Herbicidal cyclohexane-1,3-dione derivatives

Claim 2

A compound of formula I: wherein: R 1 is selected from the group consisting of: hydrogen; C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; substituted C 1 to C 6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of C 1 to C 6 alkoxy, C 1 to C 6 alkylthio, (C 1 to C 6 alkoxy)carbonyl, phenyl and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; C 1 to C 6 (alkyl) sulfonyl; benzene sulfonyl; substituted benzenesulfonyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano,C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; an acyl group; and an inorganic or organic cation; R 2 is selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 haloalkenyl; C 2 to C 6 alkynyl; C 2 to C 6 haloalkynyl; substituted C 1 to C 6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of halogen, C 1 to C 6 alkoxy, C 1 to C 6 alkylthio, phenyl and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; R 3 is selected from the group consisting of: C 1 to C 6 alkyl; C 1 to C 6 fluoroalkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; and phenyl; and n is an integer chosen from 2 to 5.

Claim 3

A compound according to claim 1 wherein: R 1 is selected from the group consisting of: hydrogen; C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; substituted C 1 to C 6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of C 1 to C 6 alkoxy, C 1 to C 6 alkylthio, phenyl and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alky l t hio; C 1 to C 6 (alkyl) sulfonyl; benzene sulfonyl; substituted benzenesulfonyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; C 2 to C 6 alkanoyl; benzoyl and substituted benzoyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; 2-furoyl; 3-furoyl; 2-thenoyl; 3-thenoyl; and an inorganic or an organic cation selected from the alkali metal ions, the alkaline earth metal ions, transition metal ions and the ammonium ion R 4 R 5 R 6 R 7 N ⊕ wherein R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of: hydrogen; C 1 to C 10 alkyl; substituted C 1 to C 10 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of hydroxy, halogen and C 1 to C 6 alkoxy; phenyl; benzyl; and the groups substituted phenyl and substituted benzyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; R 2 is selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 haloalkenyl; C 2 to C 6 alkynyl; C 2 to C 6 haloalkynyl; substituted C 1 to C 6 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of halogen, C 1 to C 6 alkoxy, C 1 to C 6 alkylthio, phenyl and substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; R 3 is selected from the group consisting of: C 1 to C 6 alkyl; C 1 to C 6 fluoroalkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; and phenyl; and n is an integer chosen from 2 to 5.

Claim 4

A compound according to claim 1 or claim 2 wherein: R 1 is selected from the group consisting of hydrogen, C 1 to C 6 alkyl, C 2 to C 6 alkenyl, C 2 to C 6 alkynyl, C 2 to C 6 alkanoyl, C 1 to C 6 alkyl substituted with C 1 to C 6 alkoxy, C 1 to C 6 alkylthio, phenyl or substituted phenyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio, benzoyl or substituted benzoyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio, C 1 to C 6 (alkyl)sulfonyl and benzenesulfonyl or substituted benzenesulfonyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio, and the group M wherein M is an alkali metal ion: R 2 is selected from the group consisting of C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 2 to C 6 alkenyl, C 2 to C 6 alkynyl and C l to C 6 alkyl substituted with C 1 to C 6 alkoxy, C l to C 6 alkylthio, phenyl or substituted phenyl wherein the benzene ring is substituted with from one to three substitutents selected from the group consisting of halogen, nitro, cyano, C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 1 to C 6 alkoxy and C 1 to C 6 alkylthio; R 3 is selected from the group consisting of C 1 to C 6 alkyl, C 2 to C 6 alkenyl and C 2 to C 6 alkynyl; n is an integer chosen from 2 to 5.

Claim 5

A compound according to claim 1 or claim 2 wherein: R 1 is selected from the group consisting of: hydrogen; C 2 to C 6 alkanoyl; benzoyl and substituted benzoyl wherein the benzene ring is substituted with from 1 to 3 substituents selected from the group consisting of halogen, nitro, C 1 to C 6 alkyl and C 1 to C 6 alkoxy; and an inorganic or organic cation selected from the alkali metal ions, the alkaline earth metal ions, transition metal ions and the ammonium ion R 4 R 5 R 6 R 7 N ⊕ wherein R 4 , R 5 , R 6 and R 7 are independently selected from the group consisting of: hydrogen; C 1 to C 10 alkyl; and substituted C 1 to C 10 alkyl wherein the alkyl group is substituted with a substituent selected from the group consisting of hydroxy and C 1 to C 6 alkoxy; R 2 is selected from the group consisting of: C 1 to C 6 alkyl; C 2 to C 6 alkenyl; C 2 to C 6 alkynyl; C 1 to C 6 haloalkyl; C 2 to C 6 haloalkenyl; C 1 to C 6 alkyl substituted with C 1 to C 6 alkoxy; C 1 to C 6 alkyl substituted with C 1 to C 6 alkylthio; and benzyl and substituted benzyl wherein the benzene ring is substituted with from one to three substituents selected from the group consisting of halogen, nitro and C 1 to C 6 alkyl; R 3 is selected from the group consisting of C 1 to C 6 alkyl; and n is an integer, chosen from 2 to 5.

Claim 6

A compound according to any one of claims 1, 2 or 4 wherein: R 1 is selected from the group consisting of hydrogen, acetyl, tertiary butyryl, benzoyl, halobenzoyl, methylbenzoyl, methoxybenzoyl, nitrobenzoyl, trimethylbenzoyl, dinitrobenzoyl, the cations of the alkali metals sodium and potassium; the cations of the alkaline earth metals magnesium, calcium and barium, the cations of the transition metals manganese, copper, zinc, iron, nickel, cobalt and silver, the ammonium ion, and the tri- and tetra- alkyl ammonium ions wherein alkyl is selected from C 1 to C 6 alkyl and C 1 to C 6 hydroxyalkyl; R 2 is selected from the group consisting of ethyl, n-propyl, n-butyl, allyl, propargyl, 2-fluoroethyl, 2-chloroallyl, methylthiomethyl, benzyl, halobenzyl, methylbenzyl and nitrobenzyl; R 3 is selected from the group consisting of methyl ethyl and n-propyl; and n is an integer selected from 2 to 5.

Claim 7

A compound according to any one of claims 1 to 5 inclusive wherein: R 1 is selected from the group consisting of hydrogen, benzoyl and the cations of the alkali metals sodium and potassium; R 2 is selected from the group consisting of ethyl, n-propyl and allyl; R 3 is selected from ethyl and n-propyl; and n is an integer selected from 3 to 5.

Claim 8

A compound according to any one of claims 1 to 6 inclusive of formula wherein: R 1 is selected from hydrogen,sodium and potassium; R 2 is selected from ethyl and allyl; and R 3 is selected from ethyl and n-propyl.

Claim 9

A compound according to any one of claims 1 to 6 inclusive of formula wherein: R 1 is selected from hydrogen, sodium and potassium; R 2 is selected from ethyl and allyl; and R 3 is selected from ethyl and n-propyl.

Claim 10

A compound according to any one of claims 1 to 6 inclusive of formula wherein: R 1 is selected from hydrogen, sodium and potassium; R 2 is selected from ethyl and allyl; and R 3 is selected from ethyl and n-propyl.

Claim 11

A compound according to any one of claims 1 to 6 inclusive selected from the group consisting of: 2-[1-(ethoxyimino)propyl]-3-hydroxy-5 mesitylcyclohex-2-en-1-one; 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,6-tetramethylphenyl)cyclohex-2-en-1-one; 2-[1-(ethoxyimino)butyl]-3-hydroxy-5-mesitylcyclohex-2-en-1-one; 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-1-one; 2-[1-(ethoxyimino)butyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-l-one; 2-[1-(ethoxyimino)propyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-I-one sodium salt; and 2-[1-ethoxyimino)butyl]-3-hydroxy-5-(2,3,4,5,6-pentamethylphenyl)cyclohex-2-en-l-one sodium salt.

Claim 12

A compound of formula IX wherein n is as defined according to any one of claims 1 to 6 inclusive.

Claim 13

A compound of formula XIII wherein n and R are as defined according to any one of claims 1 to 6 inclusive.

Claim 14

A herbicidal composition comprising as active ingredient a compound as defined according to any one of claims 1 to 10 inclusive and a carrier therefor.

Claim 15

A process for severely damaging or killing unwanted plants which process comprises applying to said plants, or to the growth medium of said plants, an effective amount of a compound as defined according to any one of claims 1 to 10 inclusive or an effective amount of a composition as defined according to claim 13.

Claim 16

A process for selectively controlling the growth of monocotyledonous weeds in dicotyledonous crops which process comprises applying to said crop, or to the growth medium of said crop, a compound as defined according to any one of claims 1 to 10 inclusive or a composition as defined according to claim 13 in an amount sufficient to severely damage or kill said weeds but insufficient to substantially damage said crop.

Claim 17

A process for selectively controlling the growth of monocotyledonous weeds in cultivated crops which process comprises applying to said crop or to the growth medium of said crop a compound as defined according to any one of claims 1 to 10 inclusive or a composition as defined according to claim 13 in an amount sufficient to severely damage or kill said weeds but sufficient to substantially damage said crop.

Claim 18

A process according to any one of claims 14 to 16 inclusive wherein the compound is applied at a rate in the range of from 0.005 to 20 kilograms per hectare.

Claim 19

A process for the synthesis of a compound of formula I as defined according to any one of claims 1 to 10 inclusive which process comprises; a) reacting a benzaldehyde derivative of formula V with acetone to give a ketone derivative of formula VI and reacting the ketone derivative of formula VI with a malonic acid ester of formula VII,wherein R is C 1 to C 6 alkyl, to give a 5-(substituted phenyl)-cyclohexane-1,3-dione derivative of formula IX; b) acylating the 5-(substituted phenyl)cyclohexane-1,3-dione derivative of formula IX with an acid anhydride of formula XIV or an acid halide of formula XV to give a 2-acyl-5-(substituted phenyl)cyclohexane-1,3-dione derivative of formula XIII; c) reacting the 2-acyl-5-(substituted phenyl)-cyclohexane-l,3-dione derivative of formula XIII with an alkoxyamine derivative of formula XVII to give a compound of the invention of formula II (formula I wherein R 1 = H ); and optionally d) reacting the compound of the invention of formula II with a compound of formula XX to give a compound of the invention of formula I

Claim 20

A compound of formula I as defined according to any one of claims 1 to 10 inclusive substantially as herein described with reference to any one of Examples 1 to 21 inclusive.

Claim 21

20 A composition as defined according to claim 13 substantially as herein described with reference to any one of Examples 22 to 26 inclusive.

Claim 22

A process as defined according to any one of claims 14 to 16 inclusive substantially as herein described with reference to any one of Examples 23 to 26 inclusive.

Claim 23

A process as defined according to claim 18 substantially as herein described with reference to any one of Examples 1 to 21 inclusive.