH.sub.3 Cl H 4-NO.sub.2 H118A H H Cl 3-CH.sub.3 C(O)N(CH.sub.3) 4-Cl H119A H H Cl 3-i-C.sub.3 H.sub.7 O 4-C.sub.2 H.sub.5 SO.sub.2 H120A H H Cl 3-CH.sub.2 ClCH.sub.2 CH.sub.2 O 4-C.sub.2 H.sub.5 SO.sub. H gum121A H H Cl H 4-t-C.sub.4 H.sub.9 S H122A H H Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 S H123A H H Cl H 4-CF.sub.3 H124A H H Cl H 4-Cl 6-Cl125A H H Cl 3-CH.sub.3 C(O)N(CH.sub.3) H H 131-135126A H H Cl 3-CH.sub.3 C(O)NH H H127A H H Cl 3-(CH.sub.3).sub.2 N 4-Cl H128A CH.sub.3 H Cl 3-CH.sub.3 O 4-CH.sub.3 SO.sub.2 H 117-122129A H H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H130A H H Br H H H131A H H Br H 4-C.sub.2 H.sub.5 OC(O) H132A H H Cl H 4-CN H 183-184133A H H Cl 3-CH.sub.3 C(O)NH H 6-NO.sub.2134A H H Cl 3-(CH.sub.3).sub.2 N H H135A H H Cl 3-Cl 4-ClCH.sub.2 CH.sub.2 SO.sub.2 H__________________________________________________________________________ *Prepared in Example 1A. ##STR82##
TABLE I-B__________________________________________________________________________ ##STR83##CompoundNumber R.sup.10 R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15 R.sup.16 R.sup.17 R.sup.18__________________________________________________________________________ 1B ##STR84## H Cl H 4-Cl H H H H 2B ##STR85## CH.sub.3 Cl H 4-Cl H H H H 3B triethanolammonium salt of Compound No. 2 4B triethanolammonium salt of Compound No. 7 5B ##STR86## CH.sub.3 Cl 3-Cl 4-Cl H H H H 6B triethanolammonium salt of Compound No. 5.sup. CH.sub.3a) CH.sub.3 Cl H 4-Cl H H H H 8B CH.sub.3 CH.sub.3 Cl H 4-Cl CH.sub.3 H H H 9B CH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-Cl H H H H10B CH.sub.3 H Cl H 4-Cl H H H H11B CH.sub.3 H Cl H 4-Cl CH.sub.3 H H H12B C.sub.5 H.sub.10 Cl H 4-Cl H H H H13B CH.sub.3 CH.sub.3 Cl 3-Cl 4-Cl H H H H14B CH.sub.3 CH.sub.3 Cl 3-Cl 4-Cl CH.sub.3 H H H15B i-C.sub.3 H.sub.7 H Cl 3-Cl 4-Cl H H H H16B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 SO.sub.2 H H H H17B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H H18B CH.sub.3 H Cl H 4-CH.sub.3 SO.sub.2 H H H H19B CH.sub.3 CH.sub.3 Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H H20B CH.sub.3 CH.sub.3 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H H21B CH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H H22B CH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H23B CH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H H24B CH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H H25B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-Cl H H H H26B CH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-Cl H H H H27B CH.sub.3 C.sub.2 H.sub.5 Cl H 4-Cl H H H H28B CH.sub.3 CH.sub.3 Cl H H H H H H29B CH.sub. 3 CH.sub.3 Cl 3-OCH.sub.3 4-Br H H H H30B CH.sub.3 CH.sub.3 Cl H 4-Br H H H H31B CH.sub.3 C.sub.2 H.sub.5 Cl 3-Cl 4-Cl H H H H32B n-C.sub.3 H.sub.7 H Cl H 4-Cl H H H H33B ##STR87## n-C.sub.3 H.sub.7 Cl H 4-Cl H H H H34B CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.3 H.sub.7 SO.sub.2 H H H H35B CH.sub.3 CH.sub.3 Cl 3-i-C.sub.3 H.sub.7 O 4-Br H H H H36B CH.sub.3 CH.sub.3 Cl H 6-F H H H H37B i-C.sub.3 H.sub.7 H Cl 3-Cl 4-Cl H H H H38B CH.sub.3 CH.sub.3 Cl 3-OC.sub.2 H.sub.5 4-Br CH.sub.3 H H H39B i-C.sub.3 H.sub.7 OC(O) H Cl H 4-Cl H H H H40B C.sub.2 H.sub.5 OC(O) n-C.sub.3 H.sub.7 Cl H 4-Cl H H H H41B C.sub.5 H.sub.10 Cl H 4-Cl H H H H42B CH.sub.3 CH.sub.3 Cl H 4-Cl H H CH.sub.3 H43B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO.sub.2 H H H H44B CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.3 H.sub.7 SO.sub.2 H H H H45B CH.sub.3 CH.sub.3 CH.sub.3 O 3-CH.sub.3 O H H H H H46B CH.sub.3 CH.sub.3 CH.sub.3 O H 4-Cl H H H H47B CH.sub.3 CH.sub.3 Cl H 4-Br CH.sub.3 H H H48B CH.sub.3 CH.sub.3 Br H H H H H H49B CH.sub.3 CH.sub.3 I H H H H H H50B CH.sub.3 CH.sub.3 F H H H H H H51B CH.sub.3 CH.sub.3 CH.sub.3 O H H H H H H52B CH.sub.3 CH.sub.3 Cl 3-allyloxy 4-Br H H H H53B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 SO.sub.2 H H CH.sub.3 H54B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 O 4-Br CH.sub.3 H H H55B CH.sub.3 CH.sub.3 Br H 4-CN H H H H56B CH.sub.3 CH.sub.3 Cl H 4N(CH.sub.3)SO.sub.2 CF.sub.3 H H H H57B CH.sub.3 CH.sub.3 Cl 3-NO.sub.2 H H H H H58B CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 O H 4-Cl H H H H59B CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.4 H.sub.9 SO.sub.2 H H H H60B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-CH.sub.3 SO.sub.2 H H H H61B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 SO.sub.2 H H H H62B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.4 H.sub.9 SO.sub.2 H H H H63B CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.4 H.sub.9 SO.sub.2 CH.sub.3 H H H64B CH.sub.3 CH.sub.3 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H H65B CH.sub.3 CH.sub.3 Cl H 4-F H H H H66B CH.sub.3 H Cl 3-CH.sub.3 O 4-Br H H H H67B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 O H H H H H68B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 S 4-n-C.sub.3 H.sub.7 SO.sub.2 H H H H69B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 S 4-C.sub.2 H.sub.5 S H H H H70B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 S 4-C.sub.2 H.sub.5 SO.sub.2 H H H H71B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 S 4-CH.sub.3 SO.sub.2 H H H H72B CH.sub.3 CH.sub.3 Cl Cl 4-i-C.sub.3 H.sub.7 SO.sub.2 H H H H73B CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.4 H.sub.9 SO.sub.2 H H H H74B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2 H.sub.5 SO.sub.2 H H H H75B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-Br H H H H76B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-n-C.sub.3 H.sub.7 SO.sub.2 H H H H77B CH.sub.3 CH.sub.3 Cl 3-n-C.sub.3 H.sub.7 O 4-C.sub.2 H.sub.5 SO.sub.2 H H H H78B CH.sub.3 CH.sub. 3 Cl H 4-(CH.sub.3).sub.2 NSO.sub.2 H H H H79B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 S 4-C.sub.2 H.sub.5 SO.sub.2 H H H H80B CH.sub.3 CH.sub.3 Cl 3-Cl 4-C.sub.2 H.sub.5 S H H H H81B CH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 S H H H H82B CH.sub.3 CH.sub.3 Cl H 4-(C.sub.2 H.sub.5).sub.2 NSO.sub.2 H H H H83B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO.sub.2 H H H H84B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 S CH.sub.3 H H H85B CH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 S(O) H H H H86B CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.3 H.sub.7 S H H H H87B CH.sub.3 CH.sub.3 Cl 3-Cl 4-n-C.sub.3 H.sub.7 S H H H H88B CH.sub.3 CH.sub.3 Cl H 4-t-C.sub.4 H.sub.9 SO.sub.2 H H H H89B CH.sub.3 CH.sub.3 Cl H 4-i-C.sub.3 H.sub.7 S CH.sub.3 H H H90B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO.sub.2 CH.sub.3 H H H91B CH.sub.3 CH.sub.3 Cl * 4-Cl H H H H92B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.2CHCH.sub.2 S H H H H93B CH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-C.sub.2 H.sub.5 S H H H H94B CH.sub.3 CH.sub.3 Cl 3-Cl 4-CH.sub.3 S CH.sub.3 H H H95B CH.sub.3 CH.sub.3 Cl H 4-CH.sub.3 S H H H H96B CH.sub.3 CH.sub.3 Cl 3-i-C.sub.3 H.sub.7 O 4-C.sub.2 H.sub.5 SO.sub.2 H H H H97B CH.sub.3 CH.sub.3 Cl 3-CH.sub.3 O 4-C.sub.2 H.sub.5 S H H H H98B CH.sub.3 CH.sub.3 Cl ** 4-Cl H H H H99B CH.sub.3 CH.sub.3 Cl ** H H H H H100B CH.sub.3 CH.sub.3 Cl 3-Cl 4-CH.sub.3 S H H H H101B CH.sub.3 CH.sub.3 CH.sub.3 O H 4-NO.sub.2 H H H H102B CH.sub.3 CH.sub.3 CH.sub.3 O H 4-CF.sub. 3 H H H H103B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO H H H H104B CH.sub.3 CH.sub.3 Cl H 4-n-C.sub.3 H.sub.7 SO CH.sub.3 H H H__________________________________________________________________________ .sup.a) Prepared in Example IB. *3-CH.sub.3 C(O)NH **3-CH.sub.3 C(O)N(CH.sub.3)
The following additional compounds can be prepared by the general method hereinbefore taught.
TABLE I-B__________________________________________________________________________ ##STR88##R.sup.10 R.sup.11 R.sup.12 R.sup.13 R.sup.14 R.sup.15 R.sup.16 R.sup.17 R.sup.18__________________________________________________________________________CH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl H 4-Cl H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl H 4-Cl CH.sub.3 H H HC.sub.2 H.sub.5 H Cl H 4-Cl H H H HC.sub.2 H.sub.5 H Cl H 4-Cl CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl H 4-Cl H H H Hn-C.sub.4 H.sub.9 H Cl H 4-Cl CH.sub.3 H H Hi-C.sub. 3 H.sub.7 H Cl H 4-Cl H H H Hi-C.sub.3 H.sub.7 H Cl H 4-Cl CH.sub.3 H H HC.sub.5 H.sub.10 Cl H 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl 4-Cl H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-Cl H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-Cl CH.sub.3 H H HCH.sub.3 H Cl 3-Cl 4-Cl H H H HCH.sub.3 H Cl 3-Cl 4-Cl CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-Cl 4-Cl H H H HC.sub.2 H.sub.5 H Cl 3-Cl 4-Cl CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-Cl 4-Cl H H H Hn-C.sub.4 H.sub.9 H Cl 3-Cl 4-Cl CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-Cl 4-Cl H H H HC.sub.5 H.sub.10 Cl 3-Cl 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl H 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl H 4-CH.sub.3 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl H 4-CH.sub.3 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl H 4-CH.sub.3 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub. 5 H.sub.10 Cl H 4-CH.sub.3 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl H 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-Cl 4-CH.sub.3 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl 3-Cl 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub. 2 H H H HC.sub.2 H.sub.5 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl 3-Cl 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HCH.sub.3 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl 3-CH.sub.3 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 H H H HC.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H HCH.sub.3 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H HC.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H Hn-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H H Hi-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 H H HC.sub.5 H.sub.10 Cl 3-CH.sub.3 4-CH.sub.3 SO.sub.2 CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-Cl H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-Cl H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 H Cl 3-CH.sub.3 4-Cl H H H HCH.sub.3 H Cl 3-CH.sub.3 4-Cl CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-Cl H H H HC.sub.2 H.sub.5 H Cl 3-CH.sub.3 4-Cl CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-Cl H H H Hn-C.sub.4 H.sub.9 H Cl 3-CH.sub.3 4-Cl CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-Cl H H H Hi-C.sub.3 H.sub.7 H Cl 3-CH.sub.3 4-Cl CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-CH.sub.3 4-Cl H H H HC.sub.5 H.sub.10 Cl 3-CH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-Cl H H H HCH.sub.3 n-C.sub.3 H.sub.7 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-Cl H H H HCH.sub.3 n-C.sub.4 H.sub.9 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 H Cl 3-OCH.sub.3 4-Cl H H H HCH.sub.3 H Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H HC.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-Cl H H H HC.sub.2 H.sub.5 H Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H Hn-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-Cl H H H Hn-C.sub.4 H.sub.9 H Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H Hi-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-Cl H H H Hi-C.sub.3 H.sub.7 H Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H HC.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-Cl H H H HC.sub.5 H.sub.10 Cl 3-OCH.sub.3 4-Cl CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl 3-n-C.sub.3 H.sub.7 O 4-Br H H H HCH.sub.3 CH.sub.3 Cl H 4-C.sub.2 H.sub.5 SO.sub.2 CH.sub.3 H H HCH.sub.3 CH.sub.3 Cl H 4-NO.sub.2 H H H HCH.sub.3 CH.sub.3 Cl 3-C.sub.2 H.sub.5 O 4-CH.sub.3 S H H H HCH.sub.3 CH.sub.3 Cl H 4-CN H H H HCH.sub.3 CH.sub.3 Cl 3-(CH.sub.3).sub.2 N 4-Cl H H H H__________________________________________________________________________
TABLE I-C__________________________________________________________________________ ##STR89##Comp. No. R.sup.21 R.sup.22 R.sup.23 R.sup.24 R.sup.25 R.sup.26 R.sup.27 R.sup.28 n.sub.D.sup.30 or m.p.__________________________________________________________________________.sup. 1C.sup.a CH.sub.3 CH.sub.3 H H H H H H oil2C H H H H H H H CN 124-140.degree. C.__________________________________________________________________________ .sup.a Prepared in Example IC.
TABLE I-D__________________________________________________________________________ ##STR90##Comp.No. R.sup.31 R.sup.32 R.sup.33 R.sup.34 R.sup.35 R.sup.36 R.sup.37 R.sup.38 n.sub.D.sup.30 or__________________________________________________________________________ m.p. 1D CH.sub.3 H H H H H H H viscous oil 2D CH.sub.3 CH.sub.3 H H CH.sub.3 H H H viscous oil 3D.sup.a) H H H H H H H H 132-135 4D CH.sub.3 CH.sub.3 H H H H H H viscous oil 5D.sup.b) H H CH.sub.3 CH.sub.3 H H H H 130-133 6D CH.sub.3 H H H CH.sub.3 H H H viscous oil 7D CH.sub.3 CH.sub.3 H H H H H CF.sub.3 52-61 8D H H H H H H H CF.sub.3 88-94 9D H H CH.sub.3 CH.sub.3 H H H CF.sub.3 89-9710D CH.sub.3 CH.sub.3 H H H H 3-CH.sub.3 H 119-12211D CH.sub.3 CH.sub.3 H H H H 3-Cl H 72-7912D CH.sub.3 CH.sub.3 H H H H H Cl 118-12113D CH.sub.3 CH.sub.3 H H H H 5-Cl H 118-12014D CH.sub.3 CH.sub.3 H H H H 5-F H 130-13315D CH.sub.3 CH.sub.3 H H H H 3-CH.sub.3 O H 139-14216D CH.sub.3 CH.sub.3 CH.sub.3 H H H H CF.sub.3 viscous oil17D CH.sub.3 CH.sub.3 H H H H H NO.sub.2 viscous oil18D CH.sub.3 CH.sub.3 H H H H H Br viscous oil19D CH.sub.3 CH.sub.3 H H H CH.sub.3 5-CH.sub.3 H viscous oil20D CH.sub.3 CH.sub.3 H H H H 5-CH.sub.3 H viscous oil21D H H H H H H H F 123-12822D CH.sub.3 CH.sub.3 H H H H H F viscous oil23D H H H H H H H Cl viscous oil24D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 CH.sub.3 130-13325D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 -n-C.sub.3 H.sub.7 viscous oil26D H H H H H H H SO.sub.2 CH.sub.3 157-15927D H H H H H H H SO.sub.2 -n-C.sub.3 H.sub.7 120-12328D CH.sub.3 CH.sub.3 H H H H 5-F H 165-19529D CH.sub.3 CH.sub.3 H H H H H SO.sub.2C.sub.2 H.sub.5 oil30D CH.sub.3 CH.sub.3 H H CH.sub.3 H H SO.sub.2CH.sub.3 gum31D CH.sub.3 n-C.sub.4 H.sub.9 H H H H H H viscous oil32D H H i-C.sub.4 H.sub.9 H H H H H viscous oil33D H H H H H H H SO.sub.2C.sub.2 H.sub.5 viscous oil34D H H H H H H H CN viscous oil35D H H H H H H H SO.sub.2 N(CH.sub.3).sub.2 158-15936D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 N(CH.sub.3).sub.2 120-13037D H H H H H H H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 158-16338D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 oil39D CH.sub.3 CH.sub.3 H H H H H ##STR91## oil40D H H CH.sub.3 CH.sub.3 H H H SO.sub.2N(C.sub.2 H.sub.5).sub.2 oil41D H H H H H H H SC.sub.2 H.sub.5 oil42D H H H H H H H S(O)-n-C.sub.3 H.sub.7 oil43D H H H H H H H S-n-C.sub.3 H.sub.7 oil44D CH.sub.3 CH.sub.3 H H CH.sub.3 H H S-n-C.sub.3 H.sub.7 oil45D CH.sub.3 CH.sub.3 H H H H H S-n-C.sub.3 H.sub.7 oil46D CH.sub.3 CH.sub.3 H H CH.sub.3 H H SC.sub.2 H.sub.5 oil47D CH.sub.3 CH.sub.3 H H H H H SC.sub.2 H.sub.5 oil48D H H H H H H H SCH.sub.3 94-9749D CH.sub.3 CH.sub.3 H H CH.sub.3 H H CF.sub.3 oil50D CH.sub.3 CH.sub.3 H H H H H SCH.sub.3 oil51D c) H i-C.sub.3 H.sub.7 H H H H H 145-14852D CH.sub.3 CH.sub.3 H H H H 5-CH.sub.3 O Br oil53D H H CH.sub.3 CH.sub.3 H H H Cl oil54D H H H H H H 3-CH.sub.3 O Cl oil55D CH.sub.3 CH.sub.3 H H H H 3-CH.sub.3 O Cl oil56D CH.sub.3 CH.sub.3 H H CH.sub.3 H H CH.sub.3 S oil57D H H H H H H H ##STR92## 120-12558D H H CH.sub.3 CH.sub.3 H H H CN 175-17759D CH.sub.3 CH.sub.3 H H H H H CN 151-15360D CH.sub.3 CH.sub.3 H H CH.sub.3 H H CN oil61D c) H H H H H H H oil62D d) H H H H H H H oil63D H H CH.sub.3 H H H H Cl 110-11564D H H CH.sub.3 H H H H SO.sub.2 -n-C.sub.3 H.sub.7 oil65D d) CH.sub.3 H H H H H Cl oil66D H H H H H H H SO.sub.2 CHCl.sub.2 oil67D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 CHCl.sub.2 oil68D H H H H H H c) Br oil69D H H H H H H H SO.sub.2 CH.sub.2 Cl oil70D CH.sub.3 CH.sub.3 H H H H H SO.sub.2 CH.sub.2 Cl wax71D d) CH.sub.3 H H H H H H oil72D H H H H H H C.sub.2 H.sub.5 O Cl oil73D CH.sub.3 CH.sub.3 H H CH.sub.3 H CH.sub.3 O CF.sub.3 oil__________________________________________________________________________ .sup.a) Prepared in Example 1D,D'. .sup.b) Prepared in Example 2D,D'. c) = C.sub. 2 H.sub.5 OC(O)- d) = iC.sub.3 H.sub.7 OC(O)-
TABLE I-E__________________________________________________________________________ ##STR93##Comp.No. n R.sup.40 R.sup.41 R.sup.42 R.sup.43 R.sup.44 R.sup.45 R.sup.46 R.sup.47 R.sup.48 m.p.__________________________________________________________________________ 1E 0 CH.sub.3 H H H H H H H H 79-81.degree. C. 2E 0 CH.sub.3 CH.sub.3 CH.sub.3 H H H H H H oil.sup. 3E.sup.a) 0 CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H H oil.sup. 4E.sup.b) 2 CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H H oil 5E 0 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H H H H H H oil 6E 2 C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H H H H H H oil 7E 0 CH.sub.3 H H H H H H 3-Cl Cl 59-64.degree. C. 8E 2 CH.sub.3 H H H H H H 3-Cl Cl 116-119.degree. C. 9E 0 CH.sub.3 H H H H H H H CF.sub.3 102-106.degree. C.10E 2 CH.sub.3 H H H H H H H CF.sub.3 oil11E 0 CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CF.sub.3 49-53.degree. C.12E 2 CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil 13E.sup.c) 1 CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil14E 0 CH.sub.3 H H H H H H 3-Cl SCH.sub.3 105-107.degree. C.15E 1 CH.sub.3 H H H H H H 3-Cl S(O)CH.sub.3 oil16E 0 CH.sub.3 H H H H H H H SO.sub.2 n-C.sub.3 H.sub.7 oil17E 0 CH.sub.3 H H H H H H H SCH.sub.3 101-103.degree. C.18E 2 CH.sub.3 H H H H H H H SO.sub.2 n-C.sub.3 H.sub.7 oil19E 2 CH.sub.3 H H H H H H H SO.sub.2 CH.sub.3 194-196.degree. C.20E 0 CH.sub.3 H H H H H H 3-CH.sub.3 H 40-42.degree. C.21E 2 CH.sub.3 H H H H H H 3-CH.sub.3 H 80-86.degree. C.__________________________________________________________________________ .sup.a) Prepared in Example 1E,E'. .sup.b) Prepared in Example 2E,E'. .sup.c) Prepared in Example 3E,E'.
TABLE I-F__________________________________________________________________________ ##STR94##Comp. n.sub.D.sup.30No. R.sup.50 R.sup.51 R.sup.52 R.sup.53 R.sup.54 R.sup.55 R.sup.56 R.sup.57 R.sup.58 or m.p.__________________________________________________________________________ 1F CH.sub.3 H H H H H H H H 35-42.degree. C. 2F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H H 47-53.degree. C. 3F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H Br oil 4F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CN oil 5F CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-NO.sub.2 H oil 6F CH.sub.3 CH.sub.3 CH.sub.3 H H H H 5-Cl H oil 7F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CH.sub.3 SO.sub.2 oil 8F CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H CH.sub.3 SO.sub.2 oil 9F CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-Cl H oil10F CH.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H C.sub.2 H.sub.5 SO.sub.2 oil11F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H C.sub.2 H.sub.5 SO.sub.2 oil12F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H n-C.sub.3 H.sub.7 SO.sub.2 oil13F CH.sub.3 H H H H H H H CH.sub.3 SO.sub.2 oil14F CH.sub.3 H H H H H H H n-C.sub.3 H.sub.7 SO.sub.2 oil15F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CH.sub.3 S oil16F C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H H H H H Br oil17F CH.sub.3 H H H H H H H CN oil18F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H F oil19F CH.sub.3 H H H H H H H C.sub.2 H.sub.5SO.sub.2 oil20F CH.sub.3 H H H H H H 3-Cl H 65-67.degree. C.21F CH.sub.3 H H H H H H 3-I H oil22F CH.sub.3 H H H H H H 3-NO.sub.2 H oil23F CH.sub.3 H H H H H H 3-CN H 96-101.degree. C.24F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H H oil25F CF.sub.3 H H H H H H H H oil26F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H Br oil27F CF.sub.3 H H H H H H H Cl 82-88.degree. C.28F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H Cl oil29F CF.sub.3 H H H H H H H C.sub.2 H.sub.5 S oil30F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H C.sub.2 H.sub.5 SO.sub.2 oil31F CF.sub.3 H H H H H H H CN oil32F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H CN oil33F.sup.a) CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H Br oil34F CH.sub.3 H H H H H H H CH.sub.335F CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-Cl C.sub.2 H.sub.5 SO.sub.2 115-117.degree. C.36F CH.sub.3 H H H H H H 3-Cl C.sub.2 H.sub.5 SO.sub.2 oil37F CH.sub.3 b) b) H H H H 3-CF.sub.3 H oil38F CH.sub.3 c) H i-C.sub.3 H.sub.7 H H H 3-NO.sub.2 H 88-108.degree. C.39F CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H CH.sub.3 S oil40F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H CH.sub.3 S oil41F CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H CH.sub.3 SO.sub.2 oil42F CH.sub.3 CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil43F CH.sub.3 H H H H H H H CF.sub.3 114-120.degree. C.44F CH.sub.3 H H H H H H 3-Cl Cl oil45F CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-Cl Cl oil46F CH.sub.3 CH.sub.3 CH.sub.3 H H H H 3-CF.sub.3 H oil47F CF.sub.3 H H H H H H H CH.sub.3 S oil48F CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H CF.sub.3 oil49F CF.sub.3 H H H H H H H CF.sub.3 oil50F CF.sub.3 CH.sub.3 CH.sub.3 H H H H H CF.sub.3 oil51F CH.sub.3 H H CH.sub.3 H H H H CH.sub.3 SO.sub.2 oil52F CF.sub.3 CH.sub.3 CH.sub.3 H H CH.sub.3 H H C.sub.2 H.sub.5 SO.sub.2 oil53F CH.sub.3 H H H H H H H Br 94-98.degree. C.54F CH.sub.3 H H H H H H d) H oil__________________________________________________________________________ .sup.a) Prepared in Example 1F,F'. b) (CH.sub.2).sub.5 c) C.sub.2 H.sub.5 OC(O)- d) 3N(CH.sub.3)COCH.sub.3
TABLE I-G__________________________________________________________________________ ##STR95##Comp.No. R.sup.60 R.sup.61 R.sup.62 R.sup.63 R.sup.64 R.sup.65 R.sup.66 m.p. .degree.C.__________________________________________________________________________ 1G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H 112-117.sup. 2G.sup.a) NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl 76-82 3G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 .sup. 176-179.degree. 4G CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 C.sub.2 H.sub.5 gum 5G CF.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 viscous oil 6G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.2 Cl oil 7G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-F gum 8G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OC.sub.2 H.sub.5 4-SO.sub.2 C.sub.2 H.sub.5 gum 9G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 CH.sub.3 gum10G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 gum11G CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-NO.sub.2 H gum12G I CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H gum13G OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum14G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-OCH.sub.3 4-Br gum15G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 nC.sub.3 H.sub.7 gum16G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2 N(CH.sub.3).sub.2 gum17G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CN .sup. 148-150.degree.18G SO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H H gum19G NO.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 gum20G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-Cl gum21G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCF.sub.3 gum22G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-OCF.sub.3 gum23G Cl CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 3-Cl 4-SO.sub.2 C.sub.2 H.sub.5 gum24G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-C(O)CH.sub.3 gum25G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SO.sub.2CH.sub.3 129-13126G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-SCH.sub.3 89-9227G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CF.sub.3 115-12528G H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H 4-CN 87-95__________________________________________________________________________ .sup.a) prepared in Example 1G,G'.
Herbicidal Screening Tests
As previously mentioned, the herein described compounds produced in the above-described manner are phytotoxic compounds which are useful and valuable in controlling various plant species. Selected compounds of this invention were tested as herbicides in the following manner.
Pre-emergence herbicide test. On the day preceding treatment, seeds of eight different weed species are planted in loamy sand soil in individual rows using one species per row across the width of a flat. The seeds used are green foxtail (FT) (Setaria viridis), watergrass (WG) (Echinochloa crusgalli), wild oat (WO) (Avena fatua), annual morningglory (AMG) (Ipomoea lacunosa), velvetleaf (VL) (Abutilon theophrasti), Indian mustard (MD) (Brassica juncea), redroot pigweed (PW) (Amaranthus retroflexus) or curly dock (CD) (Rumex crispus), and yellow nutsedge (YNG) (Cyperus esculentus). Ample seeds are planted to give about 20 to 40 seedlings per row, after emergence, depending upon the size of the plants.
Using an analytical balance, 600 milligrams (mg) of the compound to be tested are weighed out on a piece of glassine weighing paper. The paper and compound are placed in a 60 milliliter (ml) wide-mouth clear bottle and dissolved in 45 ml of acetone or substituted solvent. Eighteen ml of this solution are transferred to a 60 ml wide-mouth clear bottle and diluted with 22 ml of a water and acetone mixture (19:1) containing enough polyoxyethylene sorbitan monolaurate emulsifier to give a final solution of 0.5% (v/v). The solution is then sprayed on a seeded flat on a linear spray table calibrated to deliver 80 gallons per acre (748 L/ha). The application rate is 4 lb/acre (4.48 Kg/ha).
After treatment, the flats are placed in the greenhouse at a temperature of 70.degree. to 80.degree. F. and watered by sprinkling. Two weeks after treatment, the degree of injury or control is determined by comparison with untreated check plants of the same age. The injury rating from 0 to 100% is recorded for each species as percent control with 0% representing no injury and 100% representing complete control.
The results of the tests are shown in the following Tables.
TABLE II-A__________________________________________________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd. No. FT WG WO AMG VL MD PW CD YNS__________________________________________________________________________ 1A 100 90 20 40 65 50 35 80 2A 80 90 0 30 80 90 20 90 3A 0 0 0 40 40 40 0 0 4A 100 100 50 35 100 100 90 95 5A 100 95 65 35 90 85 50 95 6A 50 25 0 25 100 100 35 80 7A 80 90 10 60 100 100 100 80 8A 95 95 45 40 100 80 95 95 9A 95 100 55 30 100 90 100 9510A 100 100 60 20 85 100 100 9511A 85 100 30 40 100 100 100 9512A 85 85 90 75 80 95 90 9013A 85 75 10 10 85 65 95 9014A 40 10 80 0 65 40 65 10015A 40 60 20 30 100 30 75 9516A 80 80 20 55 75 90 40 9517A 20 -- 10 25 100 95 85 9018A 65 -- 30 70 100 100 85 9019A 45 60 0 30 40 0 20 6020A 30 85 20 40 95 85 40 4521A 80 100 0 80 100 100 95 9522A 20 10 0 20 75 30 45 1023A 45 95 10 0 100 85 100 9524A -- 100 0 25 70 90 -- 10025A -- 100 25 80 100 100 -- 10026A 40 15 0 0 0 10 0 3027A 40 80 10 20 60 50 30 7528A 65 75 0 65 100 95 75 5529A 100 95 55 10 80 75 85 9530A 20 20 20 10 40 40 50 2031A 75 95 20 20 100 95 75 1032A 90 85 20 0 100 85 75 3033A 80 70 0 40 20 40 90 8034A 60 40 0 20 95 100 100 6035A 0 10 0 0 10 20 20 1036A 0 0 0 20 100 100 100 037A 40 0 0 20 100 60 90 --38A 10 40 0 20 90 80 20 2039A 80 10 0 0 0 0 0 9040A 60 0 0 0 0 0 0 9041A 100 100 85 40 95 100 100 10042A 60 100 25 0 0 0 0 2543A 100 100 45 40 80 90 90 10044A 90 100 0 60 100 100 100 9545A 100 100 0 60 100 100 100 10046A 20 60 0 100 100 100 100 2047A 60 70 20 100 100 100 100 6048A 60 0 0 0 0 0 0 4049A 100 100 50 10 60 20 90 10050A 100 100 80 10 60 60 90 10051A 100 100 90 100 100 100 85 10052A 100 100 60 10 100 100 60 10053A 0 20 0 0 20 20 0 1054A 10 45 10 0 0 0 0 4055A 90 100 60 100 100 100 90 10056A 40 70 40 40 40 60 70 5057A 100 100 90 100 100 100 85 10058A 90 95 0 20 20 40 40 10059A 95 100 85 75 100 100 90 9860A 95 100 50 50 100 100 90 9861A 100 100 75 100 100 100 95 9562A 100 100 95 75 100 100 100 8063A 100 100 40 65 100 100 100 9564A 100 100 98 100 100 100 100 9065A 100 100 80 100 100 100 100 9066A 100 100 75 100 100 100 100 9873A 100 100 60 80 100 100 75 9074A 100 100 70 80 100 100 80 10075A 70 100 0 50 100 100 100 8076A 40 90 25 10 100 100 100 1077A 100 100 90 100 100 100 85 --78A 100 100 80 100 100 100 90 --79A 50 100 50 50 95 100 100 6080A 0 0 0 0 0 0 0 081A 100 100 50 15 100 100 90 10084A 100 100 85 0 0 100 20 10088A 60 95 35 95 100 100 95 8089A 75 100 40 100 100 100 95 6090A 100 100 90 100 100 100 100 85105A 80 95 25 0 95 50 70 50117A 95 100 0 25 100 100 50 95118A 100 100 60 100 100 100 100 85121A 95 100 50 75 100 95 100 80125A 100 100 50 80 100 100 100 85126A 70 100 80 80 100 100 100 80127A 100 100 100 100 100 100 -- 80128A 100 100 100 100 100 100 -- 80129A 100 100 95 90 100 100 -- 80131A 70 85 0 20 95 98 95 90132A 100 100 95 90 100 100 -- 80133A 100 100 100 100 100 100 -- 80135A 100 100 100 80 100 100 -- 80__________________________________________________________________________
TABLE II-B______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNS______________________________________ 1B 0 85 10 75 100 80 80 75 2B 90 100 65 100 100 100 100 100 4B 100 100 80 60 100 80 90 100 5B 80 100 20 40 100 100 80 100 6B 40 100 0 40 100 100 80 100 7B 100 100 100 80 100 100 90 100 8B 100 100 60 45 60 60 80 100 9B 60 100 40 20 60 60 60 10010B 100 100 40 5 80 60 80 10011B 100 100 90 10 20 20 40 10012B 0 20 0 0 10 20 10 013B 100 100 90 40 100 100 100 10015B 90 90 50 20 -- 100 100 8016B 100 100 95 100 100 100 90 10017B 100 100 100 100 100 100 100 9718B 100 100 85 100 100 100 90 9519B 100 100 95 100 100 100 100 9520B 100 100 85 100 100 100 100 9021B 100 100 100 100 100 100 100 9522B 100 100 80 100 100 100 100 9025B 100 100 75 80 100 100 100 9026B 100 100 65 30 100 100 100 9027B 20 95 60 5 100 100 90 10028B 100 100 80 20 90 40 80 10029B 100 100 70 20 100 100 100 10030B 100 100 80 60 100 100 80 10031B 80 100 40 10 60 60 80 10032B 20 40 10 0 -- 60 100 6033B 0 10 0 0 10 10 0 034B 100 100 90 80 100 100 90 10035B 100 100 90 40 90 90 90 9036B 100 100 85 0 95 85 95 9037B 90 90 50 20 -- 100 100 8039B 15 100 0 50 100 80 70 4040B 0 10 0 0 10 10 0 041B 0 20 0 0 10 20 10 042B 100 100 90 45 100 100 65 10043B 100 100 90 100 100 100 100 9044B 100 100 85 100 100 100 100 9545B 65 100 0 0 100 20 20 9046B 100 100 0 20 100 100 98 8547B 100 100 90 85 100 100 100 9548B 100 100 85 15 100 100 85 9549B 100 100 65 0 100 100 50 5050B 80 80 55 0 98 55 80 6551B 95 95 10 0 65 0 25 6052B 100 100 100 100 100 100 100 5053B 100 100 75 100 100 100 100 5054B 100 100 60 15 100 100 100 8055B 100 100 55 15 100 100 90 9556B 100 100 60 20 95 100 90 1057B 5 10 0 0 40 20 0 058B 10 40 10 10 95 40 100 8059B 100 100 75 80 100 100 100 7560B 100 100 90 100 100 100 85 --61B 100 100 80 100 100 100 100 --62B 95 100 50 95 100 100 85 --63B 100 100 70 100 90 100 100 --64B 100 100 75 100 100 100 85 --65B 100 100 55 40 100 100 90 7066B 100 100 65 35 100 100 100 9567B 100 100 30 15 100 100 95 9071B 100 100 80 100 100 100 80 --72B 100 100 40 100 100 100 90 7573B 90 100 40 100 100 100 95 5074B 100 100 85 95 100 100 90 8075B 100 100 100 70 100 100 100 9577B 100 100 55 40 100 100 90 7081B 90 95 60 10 25 75 90 082B 40 90 20 35 100 -- 75 2091B 100 100 85 100 100 100 80 90101B 85 90 0 0 95 50 50 75______________________________________
TABLE II-C______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd. No. FT WG WO AMG VL MD CD YNS______________________________________1C 65 80 65 55 90 90 35 0______________________________________
TABLE II-D______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNS______________________________________ 1D 100 100 85 30 100 100 90 90 2D 100 100 100 50 100 100 95 95 3D 100 100 85 25 100 100 100 95 4D 100 100 100 20 100 85 95 90 5D 100 100 45 25 100 100 90 90 6D 100 100 95 40 100 100 85 90 9D 100 100 90 90 100 100 80 9010D 100 90 20 10 100 70 100 9011D 90 100 50 230 100 100 90 9012D 100 100 95 80 100 100 90 9013D 40 75 0 10 80 100 100 9014D 50 0 0 0 100 80 70 9015D 65 95 20 15 100 80 90 8517D 100 100 60 30 100 100 90 3518D 100 100 100 100 100 100 100 9519D 100 100 0 50 100 100 100 9520D 75 100 0 25 100 90 65 9021D 100 100 100 80 100 100 90 9522D 100 100 100 80 100 100 95 9523D 100 100 98 95 100 100 100 9525D 100 100 80 100 100 100 80 --26D 100 100 75 100 100 100 80 --27D 90 100 50 100 100 100 100 9028D 75 50 50 0 100 100 90 6530D 100 100 85 100 100 100 95 9031D 85 75 0 25 100 25 0 3532D 83 85 35 20 95 100 75 5036D 100 100 50 100 100 100 100 7537D 20 75 0 20 100 95 100 7538D 85 95 40 60 100 100 75 8539D 85 95 45 75 100 95 70 9051D 60 60 35 0 25 0 0 3052D 75 75 0 50 90 75 40 065D 100 100 80 100 100 100 -- 80______________________________________ A blank (--) indicates that the weed was not tested.
TABLE II-E______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNS______________________________________1E 0 0 0 0 0 0 0 202E 25 30 30 0 70 0 40 303E 25 20 0 0 0 0 0 04E 100 100 90 60 100 100 100 905E 50 60 40 50 50 60 90 506E 100 95 50 40 40 60 99 7016E 80 100 50 60 100 90 90 9020E 100 100 30 15 100 100 90 8521E 100 100 -- 30 100 95 100 80______________________________________ A blank (--) indicates that the weed was not tested.
TABLE II-F______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNS______________________________________ 1F 40 20 0 0 0 0 0 100 2F 60 70 0 0 0 0 90 100 3F 100 100 50 50 100 100 85 90 4F 100 100 90 30 100 85 95 95 5F 100 100 80 10 100 100 100 95 6F 20 35 25 15 90 85 40 85 7F 100 100 90 100 100 100 100 95 8F 100 100 90 100 100 100 100 95 9F 100 100 0 0 100 80 100 9010F 100 100 100 100 100 100 100 9511F 100 100 70 100 100 100 97 9512F 100 100 60 100 100 100 100 9513F 100 100 60 100 100 100 100 9514F 80 100 50 80 100 100 90 9015F 100 100 80 100 100 100 100 --16F 50 75 0 25 100 100 95 6017F 100 100 40 100 100 100 100 8518F 100 100 0 20 100 100 80 7020F 70 75 0 25 100 95 100 6021F 50 60 0 0 100 80 80 6022F 100 95 35 25 100 100 90 5023F 95 100 40 20 100 100 90 5024F 100 100 90 0 45 85 80 9025F 100 100 25 60 100 100 100 7534F 35 40 10 0 60 25 0 7037F 50 60 0 0 60 0 50 038F 35 40 0 0 0 0 0 052F 85 100 30 95 100 100 -- 8053F 100 100 0 85 100 100 -- 8054F 100 100 90 25 100 100 -- 80______________________________________ A blank (--) indicates that the weed was not tested.
TABLE II-G______________________________________Pre-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD YNS______________________________________ 1G 100 100 90 100 100 100 80 2G 100 100 90 100 100 100 80 3G 100 100 90 100 100 100 80 4G 100 100 90 100 100 100 80 5G 100 100 90 100 100 100 80 6G* 100 100 100 100 100 -- 20 7G 100 100 80 100 100 100 80 8G 85 100 80 100 100 100 80 9G 100 100 80 100 100 100 8010G 100 100 80 100 100 100 8011G 100 100 80 100 100 100 8012G 100 100 80 90 100 100 013G 100 100 70 100 100 100 014G 100 100 75 100 100 100 9015G 100 100 80 100 100 100 9016G 100 100 90 100 100 100 8017G 100 100 80 100 100 100 8018G 100 100 90 85 100 100 8019G 100 100 100 100 100 100 8020G 70 95 10 100 100 100 021G 100 100 100 100 100 100 8022G 100 100 90 100 100 100 8023G 100 100 100 100 100 100 8024G 0 80 0 25 80 70 025G 100 100 80 100 100 100 8026G 100 100 100 80 100 100 8027G 100 100 100 100 100 100 8028G 100 100 90 100 100 100 80______________________________________ A blank (--) indicates that the weed was not tested. *Tested at 0.56 kg/ha.
Post-Emergence Herbicide Test: This test is conducted in an identical manner to the testing procedure for the pre-emergence herbicide test, except the seeds of the eight different weed species are planted 10-12 days before treatment. Also, watering of the treated flats is confined to the soil surface and not to the foliage of the sprouted plants.
The results of the post-emergence herbicide test are reported in Table III.
TABLE III-A__________________________________________________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd. No. FT WG WO AMG VL MD PW CD YNS__________________________________________________________________________ 1A 60 70 20 40 60 60 35 60 2A 30 70 0 50 90 85 30 80 3A 0 30 0 70 100 90 55 70 4A 95 98 20 98 100 100 30 95 5A 80 80 75 50 60 80 0 95 6A 40 40 10 60 100 100 75 65 7A 60 75 40 60 100 75 100 75 8A 85 80 75 70 95 80 90 90 9A 85 80 75 70 95 80 90 9010A 95 85 90 60 95 95 80 9511A 50 80 35 55 100 100 95 8012A 45 75 50 55 75 60 50 8013A 30 60 20 60 80 50 60 7014A 20 10 20 50 45 40 40 015A 65 95 0 65 95 30 100 8016A 65 80 20 85 85 30 30 8017A 75 80 30 70 100 100 85 9018A 100 95 10 100 100 100 100 9019A 60 80 40 70 100 75 80 9020A 65 80 10 85 95 95 100 7021A 30 55 0 80 100 80 65 8022A 0 30 0 20 45 0 30 2023A 85 90 40 85 100 95 100 9024A 0 80 0 70 90 74 -- 10025A 100 100 75 90 100 100 -- 10026A 45 30 0 40 70 65 0 4527A 75 80 30 65 50 45 85 8528A 75 60 60 75 100 70 80 2529A 85 85 85 75 85 65 65 8530A 75 50 20 10 0 0 20 4031A 60 60 20 40 40 70 100 4032A 60 25 20 40 90 65 20 4033A 10 0 0 10 10 10 100 4034A 10 10 0 5 50 30 80 035A 0 0 0 10 60 30 40 036A 0 0 0 20 20 20 0 037A 0 0 0 30 40 20 80 038A 10 10 10 20 10 20 20 1039A 40 40 20 0 0 0 5 8040A 90 70 40 20 60 80 20 6541A 60 85 85 20 40 60 100 10042A 60 50 40 70 20 40 60 6043A 100 80 30 60 100 100 80 10044A 80 85 0 60 90 90 100 8045A 90 90 10 100 100 100 100 9046A 80 100 0 60 100 100 100 10047A 100 100 0 60 100 100 100 10048A 40 40 20 10 10 10 90 4049A 40 40 40 80 100 100 60 6050A 80 60 60 50 50 60 80 7051A 80 80 80 95 100 100 100 9052A 60 60 20 20 40 40 90 6053A 10 20 20 0 0 0 0 2054A 20 40 20 5 0 0 0 4055A 40 40 40 60 60 60 80 9056A 100 100 75 80 100 100 100 9057A 80 80 80 95 100 100 100 9058A 60 70 10 70 10 10 20 8059A 100 100 90 100 -- 100 100 5060A 100 100 100 100 -- 100 100 7061A 90 85 90 85 -- 100 100 8062A 100 85 100 75 100 100 100 3563A 70 80 20 100 100 100 35 4064A 75 75 90 70 90 70 40 4065A 100 70 100 55 90 95 100 4066A 100 75 100 90 95 95 100 2073A 100 100 95 100 100 100 55 3074A 100 95 75 100 100 100 85 4075A 100 100 30 95 80 100 80 4076A 80 80 75 75 100 95 95 2577A 80 80 80 90 90 80 90 8078A 80 85 75 85 80 95 100 5079A 50 65 35 90 100 100 90 --80A 40 40 10 20 60 0 0 3081A 90 70 60 40 60 60 90 7084A 100 100 100 20 40 40 80 6088A 100 95 90 100 85 100 100 5089A 100 100 75 85 75 85 95 5090A 100 85 90 90 85 90 100 5591A 100 100 100 100 95 100 95 60105A 35 50 -- 35 100 80 60 30117A 40 60 0 25 50 50 80 --118A 95 85 85 100 100 90 80 80121A 65 85 40 100 100 100 60 50125A 90 95 75 70 100 90 100 60126A 40 50 20 40 60 50 100 80127A 100 95 100 95 100 100 80128A 85 95 80 60 100 95 80129A 65 90 60 60 100 98 70130A 100 95 95 95 100 100 70131A 0 20 0 0 30 75 10 0132A 95 100 100 80 95 95 50133A 80 95 90 60 85 85 60135A 70 100 100 75 100 95 70__________________________________________________________________________
TABLE III-B______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNS______________________________________ 1B 85 95 20 95 100 100 95 95 2B 90 90 80 100 90 90 -- 80 4B 60 60 90 40 60 60 90 70 5B 40 60 10 20 40 40 90 80 6B 40 50 10 60 20 20 60 50 7B 80 80 80 60 60 90 6 60 8B 100 80 60 30 80 80 80 80 9B 70 70 60 40 60 60 80 7010B 40 40 60 30 60 60 90 6011B 80 90 60 45 90 90 100 8012B 25 45 10 20 20 20 60 4513B 100 100 95 70 60 60 80 6015B 100 60 50 80 90 90 40 6016B 60 60 80 80 90 90 60 6517B 100 70 90 100 -- 90 98 7018B 100 85 100 85 -- 100 100 6519B 100 80 85 100 100 90 100 7020B 90 65 90 85 70 60 100 4021B 40 40 10 0 0 0 0 022B 40 70 80 90 90 100 95 4025B 40 70 40 40 40 60 70 5026B 65 70 80 40 90 80 70 8027B 100 80 60 20 90 90 80 4528B 90 60 60 60 60 60 40 7029B 90 70 70 40 70 70 60 6030B 100 90 70 50 100 100 80 8031B 40 50 20 10 20 20 0 4032B 25 40 40 90 100 100 40 4033B 20 40 10 60 90 90 60 4034B 90 80 80 80 100 100 80 5035B 60 50 50 20 60 60 80 6036B 100 80 80 75 -- 100 100 4537B 100 60 50 80 90 90 40 6039B 90 80 25 30 30 45 50 3040B 20 40 10 60 90 90 60 4041B 25 45 10 20 20 20 60 4542B 90 80 80 80 100 100 100 7043B 80 90 95 97 100 100 100 5044B 100 95 95 95 40 100 100 3045B 30 65 0 30 45 40 65 5046B 70 75 0 65 100 100 50 7047B 100 100 100 90 100 100 100 8548B 100 65 80 50 100 100 60 6049B 60 70 70 40 80 70 30 5050B 0 60 40 60 100 90 20 3051B 100 75 80 40 100 50 20 3052B 90 100 100 100 100 100 100 4053B 60 70 70 70 90 65 40 6054B 100 100 85 100 100 100 100 6055B 95 85 90 100 100 100 90 4556B 85 100 0 10 15 95 40 5057B 85 70 65 0 0 0 0 3558B 20 40 10 15 70 40 35 4059B 100 95 100 95 100 95 100 4060B 65 75 75 80 90 85 80 6061B 80 80 70 95 80 85 80 5062B 100 80 25 80 75 80 85 3563B 100 100 40 95 95 100 95 5064B 75 70 50 90 90 100 90 5065B 100 80 80 60 85 60 0 --66B 98 90 60 35 -- 100 60 9067B 70 65 20 15 95 40 70 4571B 95 50 50 80 80 80 65 5072B 100 85 75 75 65 85 70 6073B 100 95 95 85 75 85 95 4074B 100 85 95 90 80 95 65 5075B 100 80 80 30 50 60 100 4081B 50 80 35 70 70 90 80 1082B 25 60 50 35 50 90 50 2591B 80 60 40 60 75 90 60 75101B 10 35 -- 30 75 70 40 50______________________________________ (--) = Specie did not germinate for some reason.
TABLE III-C______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd. No. FT WG WO AMG VL MD CD YNS______________________________________1C 98 95 70 60 100 55 100 90______________________________________
TABLE III-D______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNS______________________________________ 1D 95 75 85 70 100 90 85 40 2D 45 70 95 75 100 90 100 65 3D 100 80 100 90 -- 100 100 80 4D 100 80 100 100 -- 100 85 75 5D 90 70 45 60 95 70 60 80 6D 95 75 80 70 100 90 90 65 9D 100 90 90 100 100 100 95 8510D 45 75 10 15 100 100 20 7511D 100 70 60 75 100 100 100 4512D 100 75 100 100 100 100 90 9013D 30 55 0 30 60 60 15 6014D 20 65 0 40 70 60 40 2515D 20 75 30 20 100 70 60 4017D 85 80 50 65 95 95 100 6018D 100 95 100 100 100 100 100 7519D 20 95 30 100 100 35 30 7020D 30 80 15 100 100 45 20 7021D 100 80 100 55 100 90 100 8022D 100 80 100 60 100 95 95 9523D 100 90 90 100 100 100 85 7025D 70 75 50 85 90 85 60 7526D 100 85 85 95 95 95 90 6027D 90 90 60 100 100 100 100 --28D 15 45 20 50 75 80 15 3030D 100 100 80 85 85 85 100 --31D 80 90 100 100 100 100 100 6032D 75 85 85 75 75 90 95 5036D 35 50 35 70 50 50 35 6037D 60 75 15 70 70 90 90 4038D 95 90 65 70 90 90 100 5039D 95 85 30 50 70 80 100 5051D 60 75 60 35 30 60 40 6052D 60 75 25 100 100 100 100 7565D 70 50 70 90 80 85 -- 80______________________________________ A blank (--) indicates the weed was not tested.
TABLE III-E______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNG______________________________________1E 20 20 10 20 40 40 20 402E 0 60 60 50 70 30 0 153E 20 20 0 10 0 20 0 204E 85 90 100 45 75 30 80 655E 55 50 60 50 75 85 65 --6E 70 70 50 60 80 70 90 --16E 95 95 40 100 100 100 100 9020E 95 75 35 40 95 75 35 8021E 80 70 30 45 80 90 50 70______________________________________ A blank (--) indicates the weed was not tested.
TABLE III-F______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD CD YNG______________________________________ 1F 60 40 20 30 40 40 50 60 2F 50 40 10 20 20 20 40 60 3F 100 100 85 100 100 100 100 75 4F 100 100 95 85 100 95 100 60 5F 95 95 100 65 90 25 70 45 6F 40 30 0 20 90 25 20 70 7F 100 100 100 100 100 100 100 90 8F 100 95 100 100 100 100 100 70 9F 65 65 0 20 80 65 90 8010F 100 100 100 100 100 100 100 7011F 85 90 90 85 90 80 30 6012F 100 90 65 80 100 100 100 5013F 100 95 100 100 100 100 90 --14F 100 100 100 100 100 100 100 5015F 25 35 15 30 80 25 20 016F 100 85 70 75 90 90 50 --17F 100 100 100 100 100 100 100 --18F 90 85 85 85 90 95 70 4020F 40 60 10 60 100 100 100 5021F 35 60 10 60 100 100 80 6022F 95 95 35 100 100 100 90 5023F 100 100 40 100 100 100 90 5024F 100 75 100 60 -- 100 100 6025F 95 95 90 95 100 100 95 3534F 50 40 0 35 50 70 30 5037F 20 60 0 30 30 50 50 5038F 25 50 0 25 25 50 20 2052F 0 60 50 50 10 50 -- 2053F 0 50 0 50 50 50 -- 3054F 90 75 60 50 50 80 -- 80______________________________________ A blank (--) indicates the weed was not tested.
TABLE III-G______________________________________Post-Emergence Herbicidal ActivityApplication Rate - 4.48 kg/haCmpd.No. FT WG WO AMG VL MD YNG______________________________________ 1G 100 95 90 90 100 100 80 2G 100 100 100 100 100 100 80 3G 100 100 95 100 100 100 90 4G 100 100 100 100 100 100 90 5G 100 100 100 100 100 100 100 6G* 10 80 50 75 40 -- 0 7G 70 75 70 90 90 80 80 8G 50 80 70 90 90 80 30 9G 70 80 70 90 90 80 3010G 75 80 70 80 60 50 7011G 70 80 70 80 80 80 8012G 100 75 90 75 80 80 8013G 60 70 70 100 100 100 8014G 20 70 40 60 80 80 7015G 90 70 70 75 80 90 7016G 50 70 80 60 80 90 7017G 90 60 70 65 80 80 8018G 30 50 80 95 95 80 7019G 100 100 95 90 100 100 8020G 10 40 5 70 80 90 7021G 95 90 95 95 100 100 7022G 80 90 90 80 100 100 7023G 90 80 80 80 90 80 3024G 0 30 0 40 80 20 025G 0 20 0 10 10 20 026G 80 70 70 80 80 80 7027G 90 90 90 80 80 90 6028G 70 65 50 80 80 80 70______________________________________ A blank (--) indicates the weed was not tested. *Tested at 0.56 kg/ha.
Pre-Emergence Multi-Weed Herbicide Test
Several compounds were evaluated at an application rate of 2 lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for pre-emergence activity against a larger number of weed species.
The process was generally similar to the pre-emergence herbicide test described above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.
Redroot pigweed (PW) and curly dock (CD) were eliminated in this test and the following weed species were added:
______________________________________Grasses: downy brome Bromus tectorum (DB) annual ryegrass Lolium multiflorum (ARG) rox-orange sorghum Sorghum bicolor (SHC) hemp sesbania Sesbania exaltata (SESB) nightshade Solanum sp. (SP) cocklebur Xattiium sp. (CB)______________________________________
The results of the 2.24 kg/ha test are shown in Table IV and the results of the 1.12 kg/ha test are shown in Table VI.
Post-Emergence Multi-Weed Herbicide Test
Several compounds were evalated at an application rate of 2 lb/acre (2.24 kg/ha) or 1 lb/acre (1.12 kg/ha) for post-emergence activity against the larger number of weed species that are used in the pre-emergent multi-herbicide test.
The process was generally similar to the post-emergence herbicide test describe above except that only 300 or 150 milligrams of test compound were weighed out and the application rate was 40 gallons per acre.
The results of the 2.24 kg/ha test are shown in Table V and the results for the 1.12 kg/ha test are shown in Table VII.
TABLE IV-A__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate - 2.24 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________67A 20 90 25 98 80 60 90 45 90 45 20 85 85 1568A 65 98 98 100 100 60 95 100 100 100 80 100 95 10069A 65 100 70 100 100 65 95 100 95 70 65 100 90 --70A 98 100 100 100 100 90 98 90 100 90 60 100 95 8071A 60 20 100 100 100 80 95 35 40 100 20 90 100 4072A 100 100 100 100 100 100 100 100 90 100 60 100 100 2083A 15 45 25 90 15 5 90 45 35 20 0 20 75 --86A 20 0 15 60 60 20 70 25 45 100 20 100 15 3587A 100 90 85 100 85 25 30 35 85 100 85 100 95 40__________________________________________________________________________
TABLE VI-A__________________________________________________________________________Post-Emergence Multi-weed Herbicide TestApplication Rate - 2.24 hg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________86A 60 100 50 90 50 60 90 70 100 100 20 100 20 --87A 95 100 30 100 80 70 80 95 100 100 100 100 70 --__________________________________________________________________________
TABLE V-A__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate - 1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________ 82A 35 100 85 100 65 60 90 50 90 60 30 97 90 40 85A 100 100 100 100 100 85 100 20 10 100 65 100 100 30 92A 15 20 45 100 90 40 80 95 95 100 25 100 90 40 93A 30 75 40 100 100 60 90 100 100 100 35 100 90 40 94A 30 70 40 100 100 30 65 95 85 100 0 100 90 30 95A 0 0 0 85 60 15 70 65 60 100 80 90 10 20 96A 95 100 98 100 100 70 100 100 95 90 80 100 95 -- 97A 100 100 98 100 100 100 100 100 95 100 70 100 95 100 98A 10 0 0 0 20 25 70 0 20 0 0 80 30 -- 99A 15 0 0 75 25 0 20 30 60 15 20 30 25 0100A 0 0 0 0 0 0 20 10 0 0 0 15 0 --101A 100 98 95 100 100 70 98 100 100 100 20 100 95 --102A 25 20 35 100 100 45 95 70 100 100 60 100 90 --103A 80 60 45 100 100 40 90 65 90 100 0 100 95 0106A 100 100 60 40 95 35 100 35 90 100 70 100 90 --107A 100 100 100 100 100 90 100 100 100 100 80 100 95 30108A 100 100 100 100 100 85 100 100 100 100 30 100 95 100109A.sup.a 65 20 85 100 98 60 90 30 50 100 50 100 90 100110A 0 60 30 100 65 25 65 25 30 100 0 100 60 0111A 100 100 100 100 100 75 98 100 100 100 90 100 -- 70112A 100 100 90 100 100 95 100 100 100 100 100 100 -- --113A 65 95 40 100 100 30 90 70 100 100 0 100 -- 30114A 70 100 25 100 100 40 100 100 100 100 30 100 95 80115A 100 100 100 100 100 100 100 100 100 100 45 100 85 100116A 25 15 20 100 65 35 65 45 50 100 0 100 95 10119A 100 100 100 100 100 100 100 100 100 100 95 100 95 90120A 100 100 100 100 100 95 100 100 100 100 100 100 90 100122A 80 80 45 100 60 65 70 100 100 100 100 100 90 100123A 0 100 50 100 85 0 60 100 90 100 80 100 100 20124A 25 50 65 90 65 0 40 75 80 100 40 90 80 60__________________________________________________________________________ .sup.a application rate was 0.56 kg/ha.
TABLE VII-A__________________________________________________________________________Post-Emergence Multi-weed Herbicide TestApplication Rate - 1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________ 82A 60 40 10 98 35 10 30 70 100 100 100 90 45 -- 85A 60 60 35 100 45 60 85 50 100 100 100 100 60 -- 92A 70 55 20 80 80 45 100 95 90 80 20 95 70 90 93A 90 90 70 95 95 75 90 98 95 85 35 100 60 90 94A 100 85 45 90 100 90 100 100 90 90 30 100 60 85 95A 20 60 0 80 70 0 45 60 75 90 0 65 20 -- 96A 95 100 90 95 100 80 95 100 100 100 70 100 70 90 97A 100 100 95 100 100 100 100 100 100 100 90 100 70 100 98A 20 0 0 45 10 50 30 20 65 100 0 75 35 80 99A 25 75 15 80 65 10 25 85 100 100 80 100 10 --100A 10 35 0 70 50 5 20 30 70 40 0 100 10 100101A 30 60 25 100 60 60 80 100 100 100 30 100 70 --103A 90 100 25 100 100 80 100 100 100 100 15 100 40 --104A 98 98 25 98 100 15 100 100 100 100 60 100 95 --106A 75 90 30 90 70 25 100 100 100 100 80 100 75 --107A 100 100 80 90 85 100 100 100 100 100 60 100 40 --108A 100 100 65 90 60 95 100 100 100 100 90 100 90 --109A.sup.a 90 60 45 90 70 60 98 95 95 100 98 80 55 --110A 50 50 20 100 50 10 40 100 98 98 20 100 35 45111A 85 90 80 90 70 60 95 100 90 100 65 100 80 60112A 100 100 90 100 100 95 100 100 100 100 45 100 95 70113A 70 50 20 90 60 50 80 95 95 100 60 100 -- 60114A 85 100 15 100 100 60 00 100 100 100 100 100 60 --115A 100 100 45 100 100 80 100 100 100 100 100 100 90 --116A 80 60 25 90 35 40 45 75 90 100 40 90 75 60119A 60 70 30 95 70 20 90 100 100 100 90 100 30 85120A 75 90 60 95 80 45 100 100 90 100 65 100 35 100122A 60 90 15 100 30 15 15 100 100 100 75 100 45 95123A 0 100 35 100 50 15 85 100 100 100 100 100 70 85124A 25 100 35 40 35 0 40 95 100 100 100 100 85 75__________________________________________________________________________ A = Application rate was 0.56 kg/ha. A dash mark (--) is used in Tables II-VII to indicate that no percent control number was available.
TABLE IV-B__________________________________________________________________________Pre-Emergence Multi-Weed Herbicide TestApplication Rate - 2.24 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________14B 80 100 100 100 100 80 95 70 60 100 40 85 100 1021B 85 100 90 100 100 85 100 100 100 100 70 100 95 10024B 100 100 100 100 100 100 100 100 100 100 75 100 95 --38B 100 100 100 100 100 100 100 20 10 100 20 95 100 2088B 75 100 60 100 100 70 60 20 40 100 0 100 60 2089B 20 60 30 85 95 55 40 15 20 65 0 100 35 5090B 60 100 60 100 100 45 30 100 100 100 15 100 50 85103B 95 100 75 100 100 50 85 100 100 100 80 100 80 40104B 60 100 60 100 100 45 30 100 100 100 15 100 50 85__________________________________________________________________________ (--) = Specie did not germinate for some reason.
TABLE V-B__________________________________________________________________________Post-Emergence Multi-Weed Herbicide TestApplication Rate - 2.24 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________24B 35 25 45 60 65 85 90 100 100 -- 90 100 65 --88B 60 30 30 90 100 80 100 100 100 100 30 100 20 10089B 50 70 35 90 60 35 20 100 90 100 35 100 15 10090B 30 100 40 100 70 10 25 100 100 100 30 90 50 95103B 95 100 70 100 65 75 65 100 100 100 65 100 50 100104B 30 100 40 100 70 10 25 100 100 100 30 90 50 95__________________________________________________________________________ (--) = Specie did not germinate for some reason.
TABLE VI-B__________________________________________________________________________Pre-Emergence Multi-Weed Herbicide TestApplication Rate - 1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________ 1B 25 10 30 85 55 0 -- 55 -- 100 -- 75 75 3523B 55 95 90 100 95* 95 95 98 80 -- 10 100 95 --68B 65 100 60 100 100* 6 90 100 90 100 20 100 30 4069B 70 100 60 100 100* 95 95 100 95 100 0 100 85 2570B 60 100 75 100 100* 85 100 100 90 100 25 100 90 2576B 100 100 85 100 100* 85 98 100 95 -- 35 100 9578B 40 70 15 95 75* 25 80 65 75 -- 0 100 80 --79B 100 100 100 100 100 98 100 100 85 100 85 100 95 --80B 98 100 95 100 100 60 98 99 90 100 35 100 85 --83B 20 100 60 100 100* 40 90 85 65 100 0 100 85 --84B 0 90 25 98 100* 30 90 20 35 100 5 100 50 --85B 80 100 50 100 100 60 90 100 90 100 0 100 95 --86B 60 90 40 100 100 60 70 35 60 100 100 100 -- --87B 0 90 15 100 85 15 70 40 60 100 40 90 20 --92B 20 40 10 95 40 10 60 65 30 100 0 55 60 093B 60 95 20 100 100 75 100 100 100 100 0 100 40 3594B 0 80 40 100 95 25 85 80 40 100 10 85 55 1095B 98 100 30 100 100 40 90 100 100 100 40 100 90 3096B 100 100 75 100 100 95 100 100 100 100 60 100 85 10097B 100 100 90 100 100 95 100 100 100 100 60 100 95 10098B 95 100 100 100 100 80 100 100 100 100 50 100 100 60 99B** -- 100 75 100 100* 20 75 50 75 95 0 -- 85 30100B 100 98 98 100 100 90 95 100 75 100 70 100 95 40102B 0 100 25 100 90 75 95 60 60 100 30 100 90 --__________________________________________________________________________ *seedling johnsongrass (Sroghum halepense) was substituted for roxorgange sorghum. **Application rate was 0.56 kg/ha (--) = Specie did not germinate for some reason.
TABLE VII-B__________________________________________________________________________Post-Emergence Multi-Weed Herbicide TestApplication Rate - 1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________ 1B 45 35 40 90 35 10 -- 60 -- 75 -- 60 50 5523B 90 100 80 90 90* 90 90 80 90 90 40 70 25 --68B 50 60 40 85 80* 75 100 95 90 85 55 100 40 --69B 70 80 35 90 90* 80 90 80 85 90 20 90 25 --70B 100 90 80 100 100* 95 100 100 95 80 30 75 45 9076B 100 100 98 100 100* 100 100 100 100 100 60 100 40 --78B 100 90 80 85 100* 70 90 100 100 100 0 90 45 --79B 80 35 45 70 60* 70 70 45 98 100 35 90 20 --80B 60 70 25 90 60* 60 85 70 90 100 15 100 25 10085B 95 100 65 100 80 90 100 100 100 100 25 100 85 --86B 30 60 20 75 50 50 60 50 65 100 10 100 20 8087B 0 0 0 100 45 20 30 60 90 80 0 100 30 4592B 20 80 10 85 15 0 30 100 40 100 0 60 60 3093B 70 100 25 100 100 85 100 100 100 100 100 100 80 --94B 20 70 30 90 80 30 20 100 100 100 60 30 30 10095B 60 90 15 95 95 25 90 100 100 100 75 100 70 10096B 50 80 0 90 70 30 100 100 100 100 40 100 20 10097B 65 100 35 100 75 70 80 100 100 100 50 100 50 10098B 95 100 65 95 90 100 95 100 100 90 40 80 60 95 99B** -- 100 95 90 90* 90 100 25 80 40 100 -- 35 75100B 65 75 60 80 75 60 85 100 100 100 45 100 65 60102B 30 75 20 80 60 0 40 70 100 100 30 100 75 --__________________________________________________________________________ *Seedling johnsongram (Sorghum halepense) was substituted for roxorange sorghum. **Application rate was 0.56 kg/ha. (--) = Specie did not germinate for some reason.
TABLE IV-C__________________________________________________________________________Post-Emergence Multi-weed Herbicidal TestApplication Rate - 1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________2C 0 100 0 100 -- 45 70 65 50 100 15 100 90 --__________________________________________________________________________ (--) = Not tested.
TABLE V-C__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate - 1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________2D 0 30 0 100 -- 0 60 85 95 100 100 90 40 --__________________________________________________________________________ (--) = Not tested.
TABLE IV-D__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate - 2.24 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________ 7D 100 100 100 100 100 100 100 100 100 100 100 100 95 100 8D 100 100 100 100 100 100 100 100 100 100 100 100 95 --16D.sup.a 70 100 65 100 100 60 98 55 100 100 90 100 90 --24D 100 100 100 100 100 100 100 100 100 100 100 100 100 --29D 100 100 100 100 100 100 100 100 100 100 30 100 95 8033D 75 15 60 90 90 20 95 100 100 100 60 100 95 10053D 100 100 100 100 100 90 100 100 100 100 100 100 95 10057D 100 100 25 100 100 30 25 100 100 100 100 100 95 10064D.sup.a -- 0 0 95 35 0 15 50 75 75 25 -- 75 4066D.sup.a -- 0 15 15 50 20 50 100 100 75 0 -- 90 10067D.sup.a -- 0 0 100 100 0 25 95 75 50 25 -- 30 7569D.sup.a -- 30 0 100 100 0 70 100 100 100 35 -- 95 10070D.sup.a -- 100 10 100 100 25 65 100 100 100 0 -- 95 100__________________________________________________________________________ (--) = Not tested. .sup.a Tested at 0.28 kg/ha.
TABLE V-D__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate-1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________34D 90 85 30 95 -- 45 98 75 100 100 40 100 50 --35D 100 85 70 100 -- 90 100 100 100 100 40 100 75 --40D 100 100 20 100 -- 70 100 98 98 100 20 100 50 --41D 100 100 80 100 -- 60 100 100 100 100 25 100 95 --42D 50 60 40 85 -- 30 100 100 100 100 100 100 90 --43D 90 95 60 100 -- 30 98 100 98 100 45 100 95 --44D 60 100 20 100 -- 60 100 100 90 100 20 100 80 --45D 95 100 35 100 -- 60 90 100 100 100 0 100 90 --46D 100 100 90 100 -- 95 100 100 100 100 40 100 95 --47D 100 100 100 100 -- 98 100 100 98 100 30 100 95 --48D 100 100 100 100 -- 100 100 100 100 100 90 100 100 --49D 100 100 100 100 -- 100 100 100 100 100 90 100 -- --50D 100 100 100 100 100 85 100 100 100 100 90 100 98 --54D 100 100 85 100 100 15 100 25 100 100 65 100 95 10055D 85 100 35 100 98 15 100 15 100 100 65 100 95 --56D 100 100 100 100 100 100 100 100 100 100 100 100 100 10058D 98 100 40 95 40 20 95 100 100 100 85 100 100 9559D 100 100 100 100 100 90 100 100 100 100 100 100 85 8060D 100 100 100 100 100 100 100 100 100 100 75 100 85 80__________________________________________________________________________ (--) = Not tested.
TABLE VI-D__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate-0.56 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________61D -- 100 65 100 65 20 80 20 40 80 10 -- 20 062D -- 50 35 70 50 0 0 0 25 50 0 -- 0 063D 100 100 100 100 100 95 100 90 95 100 75 100 100 8568D -- 0 20 0 0 0 0 60 100 100 90 -- 75 7571D -- 50 40 50 75 40 35 75 50 70 0 -- 75 7572D -- 35 60 100 85 50 100 25 65 100 35 -- 100 3573D -- 90 70 100 95 25 0 70 100 100 0 -- 50 25__________________________________________________________________________ (--) = Not tested.
TABLE VII-D__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate-2.24 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________ 7D 100 100 100 100 80 90 10 95 100 100 55 100 45 10016D.sup.a 100 85 35 100 100 100 100 100 100 100 100 100 85 7024D 100 100 100 100 100 100 100 100 100 100 100 100 100 --29D 100 100 60 100 90 100 100 100 100 100 100 100 100 --33D 90 98 85 100 100 80 100 100 100 100 90 100 90 10053D 100 100 60 100 100 100 100 100 100 100 100 100 100 --57D 25 40 10 100 10 0 10 100 95 100 35 100 -- 10064D.sup.a -- 0 0 90 0 0 85 40 100 80 50 -- 35 10066D.sup.a -- 0 0 65 0 0 70 75 80 75 0 -- 25 7567D.sup.a -- 0 0 75 35 0 40 70 80 60 0 -- 0 10069D.sup.a -- 0 0 80 35 0 100 90 100 100 40 -- 35 10070D.sup.a -- 100 0 100 70 90 90 100 100 100 30 -- 25 100__________________________________________________________________________ (--) = Not tested. .sup.a Tested at 0.28 kg/ha.
TABLE VIII-D__________________________________________________________________________Post-Emergence Multi-weed Herbicide TestApplication Rate-1.12 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________34D 90 85 30 95 -- 45 98 75 100 100 40 100 50 --35D 100 85 70 100 -- 90 100 100 100 100 40 100 75 --40D 75 100 5 100 -- 50 75 100 100 100 40 100 30 --41D-- -- -- -- -- -- -- -- -- -- -- -- -- -- --42D 40 100 35 100 -- 50 80 100 100 100 80 100 70 --43D 60 70 20 100 -- 55 60 100 100 100 95 100 70 --44D -- -- -- -- -- -- -- -- -- -- -- -- -- --45D -- -- -- -- -- -- -- -- -- -- -- -- -- --46D -- -- -- -- -- -- -- -- -- -- -- -- -- --47D 90 100 35 100 -- 75 90 100 100 100 25 100 45 --48D 80 100 60 100 -- 60 80 100 100 100 85 100 60 --49D -- -- -- -- -- -- -- -- -- -- -- -- -- --50D 90 80 60 95 80 90 100 100 100 100 65 100 80 --54D 35 50 30 100 30 15 90 100 100 100 100 100 95 --55D 100 100 20 100 90 20 100 90 100 100 100 100 -- --56D 75 90 75 95 90 25 100 100 100 100 90 100 90 10058D 70 100 40 100 95 30 95 100 95 100 95 100 95 8559D 90 100 95 100 100 50 100 100 100 100 95 100 100 9560D 95 100 100 100 100 75 95 100 100 100 95 100 100 100__________________________________________________________________________ (--) = Not tested.
TABLE IX-D__________________________________________________________________________Post-Emergence Multi-weed Herbicide TestApplication Rate-0.56 kg/haCmpd.No. DB FT ARG WG SHC WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________61D -- 40 0 50 35 0 40 75 95 100 0 -- 25 5062D -- 35 0 20 0 0 20 35 60 100 0 -- 0 10063D 100 100 85 98 85 100 100 100 100 100 100 85 85 9568D -- 30 40 85 0 25 60 80 95 100 95 -- 0 8071D -- 50 0 80 65 0 75 100 80 100 50 -- 25 10072D -- 90 70 80 50 50 75 85 100 100 90 -- 100 10073D -- 100 15 100 75 75 85 100 100 90 60 -- 80 100__________________________________________________________________________ (--) = Not tested.
TABLE IV-E__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate-2.24 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS__________________________________________________________________________17E 95 85 35 100 85 25 90 100 100 100 40 100 9518E 0 0 0 50 20 0 15 60 45 100 0 100 --__________________________________________________________________________
TABLE V-E__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate-1.12 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS__________________________________________________________________________ 7E 30 70 20 100 75 0 90 100 95 100 100 100 90 8E 95 95 45 100 98 25 90 100 95 100 90 100 90 9E 10 70 40 100 20 0 80 100 85 100 40 100 9510E 100 100 10 100 40 0 90 100 100 100 80 100 10011E 90 100 90 100 100 65 100 100 90 100 30 100 6512E 100 100 80 100 100 85 90 100 100 100 85 100 9013E 0 100 10 100 100 80 70 80 90 100 70 100 8015E 0 10 0 90 0 0 15 35 30 100 10 85 7519E 100 90 0 100 20 10 40 95 100 100 100 100 65__________________________________________________________________________
TABLE VI-E__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate-2.24 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS__________________________________________________________________________17E 80 100 55 95 90 20 60 100 100 100 75 100 7018E 0 100 0 98 20 0 10 70 60 100 10 100 45__________________________________________________________________________
TABLE VII-E__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate-1.12 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS__________________________________________________________________________ 7E 25 30 0 70 60 20 90 75 95 85 50 100 35 8E 80 80 20 70 70 40 80 50 80 80 60 60 35 9E 0 30 0 75 15 25 100 95 100 100 60 100 2510E 60 80 20 70 35 25 80 75 90 90 70 100 4511E 45 100 20 100 100 40 50 100 100 100 20 100 3512E 70 60 30 100 100 80 98 90 100 100 70 98 4013E 25 100 10 100 100 85 100 80 100 100 10 90 2515E 30 65 10 90 50 30 20 85 80 98 30 65 1519E 20 60 10 90 10 15 90 100 100 70 100 40 85__________________________________________________________________________
TABLE IV-F__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate-1.12 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________19F 40 35 60 100 90 30 90 100 100 -- 20 100 90 --26F 25 70 45 95 60 25 85 35 75 -- 20 100 95 9027F 45 65 40 100 60 25 80 100 85 100 40 100 95 3528F 80 100 90 100 100 90 100 70 90 100 30 100 95 3529F 90 45 75 100 85 40 90 95 90 100 40 100 95 --30F 90 45 75 100 90 75 100 100 80 100 60 100 95 --31F 60 65 75 100 100 55 95 100 100 100 100 100 95 --32F 90 100 90 100 100 65 85 100 90 100 95 100 85 --33F 100 100 95 100 100 95 100 100 100 100 25 100 90 --35F 90 100 100 100 -- 90 90 100 90 100 10 100 75 --36F 90 35 85 100 -- 15 80 95 90 100 50 100 95 --39F 100 100 100 100 100 95 100 100 100 100 100 100 98 --40F 100 100 80 100 100 70 100 100 100 100 90 100 95 --41F 100 100 100 100 100 100 100 100 100 100 60 100 98 --42F 60 100 85 100 100 70 95 100 95 100 10 100 95 5043F 85 100 25 100 60 25 98 100 100 100 100 100 90 10044F 0 80 10 85 0 0 75 0 30 100 0 100 0 1045F 25 100 40 100 60 0 65 60 60 100 50 100 70 050F -- 100 50 100 35 35 75 100 100 --__________________________________________________________________________ (--) = Not tested.
TABLE V-F__________________________________________________________________________Pre-Emergence Multi-weed Herbicide TestApplication Rate-0.56 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________46F 0 65 35 75 65 0 0 0 35 100 25 90 80 047F -- 60 35 100 100 0 90 100 100 100 70 -- 100 7548F -- 75 20 90 60 0 15 70 35 90 0 -- 20 4049F -- 60 10 100 60 0 50 100 95 100 40 -- 90 10051F -- 40 10 95 40 10 50 65 100 100 0 -- 95 65__________________________________________________________________________ (--)-Not tested.
TABLE VI-F__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate-2.24 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________19F 100 90 65 100 100 98 100 100 100 100 60 100 70 10026F 60 75 60 95 45 50 90 50 90 100 40 90 60 --27F 80 70 65 95 100 90 100 100 100 100 85 100 75 --28F 80 100 75 90 85 80 100 80 80 100 30 100 85 8529F 85 70 55 90 98 90 100 100 100 100 35 100 60 10030F 90 80 40 .90 85 80 80 70 100 100 20 100 40 --31F 100 80 20 100 100 100 100 100 100 100 100 100 85 --32F 70 90 60 100 100 98 100 100 100 100 100 100 60 --33F 95 100 80 100 90 100 100 100 100 100 70 100 40 --35F 70 90 40 100 -- 100 100 100 100 100 98 100 30 --36F 85 100 35 100 -- 20 100 100 100 100 100 100 15 --39F 100 100 85 100 100 100 100 100 100 100 100 100 90 10040F 100 100 30 100 100 100 100 100 100 100 90 100 75 --41F 100 100 35 90 70 100 90 100 100 100 50 100 70 --42F 45 100 50 100 70 55 80 100 100 100 70 100 75 10043F 25 80 15 98 35 0 20 100 100 100 100 100 60 9544F 0 15 0 65 0 0 0 70 100 100 40 100 0 10045F 0 75 35 70 35 0 60 50 85 100 50 100 75 7050F -- 40 0 75 45 40 60 100 100 95 30 -- 60 100__________________________________________________________________________ (--) = Not tested.
TABLE VII-F__________________________________________________________________________Post-Emergence Multi-Weed Herbicidal ActivityApplication Rate-0.56 kg/haCmpd.No. DB FT ARG WG JG WO BSG AMG SESB VL SP MD YNS CB__________________________________________________________________________46F 25 35 20 50 35 35 0 20 75 100 35 95 -- 5047F -- 75 25 90 40 25 80 100 100 100 80 -- 75 10048F -- 50 35 80 35 40 0 75 100 85 15 -- 50 7549F -- 35 0 75 30 0 20 100 100 100 80 -- 25 8551F -- 35 0 80 35 20 70 50 95 95 25 -- 65 50__________________________________________________________________________ (--) = Not Tested.
The compounds of the present invention and their salts are useful as herbicides and can be applied in a variety of ways at various concentrations. In practice, the compounds or salts are formulated into herbicidal compositions, by admixture, in herbicidally effective amounts, with the adjuvants and carriers normally employed for facilitating the dispersion of active ingredients for agricultural applications, recognizing the fact that the formulation and mode of application of a toxicant may affect the activity of the materials in a given application. Thus, these active herbicidal compounds or salts can be formulated as granules of relatively large particle size, as wettable powders, as emulsifiable concentrates, as powdery dusts, as flowables, as solutions or as any of several other known types of formulations, depending upon the desired mode of application. These formulations may contain as little as about 0.5% to as much as about 95% or more by weight of active ingredient. A herbicidally effective amount depends upon the nature of the seeds or plants to be controlled and the rate of application varies from about 0.01 to approximately 10 pounds per acre, preferably from about 0.02 to about 4 pounds per acre.
Wettable powders are in the form of finely divided particles which disperse readily in water or other dispersants. The wettable powder is ultimately applied to the soil either as a dry dust or as a dispersion in water or other liquid. Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic diluents. Wettable powders normally are prepared to contain about 5% to about 95% of the active ingredient and usually also contain a small amount of wetting, dispersing, or emulsifying agent to facilitate wetting and dispersion.
Emulsifiable concentrates are homogeneous liquid compositions which are dispersible in water or other dispersant, and may consist entirely of the active compound or salt with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthal, isophorone and other non-volatile organic solvents. For herbicidal application, these concentrates are dispersed in water or other liquid carrier and normally applied as a spray to the area to be treated. The percentage by weight of the essential active ingredient may vary according to the manner in which the composition is to be applied, but in general comprises about 0.5% to 95% of active ingredient by weight of the herbicidal composition.
Granular formulations wherein the toxicant is carried on relatively coarse particles, are usually applied without dilution to the area in which suppression of vegetation is desired. Typical carriers for granular formulations include sand, fuller's earth, attapulgite clay, bentonite clays, montmorillonite clay, vermiculite, perlite and other organic or inorganic materials which absorb or which may be coated with the toxicant. Granular formulations normally are prepared to contain about 0.1% to about 25% of active ingredients which may include surface-active agents such heavy aromatic naphthas, kerosene or other petroleum fractions, or vegetable oils; and/or stickers such as dextrins, glue or synthetic resins.
Typical wetting, dispersing or emulsifying agents and adjuvants used in agricultural formulations include, for example, the alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols, esters and fatty amines; and other types of surface-active agents, many of which are available in commerce. The surface-active agent, when used, normally comprises from 0.1% to 30% by weight of the herbicidal composition.
Dusts, which are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers for the toxicant, are useful formulations for soil-incorporating application.
Pastes, which are homogeneous suspensions of a finely divided solid toxicant in a liquid carrier such as water or oil, are employed for specific purposes. These formulations normally contain about 5% to about 95% of active ingredient by weight, and may also contain small amounts of a wetting, dispersing or emulsifying agent to facilitate dispersion. For application, the pastes are normally diluted and applied as a spray to the area to be affected.
Other useful formulations for herbicidal applications include simple solutions of the active ingredient in a dispersant in which it is completely soluble at the desired concentration, such as water, acetone, alkylated naphthalenes, xylene and other organic solvents. Pressurized sprays, typically aerosols, wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.
The phytotoxic compositions of this invention can be applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray or by rope wick applications because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings, as a typical example, the dust and liquid compositions can be applied to the soil according to conventional methods and can be distributed in the soil to a depth of at least 1/2 inch below the soil surface. It is not necessary that the phytotoxic compositions be mechanically admixed with the soil particles since these compositions can also be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied to the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations. In the following examples the herbicidal compound can be substituted with the herbicidal salt of the compound.
__________________________________________________________________________General Formula with Ranges Specific Formula__________________________________________________________________________EMULSIFIABLE CONCENTRATE FORMULATIONSHerbicidal compound 5-55 herbicidal compound 24surfactant(s) 5-25 proprietary blend of oil- 10solvent(s) 20-90 soluble sulfonates and 100% polyoxyethylene ethers polar solvent 27 petroleum hydrocarbon 39 100%WETTABLE POWDER FORMULATIONSherbicidal compound 3-90 herbicidal compound 80wetting agent 0.5-2 sodium dialkyl naphthalene 0.5dispersing agent 1-8 sulfonatediluent(s) 8.5-87 sodium lignosulfonate 7 100% attapulgite clay 12.5 100%EXTRUDED GRANULAR FORMULATIONSherbicidal compound 1-20 herbicidal compound 10binding agent 0-10 lignin sulfonate 5diluent(s) 70-99 calcium carbonate 85 100% 100%FLOWABLE FORMULATIONSherbicidal compound 20-70 herbicidal compound 45surfactant(s) 1-10 polyoxyethylene ether 5suspending agent(s) 0.05-1 attagel 0.05antifreeze agent 1-10 propylene glycol 10antimicrobial agent 1-10 1,2-benzisothiazoline-3-one 0.03antifoam agent 0.1-1 silicone defoamer 0.02solvent 7.95-77.85 water 39.9 100% 100%__________________________________________________________________________
When salts are used as the active ingredient in the herbicidal compositions of this invention it is recommended to use salts that are agriculturally acceptable.
The phytotoxic compositions of this invention can also contain other additives, for example, fertilizers, other herbicides and other pesticides, used as adjuvant or in combination with any of the above-described adjuvants. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate.

Number	Name	Date
3950420	Sawaki et al.	Apr 1976
3989737	Sawaki et al.	Nov 1976
4075239	Sawaki et al.	Feb 1978
4209532	Wheeler	Jun 1980
4227919	Gray et al.	Nov 1980
4350705	Hamano et al.	Sep 1982
4351666	Koerwer	Sep 1982
4422870	Wheeler	Dec 1983
4440566	Luo	Apr 1984
4659372	Wheeler	Apr 1987
4681621	Lee et al.	Jul 1987
4715882	Raju	Dec 1987
4780127	Michaely et al.	Oct 1988
4781751	Chin	Nov 1988
4816066	Michaely et al.	Mar 1989

Number	Date	Country
0007243	Jan 1980	EPX
0017195	Oct 1980	EPX
0090262	Oct 1983	EPX
137963	Apr 1985	EPX
0162336	Nov 1985	EPX
13750-76	Jul 1974	JPX
662543	May 1979	SUX
2110673	Jun 1983	GBX

	Number	Date
Parent	772593	Sep 1985
Parent	634408	Jul 1984
Parent	587331	Mar 1984
Parent	532869	Sep 1983
Parent	464251	Feb 1983
Parent	361658	Mar 1982

Certain 2-(2-chloro-3-alkoxy-4-substituted benzoyl)-5-methyl-5-1,3-cyclohexanediones as herbicides

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Entry
Akhrem et al., "A New Simple Synthesis of 2-Acylcyclohexane-1, 3-Diones", Communications, Georg Thieme Publishers, 1978, pp. 925-927.
Chemical Abstracts, vol. 85 (1976), Sawaki et al., "2-(Amino-Methylene)-1,3-Cyclohexandiones", p. 423, Abstract #85:5280f.