WO1993010081A1

WO1993010081A1 - Herbicidal 2(substituted oxime)-cyclohexan-1,3-dione derivatives

Info

Publication number: WO1993010081A1
Application number: PCT/AU1992/000612
Authority: WO
Inventors: Andris Juris Liepa; Albert Hoffman; Roland Henry Nearn; Chin Thien Bui
Original assignee: Dunlena Pty. Limited
Priority date: 1991-11-15
Filing date: 1992-11-13
Publication date: 1993-05-27
Also published as: PT101060A; CN1073675A; JPH07500841A; TW221367B

Abstract

Novel compounds of formula (1), and isomeric and/or tautomeric forms thereof, wherein A is C1-C3 alkylene or C3 alkenylene, each optionally substituted with 1 to 4 C1-C3 alkyl substituents; X is oxygen or a single bond; and R1 to R9 are various sbustituents. Agriculturally useful compositions of these compounds and methods of using these compounds as pre-emergent and/or post-emergent herbicides, and plant growth regulators.

Description

HERBICIDAL 2(SUBSTITUTED OXIME )-CYCLOHEXAN-1 ,3-DIONE DERIVATIVES

The present invention relates to organic compounds having herbicidal properties and plant growth regulating properties; to herbicidal compositions and processes utilising such compounds and to plant growth regulating compositions and processes utilising such compositions.

The use of certain cyclohexane-1,3-dione derivatives as grass herbicides is known in the art. Thus, for example, the compendium "The Pesticide Manual, 8th Edition" (C.R. Worthing Editor, The British Crop Protection Council, Thornton Heath, UK) describes the cyclohexane-1,3-dione derivatives known commercially as Alloxydim sodium methyl (E)-(RS)-3-[1-(alloxyimino)butyl]-4-hydroxy-6,6-dimethyl-2- oxocyclohex-3-ene carboxylate, Cycloxydim (RS)-2-[1-(ethoxyimino)butyl]-3-hydroxy-5-thian-3-ylcyclohex-2-enone and Sethoxydim (RS)-(ZE)-2-(1-ethoxyiminobutyl)-5-[2-(ethylthio)propyl]-3-hydroxycyclohex-2-enone as selective post-emergent herbicides. Alloxydim and Sethoxydim have been disclosed in United States Patent No. 4,011,256 and Australian Patent Application No. 35314/78 respectively.

United States Patent 4,440,566 in the name of Chevron Research Company discloses herbicidal haloalkyl, haloalkenyl and haloaryl substituted 2-[1-oxyamino)-alkylidene]-cyclohexane-1,3-diones similar to Alloxydim and Sethoxydim. In particular it discloses compounds with chloroallyl, halobenzyl, or

trifluoromethylbenzyl substituents on the oxyamino group.

United States Patent 5,022,914 in the name of BASF AG claims a range of

cyclohexanone oxime ether compounds similar to those of Formula 1 below except that the substituent on the oxyamino group consists of an optionally substituted phenyl connected by a C₄ alkylene or alkenylene bridging chain to the ether oxygen, and that the cyclohexanone ring carries a single substituent in the 4-position. It is claimed that these compounds are herbicides with high selectivity for grasses. In a recently published European Patent Application EP 0 456 069 Al, (13 November 1991) BASF AG claim herbicides differing from those of US 5,022,914 in that the bridging chains are C₃, C₅ and C₆ alkylene or alkenylene. The single substituent claimed on 4-position of the cyclohexanone ring is selected from C₁-C₄ alkoxy- C₁-C₄ alkyl, C₁-C₄ alkythio-C₁-C₆ -alkyl, optionally substituted C₃-C₇ cycloalkyl, an optionally substituted five membered saturated heterocycle containing one or two heteroatoms selected from O or S, an optionally substituted saturated or unsaturated 6 to 7 membered heterocycle containing one or two heteroatoms selected from O or S, an optionally substituted five membered heteroaromatic containing one or two nitrogen atoms and one oxygen or sulphur atom, or phenyl or pyridyl which may be substituted with a substituent selected from halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy,

C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl and C₁-C₄ haloalkoxy; these compounds are excluded from this invention. Despite the broad claim, EP 0 456 069 specifically discloses as pendent substituents at the 4-position of the cyclohexanone ring only ethylthiopropyl, cyclohexyl, cyclohexenyl, or one of a series of heterocyclic rings, e.g. tetrahydrofuranyl, tetrahydrothiophenyl, dioxolanyl, dithiolanyl,

dihydropyranyl, tetrahydropyranyl, 1,2-thiazolyl, tetrahydropyranyl,

tetrahydrothiopyranyl. We have discovered that compounds similar to those described in US 4,440,566,

US 5,022,914 and EP 0 456 069 in which the oxime capping group includes a phenyl or substituted' phenyl group other than those disclosed in US 4,440,566, US 5,022,914 or EP 0 456 069 are highly active pre-emergent and/or post-emergent herbicides or plant growth regulators and are particularly useful for controlling certain grass weeds in dryland and paddy rice.

Accordingly, this invention provides novel compounds of Formula (1), agriculturally useful compositions of these compounds and methods of using these compounds as pre-emergent and/or post-emergent herbicides, and plant growth regulators:

wherein

A is selected from the group C₁-C₃ alkylene and C₃ alkenylene each optionally substituted with 1-4 independently selected C₁-C₃ alkyl substituents;

X is selected from the group O, and a single bond;

R¹ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,

C₅-C₆ cycloalkyl, C₅-C₆ cycloalkenyl, alkanoyl, aroyl, C₁-C₄ alkylsulphonyl, arylsulphonyl, benzenesulfonyl, C₁-C₄ alkylcarbonyl, C₂-C₈ alkoxyalkyl, C₂-C₈ alkylthioalkyl, C₁-C₁₀ phenylalkyl, M, and phenyl optionally substitute with 1-3 substituents selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl, amino, and C₁-C₄ haloalkoxy;

R² is selected from the group C₁-C₆ alkyl, C₂-C₈ alkenyl, C₂-C₆ alkynyl, C₁-C₄ haloalkyl, C₁-C₄ alkylthio, C₃-C₆ cycloalkyl, C₅-C₆ cycloalkenyl, C₂-C₈ alkoxyalkyl, C₂-C₈ alkylthioalkyl, C₁-C₄ alkyl substituted with a substituent selected from the group consisting of phenyl, phenoxy and thiophenoxy wherein the aromatic ring of said substituents is optionally substituted with 1- substituents selected from halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, amino, C₁-C₄ haloalkyl and C₁-C₄ haloalkoxy, and phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl, amino, and C₁-C₄ haloalkoxy; R³and R⁴ are independently selected from the group H, C₁-C₄ alkyl, C₁-C₄ alkoxy, and cyano, or one of R³ or R⁴ can independently be taken together with one of R₅ or R₆ and the ring carbons to which they are attached to form a 5- or 6- membered ring;

R⁵ and R⁶ are independently selected from the group H, C₁-C₆ alkyl, C₂-C₄

alkenyl, C₂-C₈ alkylthioalkyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₃-C₆ cycloalkyl wherein the alkyl, alkenyl and cycloalkyl groups are optionally substituted with 1-3 substituents independently selected from the group consisting of OR¹², NR¹³R¹⁴, NR¹⁵CO(C₁-C₄ alkyl), NR¹⁸SO₂(C₁-C₄ alkyl), C(OR¹⁶)(OR¹⁷)R²², C(SR¹⁹)(SR²⁰)R²³, C₁-C₄ alkoxycarbonyl and phenyl optionally substituted with a substituent selected from halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl and

C₁-C₄ haloalkoxy;

or

R⁵ and R⁶ together with the ring carbon to which they are attached form a saturated or an unsaturated 3- to 7-membered carbocyclic ring, or a saturated or an unsaturated 5- to 7-membered heterocyclic ring containing 1-3 heteroatoms selected from the group consisting of 0-3 nitrogen, 0-2 oxygen and 0-2 sulphur atoms; the carbocyclic or heterocyclic ring being optionally substituted with 1-4 substituents independently selected from the group halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylcarbonyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ alkoxycarbonyl, -COOH, C₂-C₈ alkoxyalkyl, C₂-C₈ alkylthioalkyl, and phenyl which is optionally substituted with a substituent selected from halogen, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkyl, nitro, cyano and C₁-C₄ haloalkoxy; one of the carbon atoms of the carbocyclic and heterocyclic ring being optionally in the form of a carbonyl group or its corresponding dimethyl, diethyl or ethylene or

propylene ketal; R⁷, R⁸ and R⁹ are independently selected from the group H; halogen; C₁-C₄ alkyl;

C₁-C₄ alkoxy; C₁-C₄ alkylthio; C₁-C₄ alkylsulphinyl; C₁-C₄ alkylsulphonyl, C₁-C₄ haloalkyl; C₁-C₄ haloalkoxy; nitro; cyano; C₁-C₄ alkoxycarbonyl; C₁-C₄ alkylaminocarbonyl; C₂-C₆ dialkylaminocarbonyl; aminocarbonyl; amino; C₁-C₄ alkylamino; and C₂-C₆ dialkylamino; or a group selected from benzenesulphonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio, phenylamino and phenyl group, said group optionally substituted with 1-3 substituents independently selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, and CF₃;

M is selected from the group Li⁺, Na⁺, K⁺, NH₄ ⁺, and N(R¹¹)₄ ⁺ where R¹¹ is C₁-C₄ alkyl;

R¹² is selected from the group H, C₁-C₄ alkyl ,benzyl, CO(C₁-C₄ alkyl), and CO₂(C₁-C₄ alkyl);

R¹³, R¹⁵, R¹⁸, R²² and R²³ are independently selected from H and C₁-C₃ alkyl;

R¹⁴, R¹⁶, R¹⁷, R¹⁹ and R²⁰ are independently selected from C₁-C₃ alkyl;

R¹⁶ and R¹⁷ can be taken together as -(CH₂)₂- or -(CH₂)₃-; and

R¹⁹ and R²⁰ can be taken together as -(CH₂)₂- or -(CH₂)₃-; provided that:

a) when A is CH₂, and X is a single bond, and R¹ is H, C₁-C₄ alkylcarbonyl, arylcarbonyl or M, and R² is C₁-C₆ alkyl or phenyl, and R³ and R⁴ are H, and R⁵ and R⁶ are H, C₁-C₃ alkyl or C₂-C₈ alkylthioalkyl, then at least one of R⁷, R⁸ and R⁹ is other than H, CF₃, nitro or halogen; b) when A is C₂-C₃ alkylene, X is O, R¹ is H, R² is C₃ alkyl, R³ and R⁴ are H, R⁵ and R⁶ are CH₃, then at least one of R⁷, R⁸ and R⁹ is other than H; c) when A is CH₂, or C₃ alkylene or C₃ alkenylene optionally substituted with 1-3 C₁-C₃ alkyl groups, and X is a single bond, and R¹ is H, and R³ an R⁴ are both H, and one of R⁵ or R⁶ is hydrogen and the other is

C₂-C₈ alkylthioalkyl, C₁-C₄ alkyl substituted with O(C₁-C₄ alkyl), or C₃-C₆ cycloalkyl optionally substituted with OR¹² where R¹² is C₁-C₄ alkyl or H, then at least one of R⁷, R⁸ or R⁹ are other than H, halogen, nitro, cyano, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₂-C₄ haloalkoxy,

C₁-C₄ alkoxycarbonyl or optionally substituted phenyl. In the above definitions, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl", denotes straight chain or branched alkyl, e.g. methyl, ethyl, n-propyl, isopropyl or the different butyl, pentyl or hexyl isomers. "Alkoxy" denotes straight chain or branched alkoxy, e.g. methoxy, ethoxy, n-propoxy, isopropyloxy, and the different butyloxy isomers.

"Alkenyl" denotes groups formed from straight chain or branched alkenes, e.g. vinyl, 1-propenyl, 2-propenyl, 3-propenyl, etc.

"Alkynyl" denotes groups formed from straight chain or branched alkynes, e.g., ethynyl, 1-propynyl, 2-propynyl, and the different butynyl isomers.

"Alkylsulphonyl" denotes methylsulphonyl, ethylsulphonyl, propylsulphonyl, and the different butylsulphonyl isomers.

"Alkylthio", "alkylsulphinyl", "alkylamino", etc. are defined in an analogous manner to the above. "Cycloalkyl" denotes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.

The term "halogen", either alone or in compound words such as "haloalkyl", denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl" said alkyl may be partially halogenated or fully substituted with halogen atoms which may be the same or different. Examples of haloalkyl include CH₂CH₂F, CF₂CF₃ and CH₂CHFCl. "Alkylcarbonyl" denotes acetyl, propionyl, and the different butyryl isomers.

"Alkoxycarbonyl" denotes methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and the different butoxycarbonyl isomers.

The total number of carbon atoms in a substituent group is indicated by the C_i-C_j prefix where i and j are numbers from 1 to 10. For example, C₂-C₃ alkylthioalkyl would designate -CH₂SCH₃, -CH₂SC₂ -CH₂CH₂SCH₃ or -CH(CH₃)SCH₃, and C₂-C₅ alkoxyalkyl would represent -CH₂OCH₃ through to -(CH₂)₄OCH₃ or

-CH₂O(CH₂)₃CH₃ and the various structural isomers embraced therein.

"Alkylene" denotes methyene (-CH₂-), ethylene (-CH₂CH₂-), propylene and butylene; alkenylene denotes -CH=CHCH₂-, -CH=CHCH₂CH₂-, and

-CH₂CH=CHCH₂-.

Groups of compounds of general formula (1) which are preferred for reasons including ease of synthesis and greater herbicidal efficacy, include the following:

(1) Compounds of Formula 1 wherein

R¹ is H, alkylsulphonyl, arylsulphonyl or M; and R² is C₁-C₄ alkyl,

C₁-C₄ haloalkyl, C₁-C₄ alkenyl or C₂-C₄ alkynyl .

(2) Compounds of (1) above wherein

A is C₁-C₂ alkylene or _C3-C₄ alkenylene optionally substituted with CH₃ or C₂H₅;

R⁷, R⁸ and R⁹ are independently H, Cl, Br, F, C₁-C₃ alkyl, C₁-C₃ alkoxy, C₁-C₃ alkylthio, C₁-C₃ haloalkyl, C₁-C₃ haloalkoxy, nitro, cyano or

C₁-C₃ alkoxycarbonyl; or benzenesulphonyl, benzoyl, benzyl, benzyloxy, phenoxy, phenylthio or phenylamino optionally substituted with 1-3

substituents selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, or CF₃. (3) Compounds of (2) above wherein X is O (4) Compounds of (2) above wherein X is a single bond.

(5) Compounds of (4) above wherein:

A is -CH₂-, -CH₂CH₂-, -CH₂CH=CH- or -CH₂CMe=CH-;

R¹ is H, Li+, Na +, or K+;

R² is CH₃, C₂H₅, n-C₃H₇ or n-C₄H₉ ;

R³ and R⁴ are independently H, CH₃ or C₂H₅ ; and

R⁷ R⁸ and R⁹ are independently H, Cl, Br, F, CH₃, C₂H₅, OCH₃, OC₂H₅, SCH₃, SC₂H₅, CF₃, CHF₂, CF₂CF₃, OCHF₂, OCF₃, OCH₂CF₃, NO₂, CN CO₂CH₃ Ph, SO₂Ph, COPh, CH₂Ph, OCH₂Ph, OPh, SPh, NHPh or N(Me)Ph.

(6) Compounds of (4) above wherein R⁵ and R⁶ are independently C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylthio or C₂-C₆ alkylthioalkyl.

(7) Compounds of (4) above wherein R⁵ and R⁶ together with the carbon to which they are attached form a saturated or unsaturated 5-, 6- or 7-membered carbocyclic ring which is optionally substituted with 1-4 CH₃ groups.

(8) Compounds of (7) above wherein:

A is -CH₂-, -CH₂CH₂- or CH₂CH=CH- ; R¹ is H, Li+, Na+ or K +; R² is CH₃, C₂H₅, n-C₃H₇ or n-C₄H₉;

R³ and R⁴ are independently H or CH₃; and

R⁷, R⁸ and R⁹ are independently H, Cl, Br, F, CH₃, C₂H₅, OCH₃, OC₂H₅, SCH₃, SC₂H₅, CF₃, CHF₂ CF₂CF₃, OCHF₂, OCF₃, OCH₂CF₃, NO₂, CN, CO₂CH₃, Ph, SO₂Ph, COPh, CH₂Ph, OCH₂Ph, OPh, SPh, NHPh or N(Me)Ph.

(9) Compounds of (4) above wherein:

R⁵ and R⁶ together with the carbon to which they are attached form a saturated or unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1-2 heteroatoms selected from the group consisting of 0-2 nitrogen, 0-1 oxygen and 0-2 sulphur atoms; said ring is optionally substituted with 1-4 CH₃ groups.

(10) Compounds of (9) above wherein:

A is -CH₂-, -CH₂CH₂- or -CH₂CH=CH- ;

R¹ is H, Li +, Na+ or K+;

R² is CH₃ C₂H₅, n-C₃H₇ or n-C₄H₉;

R³ and R⁴ are independently H, CH₃ or C₂H₅ ; and

R⁷, R⁸ and R⁹ are independently H, Cl, Br, F, CH₃, C₂H₅, OCH₃, OC₂H₅, SCH₃, SC₂H₅, CF₃, CHF₂, CF₂CF₃, OCHF₂, OCF₃, OCH₂CF₃, NO₂, CN, CO₂CH₃, Ph, SO₂Ph, COPh, CH₂Ph, OCH₂Ph, OPh, SPh, NHPh or N(Me)Ph. Examples of compounds within the scope of this invention are given in the Table 1 which follows.

Table 1

Formula 1, R¹ = R⁹=H, X= Single bond

A R² R³ R⁴ R⁵ R⁶ R⁷ R⁸

1.1 CH₂ Pr H H H H 4-Ph H

1.2 CH₂ Pr H H H H 4-(4-F)Ph H

1.3 CH₂ Pr CO₂Me H H H 4-(4-F)Ph H 1.4 CH₂ Pr CO₂Et H H H 4-(4-F)Ph H

15 CH₂ Pr Me H H H 4-Ph H

1_.6 CH₂ Pr Me H H H 4-(4-F)Ph H

1.7 CH₂-CH=CH Pr Me H H H 4-F H 1.8 CH₂-CH=CH Pr Me H H H 2-F 4-Cl 1.9 CH₂-CH=CH Pr Me H H H 2-Cl 4-F

1.10 CH.-CH=CH Pr Me H H H 2-Cl 4-Cl 1.11 CH₂-CH=CH Pr Me H H H 2-F 4-F

1.12 CH₂ Pr Me CO₂Me H H 4-Ph H

1.13 CH₂ Pr Me CO₂Me H H 4-(4-F)Ph H

1.14 CH₂ Pr Me CO₂Et H H 4-(4-F)Ph H

1 15 CH₂ Pr H H Me H 4-Ph H

1_.16 CH₂ Pr H H Me H 4-(4-F)Ph H

1.17 CH₂-CH=CH Pr H H H H 4-F H

1.18 CH₂-CH=CH Pr H H H H 2-F 4-Cl 1.19 CH₂-CH=CH Pr H H H H 2-Cl 4-F

1.20 CH₂-CH=CH Pr H H H H 2-Cl 4-Cl

1.21 CH₂-CH=CH Pr H H H H 2-F 4-F

1.22 CH₂ Pr CO₂Me H Me H 4-Ph H

1.23 CH₂ Pr CO₂Me H Me H 4-(4-F)Ph H 1.24 CH₂ Pr CO₂Et H Me H 4-(4-F)Ph H

1.25 CH₂ Pr Me H Me H 4-Ph H

1.26 CH₂ Pr Me H Me H 4-(4-F)Ph H

1.27 CH₂-CH=CH Pr Me H Me H 4-F H

1.28 CH₂-CH=CH Pr Me H Me H 2-F 4-Cl 1.29 CH₂-CH=CH Pr Me H Me H 2-Cl 4-F

1.30 CH₂-CH=CH Pr Me H Me H 2-Cl 4-Cl

1.31 CH₂-CH=CH Pr Me H Me H 2-F 4-F

1.32 CH₂ Pr Me CO₂Me Me H 4-(4-F)Ph H

1.33 CH₂-CH=CH Pr H H Me Me 4-Ph H 1.34 CH₂ Me H H Me Me 4-Ph H

Et H H Me Me 4-Ph H

136 CH₂ Me H H Me Me 4-(4-F)Ph H

137 CH₂ Et H H Me Me 4-(4-F)Ph H

1 38 CH₂ Pr H H Me Me 3-Ph H 139 CH₂ Pr H H Me Me 4-Ph H

1 40 CH₂ Pr H H Me Me 2-F 4-Ph

1 41 CH₂ Pr H H Me Me 3-F 4-Ph A R² R³ R⁴ R⁵ R⁶ R⁷ R⁸

1.42 CH₂ Pr H H Me Me 4-F 3-Ph

1.43 CH₂ Pr H H Me Me 4-(4-F)Ph H

1.44 CH₂ -CH=CH Pr H H Me Me 4-F H

1.45 CH₂ -CH=CH Pr H H Me Me 2-F 4-Cl

1.46 CH₂ -CH=CH Pr H H Me Me 2-Cl 4-F

1.47 CH₂ -CH=CH Pr H H Me Me 2-Cl 4-Cl

1.48 CH₂ -CH=CH Pr H H Me Me 2-F 4-F

1.49 CH₂ Pr H H Me Me 4-(4-Ph)Ph H

1.50 CH₂ Pr CO₂Me H Me Me 4-Ph H

1.51. CH₂ Pr CO₂Et H Me Me 4-Ph H

1.52 CH₂ Pr CO₂Me H Me Me 4-(4-F)Ph H

1.53 CH₂ Pr CO₂Et H Me Me 4-(4-F)Ph H

1.54 CH₂ Pr H H Me Et 4-Ph H

1.55 CH₂ Pr H H Me Et 4-(4-F)Ph H

1.56 CH₂-CH=CH Pr H H Me Et 4-F H

1.57 CH₂- CH=CH Pr H H Me Et 2-F 4-Cl

1.58 CH₂- CH =CH Pr H H Me Et 2-Cl 4-F

1.59 CH₂- CH =CH Pr H H Me Et 2-Cl 4-Cl

1.60 CH₂- CH =CH Pr H H Me Et 2-F 4-F

1.61 CH₂ Pr H H Me iso-Pr 4-Ph H

1.62 CH₂ Pr H H Me iso-Pr 4-(4-F)Ph H

1.63 CH₂ Pr Me H Me Me 4-Ph H

1.64 CH₂ Pr Me H Me Me 4-(4-F)Ph H

1.65 CH₂ Pr Me CO₂Me Me Me 4-Ph H

1.66 CH₂ Pr Me CO₂Et Me Me 4-(4-F)Ph H

1.67 CH₂ Pr Me CO₂Me Me Me 4-Ph H

1.68 CH₂ Pr Me CO₂Et Me Me 4-(4-F)Ph H

1.69 CH₂ Pr Me H Me Et 4-(4-F)Ph H

1.70 CH₂ Pr Me H Me iso-Pr 4-Ph H

1.71 CH₂ Pr Me Me Me Me 3-Ph H

1.72 CH₂ Pr Me Me Me Me 4-Ph H

1.73 CH₂ Me Me Me Me Me 4-(4-F)Ph H

1.74 CH₂ Pr Me Me Me Et 4-Ph H

1.75 CH₂ Pr Me Me Me iso-Pr 4-Ph H

1.76 CH₂ Pr H H Et H 4-Ph H

1.77 CH₂- CH= CH Pr H H Et H 4-Ph H

1.78 CH₂ Pr H H Et H 4-(4-F)Ph H

1.79 CH₂-CH=CH Pr H H Et H 4-F H

1.80 CH₂-CH= CH Pr H H Et H 2-F 4-Cl

1.81 CH₂-CH=CH Pr H H Et H 2-Cl 4-F

1.82 CH₂-CH=CH Pr H H Et H 2-Cl 4-Cl

1.83 CH₂-CH=CH Pr H H Et H 2-F 4-F

1.84 CH₂ Pr CO₂Me H Et H 4-(4-F)Ph H

1.85 CH₂ Pr H H Pr H 4-Ph H

1.86 CH₂-CH=CH Pr H H Pr H 4-Ph H A R² R³ R⁴ R⁵ R⁶ R⁷ R⁸

1.87 CH₂ Pr H H Pr H 4-(4-F)Ph H

1.88 CH₂-CH=CH Pr H H Pr H 4-F

1.89 CH₂-CH=CH Pr H H Pr H 2-F 4-Cl

1.90 CH₂-CH=CH Pr H H Pr H 2-Cl 4-F

1.91 CH₂-CH=CH Pr H H Pr H 2-Cl 4-Cl

1.92 CH₂-CH=CH Pr H H Pr H 2-F 4-F

1.93 CH₂ Pr CO₂Me H Pr H 4-(4-F)Ph H

1.94 CH₂ Pr H H isoPr H 4-Ph H

1.95 CH₂-CH=CH Pr H H isoPr H 4-Ph H

1.96 CH₂ Pr H H isoPr H 4-(4-F)Ph H

1.97 CH₂-CH=CH Pr H H isoPr H 4-F H

1.98 CH₂-CH=CH Pr H H isoPr H 2-F 4-Cl

1.99 CH₂-CH=CH Pr H H isoPr H 2-Cl 4-F

1.100 CH₂-CH=CH Pr H H isoPr H 2-Cl 4-Cl

1.101 CH₂-CH=CH Pr H H isoPr H 2-F 4-F

1.102 CH₂ Pr CO₂Me H isoPr H 4-(4-F)Ph H

1.103 CH₂ Pr H H Bu H 4-Ph H

1.104 CH₂-CH=CH Pr H H Bu H 4-Ph H

1.105 CH₂ Pr H H Bu H 4-(4-F)Ph H

1.106 CH₂ Pr CO₂Me H Bu H 4-(4-F)Ph H

1.107 CH₂ Pr H H i-Bu H 4-Ph H

1.108 CH₂ Pr H H i-Bu H 4-(4-F)Ph H

1.109 CH₂ Pr CO₂Me H i-Bu H 4-(4-F)Ph H

1.110 CH₂ Pr H H s-Bu H 4-Ph H

1.111 CH₂ Pr H H s-Bu H 4-(4-F)Ph H

1.112 CH₂ Pr CO₂Me H s-Bu H 4-(4-F)Ph H

1.113 CH₂ Pr H H t-Bu H 4-Ph H

1.114 CH₂ Pr H H t-Bu H 4-(4-F)Ph H

1.115 CH₂ Pr CO₂Me H t-Bu H 4-(4-F)Ph H

1.116 CH₂-CH=CH Pr H H Me Me 4-Cl H

1.117 CH₂-CH=CH Me H H Me Me 2-Cl 4-Cl

1.118 CH₂-CH=CH Et H H Me Me 2-Cl 4-Cl

1.119 CH₂-CH=CH Bu H H Me Me 2-Cl 4-Cl

1.120 CH₂-CH=CH Me H H Me Me 2-F 4-F

1.121 CH₂ Pr H H CH=CMe₂ H 4-Ph H

1.122 CH₂-CH=CH Pr H H Me Me 2-NO₂ H

1.123 CH₂ Pr H H C₂H₄OMe H 4-Ph H

1.124 CH₂-CMe=CH Pr H H Me Me 4-Cl H

1.125 CH₂-CMe=CH Pr H H Me Me 4-F H

1.126 CH₂-CH=CMe Pr H H Me Me 4-Cl H Compounds specifically preferred for reasons of greatest herbicidal efficacy and/or greatest selectivity on rice and/or most favourable ease of synthesis are:

2-[1-(4-phenylbenzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (Compound 1.39 )

2-[1-(4-(4-fluorophenyl)benzyloxyamino)butylidene]-5,5-dimethylcyclohexane- 1,3-dione (Compound 1. 43)

2-[1-(3-(2,4-dichlorophenyl)allyloxyamino)butylidene]-5,5-dimethylcyclohexane- 1,3-dione (Compound 1. 47 )

2-[1-(3-(2,4-difluorophenyl)allyloxyamino)butylidene]-5,5-dimethylcyclohexane- 1,3-dione (Compound 1. 48 )

2-[1-(4-(4-fluorophenyl)benzyloxyamino)butylidene]-5-isopropylcyclohexane-1,3- dione (Compound 1. 96)

2-[1-(3-(2,4-dichlorophenyl)allyloxyamino)propylidene]-5,5-dimethylcyclohexane- 1,3-dione (Compound 1. 118 )

Similarly preferred compounds in which R is not hydrogen are:

2-[1-(3(2,4-dichlorophenyl)allyloxyamino)butylidene]-5,5-dimethyl-1-phenylsulphonyloxycyclohex-1-ene-3-one (Compound 2.1)

2-[1-(4-phenyl)benzyloxyamino)butylidene]-5,5-dimethyl-1-pheny1-sulphonyloxycyclohex-1-ene-3-one (Compound 2.2)

It should be recognised that when R¹ is hydrogen the compounds (1) of the invention may undergo tautomerisation. All tautomeric forms are included in the scope of this invention.

The compounds of the invention may be prepared by standard synthetic procedures including the process outlined in US 4,440,566. Appropriate cyclohexanediones may be acylated on oxygen and the enol esters isomerised (Fries rearrangement) to give th C-substituted products . The C-acylated derivatives may be reacted with O-substituted hydroxylamines which may in turn be generated in situ from appropriate precursors, to afford derivatives of the general Formula (1) wherein R¹ is hydrogen.

Compounds of the invention of Formula (1) wherein R¹ is not hydrogen may also b prepared by standard synthetic procedures. For example, compounds of the inventio of Formula (1) wherein R¹ is an organic or inorganic cation may be prepared from compounds of the invention of Formula (1) wherein R¹ is hydrogen by reacting thes latter compounds with an appropriate inorganic or organic base.

Sulphonylation, etherification or esterification of the vinylogous acid in compounds o the invention of Formula (1) wherein R¹ is hydrogen provides further herbicidal and growth regulating derivatives.

Activity of Compounds of the Invention Test results indicate that the compounds of the invention are highly active pre- emergent and/or post-emergent herbicides or plant growth regulants. These compounds are useful for controlling certain grass weeds in small grain cereals such as wheat (Triticum aestivum) and barley (Hordeum vulgare), examples of which include, but are not limited to, Centurk wheat, Era wheat, Igri barley and Klages barley. Many of the compounds of this invention are especially useful for the control of selected grass weeds, such as wild oats (Avena fatua), black grain (Alopecurus myosoides), crabgrass (Digitaria sanguinalis), foxtails (Setaria spp.) and Italian ryegrass (Lolium multiflonim). These compounds are also particularly useful for controlling certain grass weeds in dryland and paddy rice (Orysa sativa), examples of which include, but are not limited to, Indica and Japonica varieties of the crop. Many of the compounds of this invention are especially useful for the control of selected grass weeds, such as barnyardgrass (Echinochloa crusgalli), in paddy rice.

At the appropriate application rates, these compounds also have utility for broad-spectrum pre- and/or post-emergence weed control in areas where control of all vegetation is required. Alternatively, these compounds are useful to regulate plant growth. Rates of application for compounds of this invention are determined by a number of factors. These factors include formulation selection, method of application, amount of vegetation present, growing conditions, etc. In general, the subject compounds should be applied at rates of 0.005 to 5 kg/ha with a preferred rate range of 0.01 to 1 kg/ha. One skilled in the art can easily determine application rates necessary for the desired level of weed control.

Compounds of this invention may be used alone or in combination with other commercial herbicides, insecticides or fungicides. Accordingly, in yet a further embodiment, the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula (1) as hereinbefore defined with at least one other herbicide.

In yet a still further embodiment, the invention provides a method for regulating the growth of a plant comprising applying to the plant, to the seed of the plant, or to the growth medium of the plant an effective amount of a compound of Formula (1) as hereinbefore defined.

Rates of application of these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Weed grasses in graminaceous crops can normally be killed when treated at a rate of from less than 0.1 to about 1 kg active ingredient/ha.

The compounds of this invention can be mixed with fungicides, bactericides, acaricides, nematicides, insecticides, or other biologically active compounds in order to achieve desired results with a minimum expenditure of time, effort and material.

Amounts of these biologically active materials added for each part by weight of the composition of this invention may vary from 0.05 to 25 parts by weight. Suitable agents of this type are well known to those skilled in the art.

Formulation

Useful formulations of the compounds within the scope of this invention can be prepared in conventional ways. They include dusts, granules, pellets, solutions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be applied directly. Sprayable formulations can be extended in suitable media and used at spray volumes of from one litre to several hundred litres per hectare. High strength compositions are primarily used as intermediates for further

formulations. The formulations, broadly, contain about 1% to 99% by weight of active ingredient(s) and at least one of (a) about 0.1% to 20% surfactant(s) and (b) about 5% to 99% solid or liquid inert diluent(s). More specifically, they will contain these ingredients in the approximate proportions given in the table below:

Percent by Weight

Formulation Type Active Diluent Surfactant(s)

Ingredient

Wettable Powders 20-90 0-74 1-10

Oil Suspensions, Emulsions, 5-50 40-95 0-15

Solutions(including Emulsifiable

Concentrates)

Aqueous Suspensions 10-50 40-84 1-20

Dusts 1-25 70-99 0-5

Granules and Pellets 1-95 5-99 0-15

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

Lower or higher levels of active ingredients can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are sometimes desirable and are achieved by

incorporation into the formulation or by tank mixing.

The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier therefor, for example, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewill's earth, diatomaceous earth, and China clay. The compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also solid diluents, fillers and suspending agents.

Typical solid diluents are described in Watkins, et al., "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, N.J. The more absorptive diluents are preferred for the wettable powders and the denser ones for dusts. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, etc.

Compositions for dressing seed, for example, may contain an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed. The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable solvents are acetone, ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene amongst others. Solubility under 0.1% is preferred for suspension concentrates; solution concentrates are preferably stable against phase separation at 0°C. "McCutcheon's Detergents and Emulsifϊers Annual", MC Publishing Corp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses.

The methods of making such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, US Pat. No. 3.060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. The synthesis and biological activity of the compounds of formula 1 is illustrated by the following non-limiting examples.

Example 1:

Preparation of 2-[1-(4-phenylbenzyloxyamino)butylidene]-5,5-dimethylcyclohexane 1,3-dione (Compound 1.39)

(a) 4-Phenylbenzyl chloride

Thionyl chloride(11.8 ml) was added dropwise to a stirred suspension of

4-phenylbenzyl alcohol(10.0g) in 1,2-dichloroethane (25 ml) cooled in an ice bath.

The solution was stirred at room temperature for 2 hours then refluxed for 1 hour

The solvent and excess reagent were removed under reduced pressure and the residue was used in the next step without further purification.

(b) N-(4-Phenylbenzyloxy)phthalimide

A solution of the crude chloride in N,N-dimethylformamide (DMF) (20 ml) was added to a stirred solution of N-hydroxyphthalimide (9.7g) and

N,N-diisopropylethylamine (15.4g) in DMF (30 ml). After 48 hours at 20°C and 48 hours at 45°C the mixture was diluted with water (1000 ml) and filtered. The residue was washed thoroughly with water to give the product as a white solid (13.8g ), m.p.

196-7°C, δ (CDCl₃ and CH₃COOH), 5.3, s, CH₂; 7.2-7.6, m, 9 ArH and 7.76, s, 4 ArH (c) 2-Butyryl-5,5-dimethylcyclohexane-1,3-dione

Tri-N-propylamine (31.5g) was added dropwise to a mixture of 5,5-dimethylcyclohexane-1,3-dione(14g), butyric anhydride(17.4g) and

N,N-(4-dimethyIamino)pyridine (1g) and the mixture stirred at room temperature for 16 hours. The solution was cooled in ice, acidified to pH 3 with 2N hydrochloric acid and extracted with ether (x3). The combined ether extracts were washed with water, dried and the solvent removed under reduced pressure. The product was freed from residual butyric acid and butyric anhydride by heating at 50°C and 1mm pressure until no further material was removed and the residue was used in the next step without further purification.

(d) 2-[1-(4-Phenylbenzyloxyamino)butylideneJ-5,5-dimethylcyclohexane-1,3- dione

N,N-Diethylethylenediamine (lg) was added to a stirred suspension of

N-(4-phenylbenzyloxy)phthalimide (2.2g) in ethanol (24 ml). After a clear solution had formed the butyroyl compound (1.3g) was added and the solution was buffered t pH 4 by the addition of glacial acetic acid. After 16 hours at 20° the solvent was removed under reduced pressure, the residue was acidified to pH 2-3 with dilute hydrochloric acid and then extracted with ether (3x). The combined ether extracts were washed with water, the ether removed by evaporation and the residue was purified by chromatography over silica to give the product as a colourless solid (1.3g m.p. 49-51°C, δ (CDCl₃) 0.98, t,J 7 Hz, CH₃CH₂; 1.05, s, 2×CH₃; 1.3-1.7, m, 2H, CH₂CH₃; 1.2, 1.35, s, s, ring CH₂; 2.85-3.05, m, CH₂CH₂CH₃; 5.05, s, ArCH₂ and 7.3-7.65, m, 9 ArH.

Example 2

Preparation of 2-[1-(4-(4-fluorophenyl)benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (Compound 1.43)

(a) 4-Methyl-1-(4-fluorophenyl)cyclohexanol

The Grignard reagent prepared from 1-bromo-4-fluorobenzene (25 g) and magnesium (3.5g) in ether (200 ml) was cooled to 0°C, treated with 4-methyl cyclohexanone

(16g) added dropwise, the mixture was stirred at 20°C for 15 min then refluxed for 3 min. The solution was poured into a saturated solution of ammonium chloride (200 ml), the mixture extracted with ether (3 × 50ml) and the extract was dried over anhydrous potassium carbonate. Removal of the ether under reduced pressure left the crude product (25.5g) as a yellowish oil which was used in the next step without further purification. (b) 4-(4-Fluorophenyl)toluene

The alcohol obtained as described above (25.5g) was dissolved in formic acid (98% and the solution was stirred overnight. The mixture was poured into water and the cyclohexene produced by dehydration of the alcohol was extracted into ether (3 × 50ml). The ether extract was washed with aqueous sodium bicarbonate and then bri and finally dried over anhydrous magnesium sulphate. Following removal of the eth by evaporation, sulphur (7.7g) was added to the residue and the mixture was heated 180-200° until no further hydrogen sulphide was evolved (ca. 4 hrs). The dark brow reaction mixture was stirred with methanol (200ml) for lhr and the mixture then filtered to remove excess sulphur. Evaporation of the solvent followed by

recrystallisation of the residue from methanol afforded the product (6g) m.p. 75-79° δ (CDCl₃) 2.42, s, CH₂ and 7.0-7.7, m, 8 ArH..

(c) N-(4-Fluorophenyl)benzyloxyphthalimide

4-(4-Fluorophenyl)toluene (5.9g) and N-bromosuccinimide (6.2g) in carbon tetrachloride (100ml) containing dibenzoyl peroxide was refluxed 8 hrs. The mixture was allowed to cool to room temperature, filtered and the solvent was removed under reduced pressure. The crude benzyl bromide was dissolved in DMF (20ml) and the solution was added to a mixture of N-hydroxyphthalimide (4.6g) and N,N- diisopropylethylamine (7.4g) in DMF (20ml). The solution was stirred at room temperature for 48 hrs and the product was precipitated by addition of water (50ml) and then filtered off. The precipitate was washed with ethanol and recrystallised from chloroform to give the phthalϊmide as colourless crystals (8.2g), m.p. 161-163°C, δ (CDCl₃) 5.2, CH₂ and 7.0-7.9, m, 12 ArH.

(d) 2-[1-(4-(4-Fluorophenyl)benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (Compound 1.43)

N,N-Diethylethylenediamine (0.5g) was added to a stirred suspension of N-(4-fluorophenyl)benzyloxyphthalimide (1g) in ethanol (12ml). After a clear solution had formed the crude triketone (1c, 0.6g) was added and the reaction mixture was buffered to pH4 by the addition of glacial acetic acid. After 24hrs volatile materials were removed under reduced pressure, the residue was stirred into water (50ml) and the mixture was extracted with ether. The ether extract was washed with brine, dried and the ether removed by evaporation. The residue was purified by chromatography over silica gel using ethyl acetate-light petroleum (1:20) to elute the product which was obtained as a pale yellow oil (0.6g), δ (CDCl₃₎ 0.8-1.2, m, 2x CH₃ and CH₂CH₃; 1.4-1.7, m, CH₂CH₃; 2.2, 2.4, s, s, 2x ring CH₂; 2.8-3.1, m, CH₃CH₂CH₂; 5.06, s, ArCH₂ and 7.0-7.7, m, 8 ArH.

Example 3

The general methods used above were used to prepare the following compounds from Table 1; their melting points and nmr spectral characteristics are given after the compound number.

Compound 1.1 m.p. 70°C, CDCl₃, δ 0.98, t, J7Hz, CH₃; 1.4-2.1, m,

CH₃CH₂ and CH₂CH₂CH₂; 2.2-2.7, m, CH₂CHoCH₂; 2.9, t, J7Hz; CH₂CH₂CH₃; 5.1. s. CH₂Ar and 7.3-7.7, m, 9ArH

Compound 1.2 m.p.122°C, CDCl₃, δ 0.96, t, J7Hz, CH₃; 1.2-2.0, m,

CH₃CH₂ and CH₂CH₂CH₂; 2.3-2.7, m, CH₂CH₂CH₂; 2.9, t, J7Hz, CH₂CH₂CH₃; 5.1. s. CH₂Ar and 7.3-7.7, m, 8ArH

Compound 1.15 oil, CDCl₃, δ 0.85-1.1, m , CH₃CH₂ and CH₃CH; 1.4-1.8, m, CH₃CH₂; 1.9-2.7, m, CH₃CH and 2 x CH₂CO; 2.95, t, J7Hz, CH₃CH₂CH₂; 5.1, s, CH₂Ar and 7.3-7.7, m, 9 ArH Compound 1.16 oil, CDCl₃, δ 0.88, t, J 7Hz, CH₃CH₂; 1.04, d, J3Hz, CH₃CH ; 1.3-2.6, m, CH₃CH₂, 2 × CH₂CO and CH₃CH; 2.92, t, J7Hz, CH₃CH₂CH₂; 5.1, s, CH₂Ar and 7.0-7.6, m, 8 ArH

Compound 1.25 oil, CDCl₃ δ 0.85-2.4, m, 15 aliphatic H; 2.9, t, J7Hz, CH₃CH₂CH₂; 5.05, s, CH₂Ar and 7.3-7.8, m, 9 ArH

Compound 1.35 colourless oil, CDCl₃, δ 0.96, s, 2 x CH₃; 1.06, t, J7Hz,

CH₃CH₂; 2.1-2.4, m, 2 × CH₂CO; 2.9, t, J7Hz, CH₃CH₂; 5.0, s, CH₂Ar and 7.2-7.7, m, 9 ArH

Compound 1.38 oil; CDCl₃, δ 0.94, s, 2 × CH₃;0.92, t, J7Hz, CH₃CH₂; 1.3- 1.7, m, CH₃CH₂; 2.2 and 2.4, each broad s, 2 × CH₂CO; 2.9, t, J7Hz, CH₃CH₂CH₂; 5.04, s, CH₂Ar and 7.0-7.6, m, 9 ArH Compound 1.44 oil; CDCl₃, δ 0.92, t, J7Hz, CH₃CH₂; 1.04, s, 2 × CH₃; 1.35- 1.7, m, CH₃CH₂; 2.31, broad s, 2 × CH₂CO; 2.91, t, J7Hz, CH₃CH₂CH₂; 4.65, d, J5Hz, CH₂Ar; 6.1-7.5, m, CH=CH and 4 ArH. Compound 1.48 oil; CDCl₃, δ 0.96, t, J7Hz, CH₃CH₂; 1.08, s, 2 × CH₃; 1.4

1.8, m, CH₃CH₂; 2.32 and 2.42, each broad s, 2 × CH₂CO; 2.95, t, J7Hz,

CH₃CH₂CH₂; 4.88, d, J5Hz, CH₂Ar and 6.15-7.6, m, 3 ArH and CH=CH

Compound 1.55 oil; CDCl₃, δ 0.72-1.08, 2t, 2×CH₃CH₂; 1.07, s, 2 × CH₃;

1.2-1.8, m, 2×CH₃CH₂; 2.34, broad s, 2 × CH₂CO; 3.01, t, J7Hz, CH₃CH₂CH₂; 5.1 s, CH₂Ar and 7.01-7.7, m, 8 ArH

Compound 1.56 oil; CDCl₃, δ 0.72-1.04, 2t, 2×CH₃CH₂; 0.98, s, 2 × CH₃; 1.2-1.7, m, 2×CH₃CH₂; 2.32, broad s, 2 × CH₂CO; 2.92, t, J7Hz, CH₃CH₂CH₂; 4.6 d, J5Hz, CH₂Ar and 6.1-7.5, m, 3 ArH and CH=CH

Compound 1.96 oil; CDCl₃, δ 0.85-1.05, m, CH₃CH₂ and CH(CH₃)₂; 1.3- 1.7, m, CH₃CH₂, 2 × CH₂CO and CH-CH; 2.94, t, J7Hz, CH₃CH₂CH₂; 5.1, s, CH₂Ar and 7.0-7.6, m. 8 ArH

Compound 1.107 oil; CDCl₃, δ 0.8-1.2,m , 3 × CH₃ and CH₃CH2; 1.4-2.7, m,

CH₃CH₂- 2 × CH₂CO and CH; 3.0, t, J7Hz, CH₃CH₂CH₂; 5.15, s, CH₂Ar and 7.1-7.7, m, 8 ArH

Compound 1.116 oil; CDCl₃, δ 0.94, t, J7Hz, CH₃CH₂; 1.04, s, 2 × CH₃; 1.4-1.8, m, CH₃CH₂; 2.33, broad s, 2 × CH₂CO; 2.93, t, J7Hz, CH₃CH₂CH₂; 4.65, d, J5Hz, CH₂Ar; 6.1-6.8, m, CH=CH and 7.3, s, 4 ArH. Compound 1.117 oil; CDCl₃, δ1.14, s, 2×CH₃; 2.32 and 2.42, each broad s, 2 × CH₂CO; 2.44, s, CH₃; 4.78, d, J5Hz, CH₂Ar and 6.15-7.6, m, 3 ArH and CH=CH

Compound 1.118 oil; CDCl₃, δ 1.07, t, J7Hz, CH₃CH₂; 1.04, s, 2 × CH₃; 2.3 and 2.36, each broad s, 2 × CH₂CO; 2.92, t, J7Hz, CH₃CH₂; 4.68, d, J5Hz, CH₂Ar and 6.15-7.5, m, 3 ArH and CH=CH

Compound 1.119 oil; CDCl₃, δ 0.92, t, J7Hz, CH₃CH₂; 1.08, s, 2 × CH₃; 1.3-1.7 m, CH₃CH₂CH₂CH₂; 2.26 and 2.38, each broad s, 2 × CH₂CO; 2.95, t, J7Hz, CH₃CH₂CH₂CH₂; 4.69, d, J5Hz, CH₂Ar and 6.15-7.6, m, 3 ArH and CH=CH Compound 1.120 oil; CDCl₃, δ 1.08, s, 2×CH₃; 2.47, s, 2 × CH₂CO; 2.49, s, CH 4.67, d, J5Hz, CH₂Ar and 6.15-7.6, m, 3 ArH and CH=CH

Compound 1.121 oil, CDCl₃, δ 0.96, t, J7Hz, CH₃CH₂; 1.58, 1.64, s, s, 2 × CH₃; 2.1-2.6, m, 2 × CH₂CO and CH; 2.94, t, J7Hz, CH₃CH₂; 5.06, s, CH₂Ar and 7.2-7. m, 9 ArH

Compound 1.122 oil; CDCl₃, δ 0.93, t, J7Hz, CH₃CH₂; 1.06, s, 2 × CH₃; 1.4- 1.8, m, CH₃CH₂; 2.36, s, 2 × CH₂CO; 2.93, t, J7Hz, CH₃CH₂CH₂; 4.75, d, J5Hz, CH₂Ar; 6.1-7.9, m, CH=CH and 4 ArH.

Compound 1.123 oil, CDCl₃, δ 0.96, t, J7Hz, CH₃CH₂; 1.2-2.5, m, 2 × CH₂C

CH₃CH₂ and CHCH₂ ; 2.93, t, J7Hz, CH₃CH₂CH₂; 3.32, s, OCH₃; 3.39, t, J5Hz, CH₂COCH₃. 5.06, s, CH₂Ar and 7.2-7.6, m, 9 ArH

Compound 1.124 oil; CDCl₃, δ 0.97, t, J7Hz, CH₃CH₂; 1.08, s, 2 × CH₃; 1.4- 1.8, m, CH₃CH₂; 1.88, s, CH₃; 2.36, s, 2 × CH₂CO; 2.93, t, J7Hz, CH₃CH₂CH₂; 4.61, s, CH₂Ar; 6.47, s, C=CH and 7.3, s, 4 ArH.

Compound 1.125 oil; CDCl₃, δ 0.95, t, J7Hz, CH₃CH₂; 1.13, s, 2 × CH₃; 1.4- 1.7, m, CH₃CH₂; 1.83, s, CH₃; 2.37, s, 2 × CH₂CO; 2.93, t, J7Hz, CH₃CH₂CH₂; 4.54, s, CH₂Ar; 6.51, s, C=CH and 6.9-7.4, m, 4 ArH.

Compound 1.126 oil; CDCl₃, δ 0.95, t, J7Hz, CH₃CH₂; 1.03, s, 2 × CH₃; 1.4-

1.7, m, CH₃CH₂; 2.07, s, CH₃; 2.35, s, 2 × CH₂CO; 2.92, t, J7Hz, CH₃CH₂CH₂; 4.69, d, J5Hz, CH₂Ar; 5.87, t, J5Hz, C=CH and 7.29, s, 4 ArH.

Further examples showing the general approach to the preparation of the compounds of the invention where R₁ is other than hydrogen follow.

Example 4

(a) Preparation of 2-[1-(3-(2,4-dichlorophenyl)allyloxyamino)butylidene]-5,5- dimethylcyclohexane-1,3-dione (Compound 1. 47 )

A mixture of N-[3-(2,4-dichlorophenyl)allyl]oxyphthlamide (0.7g) and N,N-diethylethylenediamine (0.35g) in ethanol (8ml) was stirred at room temperature until a clear solution was formed. 2-Butyryl-5,5-dimethylcyclohexane-1,3-dione (0.42g) was added and the mixture was adjusted to pH 4 by the addition of acetic acid. After 16 hrs at room temperature, the ethanol was removed under reduced pressure, the residue was dissolved in ether and extracted with 5% sodium hydroxide. The alkaline extract was acidified to pH 4 with dilute hydrochloric acid, the organic material collected by extraction with ether and purified by chromatography over silica gel following removal of the ether to give the product as a colourless oil (220mg), CDCl₃, δ 0.98, t, J7Hz, CH₃CH₂; 1.04, s, 2 × CH₃; 1.4-1.7, m, CH₃CH₂; 2.32, broad s, 2x CH₂CO; 2.94, t, J7Hz, CH₃CH₂CH₂; 4.69, d, J5Hz, CH₂Ar and 6.1-7.5, m, 3 ArH. and CH=CH.

(b) Preparation of 2-[1-(3-(2,4-dichlorophenyl)allyloxyamino)butylidene]-5,5- dimethyl-1-phenyIsulphonyloxycyclohex-1-ene-3-one (Compound 2.1)

To a solution of the oxime (0.78g, prepared as in (a) above) in pyridine (1.5ml) cooled to 0° was added benzene sulphonyl chloride with stirring. After 48 hrs at room temperature, the reaction mixture was diluted with aqueous citric acid (20ml, 20%) and extracted with ether (3x). Following evaporation of the ether, the residue was purified by chromatography over silica gel to give the product (0.62g) as a colourless oil, CDCl₃, δ 0.82, t, J7Hz, CH₃CH₂; 1.02, 1.04, s, s, 2 x CH₃; 1.2-1.5, CH₃CH₂; 2.15, t, J7Hz, CH₃CH₂CH₂; 2.32 and 2.79, each s, 2 x CH₂CO; 4.58, d, J5Hz, CH₂Ar and 6.1-7.9, m, 8 ArH. and CH=CH.

Example 5 (a) Preparation of 2-[1-(4-phenyl)benzyloxyamino)butylidene]-5,5-dimethyl-1- phenylsulphonyloxycyclohex-1-ene-3-one (Compound 2.2)

Using the method of Example 4(b) above, 2-[1-(4-phenyl)-benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione (Compound 1.39) was reacted with benzene sulphonyl chloride to produce the title compound as a colourless oil with an nmr in CDCl₃, δ 0.81, t, J7Hz, CH₂CH₂CH₃; 1.12, s, 2x CH₃: 1.2-1.6, m, CH₂CH₂CH₃; 2.3, t, J7Hz, CH₂CH₂CH₃; 2.31, 2.78, each s, 2×CH₂; 5.01,. s,. CH₂Ar and 7.2-7.9, m, 14 ArH

Example 6 To demonstrate the effectiveness of compounds of Formula (1) of the present invention as herbicidal agents, the compounds of Formula (1) listed in Table 2 were applied to bamyardgrass and rice postemergent at 0.1 and 0.4 kg/hectare. The herbicidal data are shown in Table 2 In the table 0 signifies no effect and 10 signifies plant dead. As can be seen the compounds of Formula (1) selectively control bamyardgrass in rice, although a few of the compounds, notably 1.48 and 1.118 are sufficiently active to kill rice at the test concentrations. In secondary screening tests at lower application rates (30 and 60 g/ha) these compounds show good selectivity.

Table 2

Compound (0.1 Kg/Ha) (0.4 Kg/Ha)

(Table 1 Bamyardgrass Rice Bamyardgrass Rice

1.15 10 1 10 8

1.16 10 1 10 4

1.25 9 2 10 1

1.35 9 2 9 1

1.38 9 0 10 0

1.39 9 2 9 2

1.43 10 3 10 8

1.44 9 10 2 8

1.48 10 9 10 8

1.55 9 1 9 3

1.56 9 2 10 6

1.96 10 0 10 2

1.116 10 6 10 9

1.117 9 2 10 5

1.118 10 8 10 9

1.119 3 0 5 0

1.120 9 1 10 7

1.121 9 1 10 0

1.122 9 5 9 6

1.123 10 2 10 4

1.124 10 2 10 7

1.125 10 2 10 8

1.126 10 1 10 4

Table 3

Compound (0.03 Kg/Ha) (0.06 Kg/Ha) (Table 1) Bamyardgrass Rice Bamyardgrass Rice

1.48 9 0 10 2 1.118 10 0 10 0

Claims

1. Compounds of Formula (1), and isomeric and/or tautomeric forms thereof:

wherein

X is selected from the group O, and a single bond;

R¹ is selected from the group H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₅-C₆ cycloalkyl, C₅-C₆ cycloalkenyl, alkanoyl, aroyl, C₁-C₄ alkylsulphonyl, arylsulphonyl, benzenesulfonyl, C₁-C₄ alkylcarbonyl, C₂-C₈ alkoxyalkyl, C₂-C₈ alkylthioalkyl, C₄-C₁₀ phenylalkyl, M, and phenyl optionally substitute with 1-3 substituents selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl, amino, and C₁-C₄ haloalkoxy;

R² is selected from the group C₁-C₆ alkyl, C ₂-C₆ alkenyl, C₂-C₆ alkynyl, C₁-C₄ haloalkyl, C₁-C₄ alkylthio, C₃-C₆ cycloalkyl, C₅-C₆ cycloalkenyl, C2~C₈ alkoxyalkyl, C₂-C₈ alkylthioalkyl, C₁-C₄ alkyl substituted with a substituent selected from the group consisting of phenyl, phenoxy and thiophenoxy wherein the aromatic ring of said substituents is optionally substituted with 1- substituents selected from halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, amino, C₁-C₄ haloalkyl and C₁-C₄ haloalkoxy, and phenyl optionally substituted with 1-3 substituents selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl, amino, and C₁-C₄ haloalkoxy;

R³and R⁴ are independently selected from the group H, C₁-C₄ alkyl, C₁-C₄ alkoxy, and cyano, or one of R³ or R⁴ can independently be taken together with one of

R₅ or R₆ and the ring carbons to which they are attached to form a 5- or 6-membered ring;

R⁵ and R⁶ are independently selected from the group H, C₁-C₆ alkyl, C₂-C₄ alkenyl, C₂-C₈ alkylthioalkyl, C₁-C₄ haloalkyl, C₂-C₄ haloalkenyl, C₃-C₆ cycloalkyl wherein the alkyl, alkenyl and cycloalkyl groups are optionally substituted with

1-3 substituents independently selected from the group consisting of OR¹², NR¹³R¹⁴, NR¹⁵CO(C₁-C₄ alkyl), NR¹⁸SO₂(C₁-C₄ alkyl), C(OR¹⁶)(OR¹⁷)R²², C(SR¹⁹)(SR²⁰)R²³, C₁-C₄ alkoxycarbonyl and phenyl optionally substituted with a substituent selected from halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy,

C₁-C₄ alkylthio, nitro, cyano, C₁-C₄ haloalkyl and C₁-C₄ haloalkoxy;

or

R⁵ and R⁶ together with the ring carbon to which they are attached form a saturated or an unsaturated 3- to 7-membered carbocyclic ring, or a saturated or an unsaturated 5- to 7-membered heterocyclic ring containing 1-3 heteroatoms selected from the group consisting of 0-3 nitrogen, 0-2 oxygen and 0-2 sulphur atoms; the carbocyclic or heterocyclic ring being substituted with 1-4 substituents independently selected from the group halogen, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylcarbonyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ alkoxycarbonyl, -COOH, C₁-C₈ alkoxyalkyl, C₂-C₈ alkylthioalkyl, and phenyl which is optionally substituted with a substituent selected from halogen, C₁-C₄ alkoxy, C₁-C₄ alkylthio, C₁-C₄ haloalkyl, nitro, cyano and C₁-C₄ haloalkoxy; one of the carbon atoms of the carbocyclic and heterocyclic ring being optionally in the form of a carbonyl group or its corresponding dimethyl, diethyl or ethylene or propylene ketal;

R⁷, R⁸ and R⁹ are independently selected from the group H; halogen; C₁-C₄ alkyl;

C₁-C₄ alkoxy; C₁-C₄ alkylthio; C₁-C₄ alkylsulphinyl; C₁-C₄ alkylsulphonyl, C₁-C₄ haloalkyl; C₁-C₄ haloalkoxy; nitro; cyano; C₁-C₄ alkoxycarbonyl; C₁-C₄ alkylaminocarbonyl; C^-Cg dialkylaminocarbonyl; aminocarbonyl; amino; C₁-C₄ alkylamino; and C₂-C₆ dialkylamino; or a group selected from benzenesulphonyl, benzoyl, benzyl, benzyloxy, pyridyl, phenoxy, phenylthio, phenylamino and phenyl group, said group optionally substituted with 1-3 substituents independently selected from the group consisting of halogen,

C₁-C₄ alkyl, C₁-C₄ alkoxy, and CF₃;

R¹² is selected from the group H, C₁-C₄ alkyl ,benzyl, CO(C₁-C₄ alkyl), and

CO₂(C₁-C₄ alkyl);

R¹³, R¹⁵, R¹⁸, R²² and R²³ are independently selected from H and C₁-C₃ alkyl; R¹⁴, R¹⁶, R¹⁷, R¹⁹ and R²⁰ are independently selected from C₁-C₃ alkyl;

R¹⁶ and R¹⁷ can be taken together as -(CH₂)₂- or -(CH₂)₃-; and

R¹⁹ and R²⁰ can be taken together as -(CH₂)_2- or -(CH₂)₃-; provided that:

a) when A is CH₂, and X is a single bond, and R¹ is H, C₁-C₄ alkylcarbonyl, arylcarbonyl or M, and R² is C₁-C₆ alkyl or phenyl, and R³ and R⁴ are H, and R⁵ and R⁶ are H, C₁-C₃ alkyl or C₂-C₈ alkylthioalkyl, then at least one of

R⁷, R⁸ and R⁹ is other than H, CF₃, nitro or halogen; b) when A is C₂-C₃ alkylene, X is O, R¹ is H, R² is C₃ alkyl, R³ and R⁴ are H, R⁵ and R⁶ are CH₃, then at least one of R⁷, R⁸ and R⁹ is other than H; c) when A is CH₂, or C₃ alkylene or C₃ alkenylene optionally substituted with 1-3 C₁-C₃ alkyl groups, and X is a single bond, and R¹ is H, and R³ an R⁴ are both H, and one of R⁵ or R⁶ is hydrogen and the other is

C₂-C₈ alkylthioalkyl, C₁-C₄ alkyl substituted with O(C₁-C₄ alkyl), or C₃-C₆ cycloalkyl optionally substituted with OR¹² where R¹² is C₁-C₄ alkyl or H, then at least one of R⁷, R⁸ or R⁹ are other than H, halogen, nitro, cyano, C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkyl, C₁-C₄ haloalkoxy, C₁-C₄ alkoxycarbonyl or optionally substituted phenyl.

2. Compounds of Formula 1, as claimed in Claim 1, wherein

R¹ is H, alkylsulphonyl, arylsulphonyl or M; and

R² is C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl .

3. Compounds of Formula 1, as claimed in Claim 2, wherein

A is C₁-C₂ alkylene or C₃-C₄ alkenylene optionally substituted with CH₃ or C₂H₅;

substituents selected from the group consisting of halogen, C₁-C₄ alkyl, C₁-C₄ alkoxy, or CF₃.

4. Compounds of Formula 1, as claimed in Claim 3, wherein X is O.

5. Compounds of Formula 1, as claimed in Claim 3, wherein X is a single bond.

6. Compounds of Formula 1, as claimed in Claim 5, wherein

A is -CH₂-, -CH₂CH₂- -CH₂CH=CH- or -CH₂CMe=CH- ;

R¹ is H, Li+, Na +, or K+;

R² is CH₃, C₂H₅, n-C₃H₇ or n-C₄H₉ ;

R³ and R⁴ are independently H, CH₃ or C₂H₅ ; and R⁷, R⁸ and R⁹ are independently H, Cl, Br, F, CH₃, C₂H₅, OCH₃, O C₂H₅, SCH₃, SC₂H₅, CF₃, CHF₂, CF₂CF₃, OCHF₂, OCF₃, OCH₂CF₃, NO₂, CN CO₂CH₃ Ph, SO₂Ph, COPh, CH₂Ph, OCH₂Ph, OPh, SPh, NHPh or N(Me)Ph.

7. Compounds of Formula 1, as claimed in Claim 5, wherein

R⁵ and R⁶ are independently C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkylthio or C₂-C₈ alkylthioalkyl. 8. Compounds of Formula 1, as claimed in Claim 5, wherein

R⁵ and R⁶ together with the carbon to which they are attached form a saturated or unsaturated 5-, 6- or 7-membered carbocyclic ring which is optionally substituted with 1-4 CH₃ groups. 9. Compounds of Formula 1, as claimed in Claim 8, wherein:

A is -CH₂-, -CH₂CH₂-, -CH₂CH=CH- or -CH₂CMe=CH- ; R¹ is H, Li+,

Na+ or K+; R² is CH₃, C₂H₅, n- C₃H₇ or n-C₄H₉;

R³ and R⁴ are independently H or CH₃; and

R⁷, R⁸ and R⁹ are independently H, Cl, Br, F, CH₃, C₂H₅, OCH₃, OC₂H₅, SCH₃, SC₂H₅, CF₃, CHF₂ CF₂CF₃, OCHF₂, OCF₃, OCH₂CF₃, NO₂, CN,

CO₂CH₃, Ph, SO₂Ph, COPh, CH₂Ph, OCH₂Ph, OPh, SPh, NHPh or N(Me)Ph.

10. Compounds of Formula 1, as claimed in Claim 5, wherein:

11. Compounds of Formula 1, as claimed in Claim 10, wherein:

A is -CH₂- -CH₂CH₂-, -CH₂CH=CH- or -CH₂CMe=CH-;

R¹ is H, Li+, Na+ or K+;

R² is CH₃, C₂H₅, n-C₃H₇ or n-C₄H₉;

R³ and R⁴ are independently H, CH₃ or C₂H₅ ; and

R⁷ R⁸ and R⁹ are independently H, Cl, Br, F, CH₃, C₂H₅, OCH₃, OC₂H₅, SCH₃, SC₂H₅, CF₃, CHF₂, CF₂CF₃, OCHF₂, OCF₃, OCH₂CF₃, NO₂, CN,

CO₂CH₃, Ph, SO₂Ph, COPh, CH₂Ph, OCH₂Ph, OPh, SPh, NHPh or N(Me)Ph.

12. 2-[1-(4-phenylbenzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3- dione .

13. 2-[1-(4-(4-fluorophenyl)benzyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione. 14. 2-[1-(3-(2,4-dichlorophenyl)allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione.

15. 2-[1-(3-(2,4-difluorophenyl)allyloxyamino)butylidene]-5,5-dimethylcyclohexane-1,3-dione.

16. 2-[1-(4-(4-fluorophenyl)benzyloxyamino)butylidene]-5-isopropylcyclohexane-1,3-dione.

17. 2-[1-(3-(2,4-dichlorophenyl)allyloxyamino)propylidene]-5,5-dimethylcyclohexane-1,3-dione.

18. 2-[1-(3(2,4-dichlorophenyl)allyloxyamino)butylidene]-5,5-dimethyl-1- phenylsulphonyloxycyclohex-1-ene-3-one.

19. 2-[1-(4-phenyl)benzyloxyamino)butylidene]-5,5-dimethyl-1-phenylsulphonyloxycyclohex-1-ene-3-one.

20. Any one of the compounds listed in Table 1.

21. A plant growth inhibiting, plant damaging, or plant killing composition characterised in that it comprises a compound of formula (1), as defined in Claim 1, and an inert carrier therefor.

22. A method for regulating the growth of a plant, characterised in that there is applied to the plant, to the seed of the plant, or to the growth medium of the plant, an effective amount of a compound of formula (1), as defined in Claim 1.

23. A method for selectively inhibiting, damaging or killing weed grasses in a crop, characterised in that there is applied to the crop or its locus an effective amount of a compound of formula (1), as defined in Claim 1.

23. A herbicidal composition characterised in that it comprises a compound of formula (1), as defined in Claim 1, and at least one other herbicide.

25. A plant growth regulating composition characterised in that it comprises a compound of formula (1), as defined in Claim 1, and an inert carrier therefor.

26. The use of a compound of formula (1) as herbicide or plant growth regulator.