WO2014131735A1 - Use of chemical compounds as herbicides - Google Patents

Abstract

The present invention relates to the use of heterocyclic amide derivatives as herbicides, and to herbicidal compositions comprising them, and their use in controlling plants or inhibiting plant growth.

Description

USE OF CHEMICAL COMPOUNDS AS HERBICIDES

The present invention relates to the use of of heterocyclic amide derivatives derivatives as herbicides, and to herbicidal compositions comprising them, and their use in controlling plants or inhibiting plant growth.

Various chemical derivatives have been described, for example, in WO2008/049729, WO2009/109570 and Chemistry & Biology (2009), 16, p.594-604 and have been described to have useful plant growth regulating properties.

It has now surprisingly been found that certain new heterocyclic amide derivatives have properties that are useful as herbicides, for controlling weeds and unwanted plant growth.

Summary of the Invention

In a first aspect, the invention provides the herbicidal use of the compounds of the formula (A):

A1 , A2 and A4 are each independently C-R1 or nitrogen, wherein each R1 may be the same or different; A3 is C-X;

R1 is H, CrC₆haloalkyl, cyano, halogen, d-C₆alkoxy, CrC₆alkyl or CrC₆alkyl substituted by one or more cyano, hydroxyl, amine, carbonylamine; X is halogen, CrC₆haloalkyl, cyano, thiocyanate, nitro, CrC₆alkoxy, CrC₆haloalkoxy, CrC₆alkylthio, Ci-C₆haloalkylthio, CrC₆alkylsulfinyl, CrC₆haloalkylsulfinyl, CrC₆alkyl- sulfonyl, Ci-C₆haloalkylsulfonyl, C₂-C₆alkenyl, C₂-C₆alkynyl, amine, N- CrC₆alkyl amine, N,N-di-Ci-C₆alkyl amine, CrC₆alkylcarbonyl, CrC₆alkoxycarbonyl, Ci- C₆haloalkoxycarbonyl, CrC₆haloalkylcarbonyl, C₃-C₈cycloalkyl, formyl or mercapto; or X is heteroaryl or heteroaryl subtituted by one or more halogen, cyano, CrC₃alkyl, d- C₃haloalkyl;

R2 is H, CrC₆alkyl, CrC₆haloalkyl, Ci-C₄alkylcarbonyl, CrC₆alkoxycarbonyl;

or R2 is CrC₆alkyl substituted by one or more cyano, amine, carbonylamine;

Q is a group according to formula (i)

wherein W are independently O or S; wherein R3, R4, R5 and R6 are independently hydrogen, halogen, nitro, cyano, C C₃alkyl, Ci-C₃haloalkyl, Ci-C₃ alkoxy, hydroxyl, -OC(0)R9, amine, N-Ci-C₃alkyl amine or N,N-di-Ci-C₃alkyl amine;

R7 is hydrogen, CrC₉alkyl, CrC₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂- C₆alkynyl, C₂-C₆haloalkynyl, C₄-C₆alkylcycloalkyl, aryl or aryl substituted by one to five substituents R10, heterocyclyl or heterocyclyl substituted by one to ten substituents R10, C₃-C₇cycloalkyl or C₃-C₇cycloalkyl substituted by one to five substituents R10; or R7 is Ci-C₉alkyl substituted by one or more cyano, nitro, amine, hydroxyl, d- C₆alkoxy, CrC₆haloalkoxy, CrC₆alkylthio, CrC₆haloalkylthio, CrC₆alkylsulfinyl, Ci-C₆haloalkylsulfinyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylsulfonyl, C₂-C₆alkenyl, C₂- C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₇cycloalkyl, C₄-C₆alkylcycloalkyl, N- CrC₆alkyl amine, N,N-di-CrC₆alkyl amine, aryl or aryl substituted by one to five substituents R10, heterocyclyl or heterocyclyl substituted by one to ten substituents R10;

R9 is hydrogen, CrC₆alkyl, CrC₆alkoxy, or d-C₆haloalkyl; each R10 is independently cyano, nitro, amino, hydroxy, halogen, CrC₆alkyl, d-C₆halo- alkyl, Ci-C₄alkoxy-Ci-C₄alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂- C₆haloalkynyl, C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl, Ci-C₆alkoxy, CrC₆haloalkoxy, C C₄alkoxy-Ci-C₄alkoxy, CrC₆alkylthio, CrC₆haloalkylthio, CrC₆alkylsulfinyl, d- C₆haloalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylsulfonyl, N-d-dalkylamino, N,N- di-(d-dalkyl)amino, N,N-di-(d-C₆alkyl)aminocarbonyl, N,N-di-(d-dalkyl)- aminosulfonyl, d-C₆alkylcarbonyl, d-dalkylcarbonyloxy, d-C₆alkoxycarbonyl, d- C₆alkylcarbonylamino; or salts or N-oxides thereof.

The compounds of Formula (A) thus exist as:

Formula (I)

Or Formula (II)

Compounds of formula (A) may exist in different geometric or optical isomers (diastereoisomers and enantiomers) or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. The invention also covers all salts, N-oxides, and metalloidic complexes of the compounds of Formula (A).

In a second aspect, the invention provides herbicidal compositions comprising a compound of the invention together with at least one agriculturally acceptable adjuvant or diluent. In a third aspect, the invention provides a method of controlling weeds in crops of useful plants, comprising applying to said weeds or to the locus of said weeds, or to said useful crop plants, a compound or a composition of the invention.

Detailed Description

The compounds of formula (A) may exist in different geometric or optical isomers (diastereoisomers and enantiomers) or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. The invention also covers all salts, N-oxides, and metalloidic complexes of the compounds of formula (A).

Each W is independently O or S. Preferably, both W are the same. More preferably, both W are O.

In one embodiment, at least one of A1 , A2 or A4 is nitrogen. Preferably, A1 is CR1 and at least one of A2 or A4 is N. More preferably, A1 and A4 are C-R1 and A2 is N, respectively.

In particularly preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10, in formula (A), are as set out below.

A1 and A4 are C-R1

A2 is N;

R1 is H, cyano, halogen, d-Cealkyl, or R1 is d-Cealkyl substituted by one or more halogen, hydroxyl or amine;

A3 is C-X;

X is halogen, d-Cehaloalkyl, cyano, d-Cehaloalkoxy, CrCehaloalkylthio,

C-|-C₆haloalkylsulfinyl, C-|-C₆haloalkylsulfonyl; or X is heteroaryl or heteroaryl subtituted by one or more halogen, cyano, d-Csalkyl;

Q is formula (i);

W is O;

R2 is H or C C₆alkyl;

R3, R4, R5 and R6 are independently hydrogen, halogen, cyano, CrC₃alkyl or d- C₃haloalkyl; R7 is hydrogen, CrC₆alkyl, CrC₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, or R7 is CrC₆ alkyl substituted by Ci-C₆alkoxy or d-C₆alkylthio.

In even more preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10, in formula (A), are as set out below.

A1 and A4 are C-R1

A2 is N;

R1 is H;

A3 is C-X;

X is halogen, CrC₆haloalkyl, cyano;

Q is formula (i);

W is O;

R3, R4, R5 and R6 are independently hydrogen.

R7 is hydrogen, CrC₆alkyl, CrC₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, or R7 is CrC₆ alkyl substituted by Ci-C₃alkoxy or Ci-C₃alkylthio.

In particularly preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10 in formula (A), are as set out below.

A1 and A4 are C-R1

A2 is N;

R1 is H, cyano, halogen, Ci-C₆alkyl, or R1 is d-C₆alkyl substituted by one or more halogen, hydroxyl or amine;

A3 is C-X;

X is halogen, CrC₆haloalkyl, cyano, Ci-C₆haloalkoxy, CrC₆haloalkylthio,

CrC₆haloalkylsulfinyl, Ci-C₆haloalkylsulfonyl; or X is heteroaryl or heteroaryl subtituted by one or more halogen, cyano, d-C₃alkyl;

R2 and Q form the cyclic group according to formula (ii);

W is O;

R3, R4, R5 and R6 are independently hydrogen, halogen, cyano, CrC₃alkyl or d- C₃haloalkyl. In even more preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6 , R7 , R10, in formula (A), are as set out below.

A1 and A4 are C-R1

A2 is N;

R1 is H;

A3 is C-X;

X is halogen, CrC₆haloalkyl, cyano

R2 and Q form the cyclic group according to formula (ii);

W is O;

R3, R4, R5 and R6 are independently hydrogen.

In particularly preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10, in formula (A), are as set out below.

A1 , A2, and A4 are C-R1 ;

R1 is H, cyano, halogen, d-C₆alkyl, or R1 is CrC₆alkyl substituted by one or more halogen, hydroxyl or amine;

A3 is C-X;

X is halogen, d-Cehaloalkyl, cyano, d-Cehaloalkoxy, CrCehaloalkylthio,

CrC₆haloalkylsulfinyl, Ci-C₆haloalkylsulfonyl; or X is heteroaryl or heteroaryl subtituted by one or more halogen, cyano, CrC₃alkyl;

Q is formula (i);

W is O;

R2 is H or C C₆alkyl;

R3, R4, R5 and R6 are independently hydrogen, halogen, cyano, C-|-C₃alkyl or C

C₃haloalkyl;

R7 is hydrogen, CrC₆alkyl, CrC₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, or R7 is CrC₆ alkyl substituted by d-Cealkoxy or d-Cealkylthio.

In even more preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10, in formula (A), are as set out below.

A1 , A2, and A4 are C-R1 ;

R1 is H;

A3 is C-X; X is halogen, CrC₆haloalkyl, cyano

Q is formula (i);

W is O;

R3, R4, R5 and R6 are independently hydrogen.

R7 is hydrogen, CrC₆alkyl, CrC₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, or R7 is CrC₆ alkyl substituted by Ci-C₃alkoxy or d-C₃alkylthio.

In particularly preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10, in formula (A), are as set out below.

A1 , A2 and A4 are C-R1 ;

R1 is H, cyano, halogen, Ci-C₆alkyl, or R1 is CrC₆alkyl substituted by one or more halogen, hydroxyl or amine;

A3 is C-X;

X is halogen, CrC₆haloalkyl, cyano, Ci-C₆haloalkoxy, CrC₆haloalkylthio,

CrC₆haloalkylsulfinyl, Ci-C₆haloalkylsulfonyl; or X is heteroaryl or heteroaryl subtituted by one or more halogen, cyano, d-Caalkyl;

R2 and Q form the cyclic group according to formula (ii);

W is O;

R3, R4, R5 and R6 are independently hydrogen, halogen, cyano, CrC₃alkyl or d- C₃haloalkyl.

In even more particularly preferred embodiments of the invention, the preferred groups for W, X, A1 , A2, A3, A4, R1 , R2, R3, R4, R5, R6, R7, R10, in formula (A), are as set out below.

A1 , A2, and A4 are C-R1 ;

R1 is H or halogen;

A3 is C-X;

X is halogen, d-Cehaloalkyl, cyano

R2 and Q form the cyclic group according to formula (ii);

W is O;

R3, R4, R5 and R6 are independently hydrogen.

In any one of the above:

More preferably, X is halogen, Ci-C₆ haloalkyl or cyano. More preferably R1 , R2, R3, R4, R5 and R6 are independently hydrogen or Ci-C₃alkyl. Most preferably, R1 , R2, R3, R4, R5 and/or R6 are hydrogen.

Preferably, when A2 is C-R1 , R1 is hydrogen, CrC₃alkyl or Ci-C₃alkoxy.

More preferably R7 is hydrogen, methyl or ethyl. Most preferably, R7 is hydrogen or methyl.

All preferred combinations of substituents are herewith disclosed.

The herbicidal compounds of formula (A) may exist as different geometric isomers, or in different tautomeric forms. This invention covers all such isomers and tautomers, and mixtures thereof in all proportions, as well as isotopic forms such as deuterated compounds.

The herbicidal compounds of this invention may contain an asymmetric carbon atom and some of the compounds of this invention may contain one or more asymmetric centers and may thus give rise to optical isomers and diastereomers. While shown without respect to stereochemistry, the present invention includes such optical isomers and diastereomers; as well as the racemic and resolved, enantiomerically pure R and S stereoisomers; as well as other mixtures of the R and S stereoisomers and agrochemically acceptable salts thereof. It is recognized that one optical isomer, including diastereomer and enantiomer, or stereoisomer may have favorable properties over the other. Thus when disclosing and claiming the invention, when one racemic mixture is disclosed, it is clearly contemplated that both optical isomers, including diastereomers and enantiomers, or stereoisomers substantially free of the other are disclosed and claimed as well.

Each alkyl moiety either alone or as part of a larger group (such as alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl) is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or isopentyl, neo-pentyl, n-hexyl, and isohexyl. The alkyl groups are preferably Ci to C₆ alkyl groups, more preferably Ci to C₄ and most preferably Ci toC₃ alkyl groups.

Each alkenyl moiety either alone or as part of a larger group (such as alkenoxy, alkenoxycarbonyl, alkenylcarbonyl, alkenylaminocarbonyl, dialkenylaminocarbonyl) is having at least one carbon-carbon double bond , preferably one double bond, is, for example, vinyl, allyl. The alkenyl groups are preferably C₂ to C₆alkenyl groups, more preferably C₂-C₄alkenyl groups e. g. of 2 to 6 carbon atoms such as ethenyl (vinyl), prop- 1-enyl, prop-2-enyl (allyl), isopropenyl, but-1 -enyl, but-2-enyl, but-3-enyl, 2- methylpropenyl.

Each alkynyl moiety either alone or as part of a larger group (such as alkynoxy, alkynoxycarbonyl, alkynylcarbonyl, alkynylaminocarbonyl, dialkynylaminocarbonyl) is having at least one carbon-carbon triple bond and is, for example, ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl) but-1-ynyl, but-2-ynyl and but-3-ynyl. The alkynyl groups are preferably C₂ to C₆alkynyl groups, more preferably C₂-C₄alkynyl groups. The term "alkynyl", as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon triple bond wherein alkyl is as defined above.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups (either alone or as part of a larger group, such as haloalkoxy or haloalkylthio) are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, -CF₃, -CF₂CI, -CH₂CF₃ or -CH₂CHF₂.

Hydroxyalkyl groups are alkyl groups which are substituted with one or more hydroxyl group and are, for example, -CH₂OH, -CH₂CH₂OH or -CH(OH)CH₃.

In the context of the present specification the term "aryl" refers to a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl,

naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.

Unless otherwise indicated, alkenyl and alkynyl, on their own or as part of another substituent, may be straight or branched chain and may preferably contain 2 to 6 carbon atoms, preferably 2 to 4, more preferably 2 to 3, and where appropriate, may be in either the (E)- or (Z)-configuration. Examples include vinyl, allyl and propargyl.

Unless otherwise indicated, cycloalkyi may be mono- or bi-cyclic, may be optionally substituted by one or more CrC₆alkyl groups, and preferably contain 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms. Examples of cycloalkyi include cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Cycloalkyi, as used herein, refers to a cyclic, saturated hydrocarbon group having from 3 to 6 ring carbon atoms. Examples of cycloalkyi groups are cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

Alkoxy as used herein refers to the group -OR, wherein R is alkyl as defined above. Examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n- butoxy, isobutoxy, sec-butoxy, t-butoxy, n-pentoxy, isopentoxy, neo-pentoxy, n- hexyloxy, and isohexyloxy.

Alkenyloxy refers to the group -OR, wherein R is alkenyl as defined above. Examples of alkenyloxy groups are ethenyloxy, propenyloxy, isopropenyloxy, but-1- enyloxy, but-2-enyloxy, but-3-enyloxy, 2-methypropenyloxy etc.

Alkynyloxy refers to the group -OR, wherein R is alkynyl is as defined above. Examples of alkynyloxy groups are ethynyloxy, propynyloxy, but-1 -ynyloxy, but-2- ynyloxy and but-3-ynyloxy.

Alkoxyalkyl as used herein refers to the group -ROR, wherein each R is, independently, an alkyl group as defined above.

Alkoxyalkenyl as used herein refers to the group -ROR', wherein R is an alkyl group as defined above and R' is an alkenyl group as defined above

Alkoxyalkynyl as used herein refers to the group -ROR', wherein R is an alkyl group as defined above and R is an alkynyl group as defined above.

Cyanoalkyl as used herein refers to an alkyl group substituted with one or more cyano groups.

Cyanoalkenyl as used herein refers to an alkenyl group substituted with one or more cyano groups.

Cyanoalkynyl as used herein refers to an alkynyl group substituted with one or more cyano groups.

Cyanocycloalkyl as used herein refers to an cycloalkyl group substituted with one or more cyano groups.

Cyanoalkoxy as used herein refers to the group -OR, wherein R is cyanoalkyl as defined above.

Halogen, halide and halo refer to iodine, bromine, chlorine and fluorine.

Haloalkyi as used herein refers to an alkyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Examples of haloalkyi groups include chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl and trifluoromethyl. Preferred haloalkyi groups are fluoroalkyi groups {i.e. haloalkyi groups, containing fluorine as the only halogen). More highly preferred haloalkyi groups are perfluoroalkyi groups, i.e. alkyl groups wherein all the hydrogen atoms are replaced with fluorine atoms.

Haloalkenyl as used herein refers to an alkenyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above. Haloalkynyl as used herein refers to an alkynyl group as defined above wherein at least one hydrogen atom has been replaced with a halogen atom as defined above.

Haloalkoxy as used herein refers to the group -OR, wherein R is haloalkyl as defined above.

Haloalkenyloxy as used herein refers to the group -OR, wherein R is haloalkenyl as defined above.

Haloalkynyloxy as used herein refers to the group -OR, wherein R is haloalkynyl as defined above.

Alkylthio as used herein refers to the group -SR, wherein R is an alkyl group as defined above. Alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, tert-butylthio, and the like.

Alkylthioalkyl as used herein refers to the group -RSR, wherein each R is, independently, an alkyl group as defined above

Haloalkylthio as used herein refers to the group -SR, wherein R is a haloalkyl group as defined above.

Alkylsulfinyl as used herein refers to the group -S(0)R, wherein R is an alkyl group as defined above.

Alkylsulfonyl as used herein refers to the group -S(0)₂R, wherein R is an alkyl group as defined above.

Haloalkylsulfinyl as used herein refers to the group -S(0)R, wherein R is a haloalkyl group as defined above.

Haloalkylsulfonyl as used herein refers to the group -S(0)₂R, wherein R is a haloalkyl group as defined above.

Alkylsulfonyloxy, as used herein refers to the group -OS0₂R, wherein R is an alkyl group as defined above.

Alkylcarbonyl, as used herein refers to the group -COR, wherein R is an alkyl group as defined above. Examples of alkylcarbonyl groups include ethanoyl, propanoyl, n-butanoyl, etc.

Alkenylcarbonyl, as used herein refers to the group -COR, wherein R is an alkenyl group as defined above.

Alkynylcarbonyl, as used herein refers to the group -COR, wherein R is an alkynyl group as defined above.

Haloalkylcarbonyl, as used herein refers to the group -COR, wherein R is a haloalkyl group as defined above.

Haloalkenylcarbonyl, as used herein refers to the group -COR, wherein R is a haloalkenyl group as defined above. Haloalkynylcarbonyl, as used herein refers to the group -COR, wherein R is a haloalkynyl group as defined above.

Alkoxycarbonyloxy as used herein, refers to the group -OC(0)OR, wherein R is an alkyl group as defined above. Examples of alkoxycarbonyloxy groups are methoxycarbonyloxy, ethoxycarbonyloxy, propoxycarbonyloxy, but-1-oxycarbonyloxy, but-2-oxycarbonyloxy and but-3-oxycarbonyloxy.

Alkenyloxycarbonyloxy, as used herein, refers to the group -OC(0)OR, wherein R is an alkenyl group as defined above.

Alkynyloxycarbonyloxy, as used herein, refers to the group -OC(0)OR, wherein R is an alkynyl group as defined above.

Haloalkoxycarbonyloxy, as used herein, refers to the group -OC(0)OR, wherein R is a haloalkyl group as defined above.

Formyl, as used herein, refers to the group -C(0)H.

Hydroxy or hydroxyl, as used herein, refers to the group -OH.

Nitro, as used herein, refers to the group -N0₂.

Cyano as used herein, refers to the group -CN.

Aryl, as used herein, refers to an unsaturated aromatic carbocyclic group of from 6 to 10 carbon atoms having a single ring (e. g., phenyl) or multiple condensed (fused) rings, at least one of which is aromatic (e.g., indanyl, naphthyl). Preferred aryl groups include phenyl, naphthyl and the like. Most preferably, an aryl group is a phenyl group.

Aryloxy, as used herein, refers to the group -O-aryl, wherein aryl is as defined above. Preferred aryloxy groups include phenoxy, naphthyloxy and the like.

Benzyl, as used herein, refers to the group -CH₂C₆H₅.

Benzyloxy, as used herein, refers to the group -OCH₂C₆H₅.

Heterocyclyl, as used herein, is defined to include heteroaryl and in addition their saturated, unsaturated or partially unsaturated analogues, and refers to a non-aromatic ring system containing 3 to 10 ring atoms, at least one ring heteroatom and consisting either of a single ring or of two or more fused rings. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyrrolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, quinuclidinyl, morpholinyl, together with unsaturated or partially unsaturated analogues such as 4,5,6,7-tetrahydro- benzothiophenyl, chromen-4-onyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-l,4-dioxepinyl, 2,3-dihydro-benzofuranyl, piperidinyl, 1 ,3-dioxolanyl, 1 ,3-dioxanyl, 4,5-dihydro- isoxazolyl, tetrahydrofuranyl and morpholinyl. Heteroaryl, as used herein, refers to a ring system containing 5 to 10 ring atoms, 1 to 4 ring heteroatoms and consisting either of a single aromatic ring or of two or more fused rings, at least one of which is aromatic. Preferably, single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur. Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl. Examples of bicyclic groups are benzothiophenyl, benzimidazolyl, benzothiadiazolyl, quinolinyl, cinnolinyl, quinoxalinyl and pyrazolo[1 ,5-a]pyrimidinyl.

Optionally substituted' as used herein means the group referred to can be substituted at one or more positions by any one or any combination of the radicals listed thereafter. For most groups, one or more hydrogen atoms are replaced by the radicals listed thereafter. For halogenated groups, for example, haloalkyl groups, one or more halogen atoms are replaced by the radicals listed thereafter.

Suitable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines. Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N⁺(R¹⁹R²⁰R²¹ R²²) wherein R¹⁹, R²⁰, R²¹ and R²² are independently selected from hydrogen, C-|-C₆ alkyl and C-|-C₆ hydroxyalkyl. Salts of the compounds of Formula I can be prepared by treatment of compounds of Formula I with a metal hydroxide, such as sodium hydroxide, or an amine, such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine. Amine salts are often preferred forms of the compounds of Formula I because they are water-soluble and lend themselves to the preparation of desirable aqueous based herbicidal compositions.

Acceptable salts can be formed from organic and inorganic acids, for example, acetic, propionic, lactic, citric, tartaric, succinic, fumaric, maleic, malonic, mandelic, malic, phthalic, hydrochloric, hydrobromic, phosphoric, nitric, sulfuric, methanesulfonic, naphthalenesulfonic, benzenesulfonic, toluenesulfonic, camphorsulfonic, and similarly known acceptable acids when a compound of this invention contains a basic moiety.

The compounds of formula (A) can be prepared according to the applications filed as EP1 1 181633.6 (EP 2 570 406), EP1 1 181635.1 (EP 2 570 404), GB1 121539.9, and GB1207758.2. The compounds of formula (A) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herbicidal compositions in various ways using formulation adjuvants, such as carriers, solvents and surface-active substances. Therefore, the invention also relates to a herbicidal composition which comprises a herbicidally effective amount of a compound of formula (A) in addition to formulation adjuvants. The formulations can be in various physical forms, e.g. in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-flowables, aqueous dispersions, oily dispersions, suspo-emulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water- miscible organic solvent as carrier), impregnated polymer films or in other forms known e.g. from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999. Such formulations can either be used directly or they are diluted prior to use. The dilutions can be made, for example, with water, liquid fertilizers, micronutrients, biological organisms, oil or solvents.

The formulations can be prepared e.g. by mixing the active ingredient with the formulation adjuvants in order to obtain compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof. The active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredients to be released into the environment in controlled amounts (e.g. slow-release). Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural or synthetic rubbers, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyesters, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers that are known to the person skilled in the art in this connection. Alternatively, very fine microcapsules can be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of base substance, but the microcapsules are not themselves encapsulated.

The formulation adjuvants that are suitable for the preparation of the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2- butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloropropane, diethanolamine, p- diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, Λ/,/V-dimethyl- formamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidone, ethyl acetate, 2- ethylhexanol, ethylene carbonate, 1 ,1 ,1 -trichloroethane, 2-heptanone, alpha-pinene, d- limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n- octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and alcohols of higher molecular weight, such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, /V-methyl-2-pyrrolidone and the like. Water is generally the carrier of choice for diluting the concentrates. Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances, as described, for example, in CFR 180.1001 . (c) & (d). A large number of surface-active substances can advantageously be used in both solid and liquid formulations, especially in those formulations which can be diluted with a carrier prior to use. Surface-active substances may be anionic, cationic, non-ionic or polymeric and they can be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol/alkylene oxide addition products, such as nonylphenol ethoxylate; alcohol/alkylene oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonat.es, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di- alkylphosphate esters; and also further substances described e.g. in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 .

Further adjuvants that can usually be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing auxiliaries, antifoams, complexing agents, neutralizing or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, antifreezes, microbicides, and also liquid and solid fertilizers.

The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally from 0.01 to 10 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rhone-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers. Especially preferred oil additives comprise alkyl esters of C₈-C₂2 fatty acids, especially the methyl derivatives of Ci₂-Ci₈ fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being of importance. Those esters are known as methyl laurate (CAS-1 1 1-82-0), methyl palmitate (CAS-1 12-39-0) and methyl oleate (CAS-1 12-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH). Those and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.

The application and action of the oil additives can be further improved by combination with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485. Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available surfactants are the Genapol types (Clariant AG). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants. The concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight. Examples of oil additives consisting of mixtures of oil or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Syngenta AG, CH) or ActipronC (BP Oil UK Limited, GB).

If desired, it is also possible for the mentioned surface-active substances to be used in the formulations on their own, that is to say, without oil additives.

Furthermore, the addition of an organic solvent to the oil additive/surfactant mixture may contribute to an additional enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) or Aromatic Solvent® (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight. Oil additives that are present in admixture with solvents are described, for example, in US- A-4,834,908. A commercially available oil additive disclosed therein is known by the name MERGE® (BASF Corporation). A further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada). In addition to the oil additives listed above, for the purpose of enhancing the action of the compositions according to the invention it is also possible for formulations of alkylpyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-1 -p-menthene (e.g. Bond®, Courier® or Emerald®) may also be used. It is also possible for solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, to be added to the spray mixture as action-enhancing agent.

The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of formula (A) and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The rates of application of compounds of formula (A) may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the grass or weed to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of formula (A) according to the invention are generally applied at a rate of from 10 to 2000 g/ha, especially from 50 to 1000 g/ha.

Preferred formulations have especially the following compositions (% = percent by weight):

Emulsifiable concentrates

active ingredient: 1 to 95 %, preferably 60 to 90 %

surface-active agent: 1 to 30 %, preferably 5 to 20 %

liquid carrier: 1 to 80 %, preferably 1 to 35 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 5 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 % Suspension concentrates:

active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.1 to 30 %, preferably 0.1 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The following Examples further illustrate, but do not limit, the invention. Formulation Examples for herbicides of formula (A) (% = % by weight)

F1 . Emulsifiable concentrates a) b) c)

d)

active ingredient 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % - 4 % 4 %

(36 mol of ethylene oxide)

octylphenol polyglycol ether - 4 % - 2 %

(7-8 mol of ethylene oxide)

NMP - - 10 % 20 % arom. hydrocarbon mixture 85 % 78 % 55 % 16 %

Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.

F2. Solutions a) b) c) d) active ingredient 5 % 10 % 50 % 90 %

1 -methoxy-3-(3-methoxy- propoxy)-propane - 20 % 20 %

polyethylene glycol MW 400 20 % 10 %

NMP - - 30 % 10 % arom. hydrocarbon mixture 75 % 60 %

The solutions are suitable for use in the form of microdrops. F3. Wettable powders a) b) c) d) active ingredient 5 % 25 % 50 % 80 % sodium lignosulfonate 4 % - 3 %

sodium lauryl sulfate 2 % 3 % - 4 % sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2 %

(7-8 mol of ethylene oxide)

highly dispersed silicic acid 1 % 3% 5% 10% kaolin 88% 62% 35%

The active ingredient is mixed thoroughly with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.

F4. Coated granules a) b) c)

active ingredient 0.1 % 5% 15%

highly dispersed silicic acid 0.9 % 2% 2%

inorganic carrier 99.0 % 93% 83%

(diameter 0.1 - 1 mm)

e.g. CaC0₃ orSi0₂

The active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.

F5. Coated qranules a) b) c)

active ingredient 0.1 % 5% 15% polyethylene glycol MW 200 1.0 % 2% 3% highly dispersed silicic acid 0.9 % 1 % 2% inorganic carrier 98.0 % 92% 80%

(diameter 0.1 - 1 mm)

e.g. CaC0₃ orSi0₂ The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

F6. Extruder qranules a) b) c) d) active ingredient 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethyl cellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79%

The active ingredient is mixed and ground with the adjuvants, and the mixture i moistened with water. The mixture is extruded and then dried in a stream of air.

F7. Dusts a) b) c)

active ingredient 0.1 % 1 % 5%

talcum 39.9 % 49% 35%

kaolin 60.0 % 50% 60%

Ready-to-use dusts are obtained by mixing the active ingredient with the carriers an grinding the mixture in a suitable mil I.

F8. Suspension concentrates a) b) c) d) active ingredient 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenol polyglycol ether - 1 % 2% -

(15 mol of ethylene oxide)

sodium lignosulfonate 3% 3% 4% 5% carboxymethyl cellulose 1 % 1 % 1 % 1 %

37 % aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution

silicone oil emulsion 0.8 % 0.8 % 0.8 % 0.8 % water 87% 79% 62% 38%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. The invention also relates to a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (A). The invention also relates to a method of inhibiting plant growth which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound of formula (A).

The invention also relates to a method of selectively controlling grasses and weeds in crops of useful plants which comprises applying to the useful plants or locus thereof or to the area of cultivation a herbicidally effective amount of a compound of formula (A).

The term "herbicide" as used herein means a compound that controls or modifies the growth of plants. The term "herbicidally effective amount" means the quantity of such a compound or combination of such compounds that is capable of producing a controlling or modifying effect on the growth of plants. Controlling or modifying effects include all deviation from natural development, for example: killing, retardation, leaf burn, albinism, dwarfing and the like. The term "plants" refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits. The term "locus" is intended to include soil, seeds, and seedlings, as well as established vegetation and includes not only areas where weeds may already be growing, but also areas where weeds have yet to emerge, and also to areas under cultivation with respect to crops of useful plants. "Areas under cultivation" include land on which the crop plants are already growing and land intended for cultivation with such crop plants. The term "weeds" as used herein means any undesired plant, and thus includes not only agronomically important weeds as described below, but also volunteer crop plants. The compounds of the invention can be applied before or after planting of the crops, before weeds emerge (pre-emergence application) or after weeds emerge (post- emergence application), and are particularly effective when applied post-emergence to the weeds. Crops of useful plants in which the composition according to the invention can be used include, but are not limited to, perennial crops, such as citrus fruit, grapevines, nuts, oil palms, olives, pome fruit, stone fruit and rubber, and annual arable crops, such as cereals, for example barley and wheat, cotton, oilseed rape, maize, rice, soy beans, sugar beet, sugar cane, sunflowers, ornamentals, switchgrass, turf and vegetables, especially cereals, maize and soy beans.

The grasses and weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eriochloa, Lolium, Monochoria, Panicum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sida and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Galium, Ipomoea, Kochia, Nasturtium, Polygonum, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.

Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides (e.g. auxins or ALS-, EPSPS-, PPO- and HPPD-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®, respectively.

Crops are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesize such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding ("stacked" transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.

Crops are also to be understood as being those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavor).

Any method of application to weeds/crop of useful plant, or locus thereof, which is routinely used in agriculture may be used, for example application by spray or broadcast method typically after suitable dilution of a compound of formula (A) (whether said compound is formulated and/or in combination with one or more further active ingredients and/or safeners, as described herein).

The compounds of formula (A) according to the invention can also be used in combination with other active ingredients, e.g. other herbicides, and/or insecticides, and/or acaricides, and/or nematocides, and/or molluscicides, and/or fungicides, and/or plant growth regulators. Such mixtures, and the use of such mixtures to control weeds and/or undesired plant growth, form yet further aspects of the invention. For the avoidance of doubt, mixtures of invention also include mixtures of two or more different compounds of formula (A). In particular, the present invention also relates to a composition of the invention which comprises at least one further herbicide in addition to the compound of formula (A).

In a further aspect of the present invention, the herbicidal compounds or composition of the present invention may be applied in combination with one or more compounds having a pesticidal effect. Such compounds include those that possess fungicidal, safening, plant growth regulation, insecticidal, nematicidal or acaricidal activity, or even other compounds also having herbicidal activity.

In a further aspect of the present invention, the compounds or composition of the present invention may be applied in combination with one or more other compounds having a crop enhancement effect. Such compounds include micronutrients, saccharides, amino acids, flavonoids, quinines, and plant activators / growth stimulators. For example, such compounds include natural or synthetic hormones, auxins, brassinosteroids, gibberellins, abscisic acid, cytokinins, jasmonates, strigolactones, salicylic acid, ethylene, 1-methylcyclopropene, trinexapac-ethyl or derivatives thereof. Such compounds also include pesticides that have a crop enhancement effect, for example strobilurins (including azoxystrobin, pyraclostrobin), and neonicotinoids

(including thiamethoxam, and imidacloprid).

The mixing ratio of the compound of formula (A) to the mixing partner is preferably from 1 : 1000 to 1000: 1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (A) with the mixing partner).

The compounds of formula (A) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of formula (A) according to the invention with one or more further active ingredients, in particular with one or more further herbicides, can also be used in combination with one or more safeners. The term "safener" as used herein means a chemical that when used in combination with a herbicide reduces the undesirable effects of the herbicide on non- target organisms, for example, a safener protects crops from injury by herbicides but does not prevent the herbicide from killing the weeds. Where a compound of formula (A) is combined with a safener, the following combinations of the compound of formula (A) and the safener are particularly preferred. Compound of formula (A) + AD 67 (MON 4660), compound of formula (A) + benoxacor, compound of formula (A) + cloquintocet- mexyl, compound of formula (A) + cyometrinil and a compound of formula (A) + the corresponding (Z) isomer of cyometrinil, compound of formula (A) + cyprosulfamide (CAS RN 221667-31-8), compound of formula (A) + dichlormid, compound of formula (A) and dicyclonon, compound of formula (A) and dietholate, compound of formula (A) + fenchlorazole-ethyl, compound of formula (A) + fenclorim, compound of formula (A) + flurazole, compound of formula (A) + fluxofenim, compound of formula (A) + furilazole and a compound of formula (A) + the corresponding R isomer or furilazome, compound of formula (A) + isoxadifen-ethyl, compound of formula (A) + mefenpyr-diethyl, compound of formula (A) and mephenate, compound of formula (A) + oxabetrinil, compound of formula (A) + naphthalic anhydride (CAS RN 81-84-5), compound of formula (A) and TI-35, compound of formula (A) + N-isopropyl-4-(2-methoxy- benzoylsulfamoyl)-benzamide (CAS RN 221668-34-4) and a compound of formula (A) + N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]benzenesulfonamide.

Particularly preferred are mixtures of a compound of formula (A) with benoxacor, a compound of formula (A) with cloquintocet-mexyl, a compound of formula (A) + cyprosulfamide and a compound of formula (A) with N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide.

The safeners of the compound of formula (A) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 14th Edition (BCPC), 2006. The reference to cloquintocet-mexyl also applies to cloquintocet and to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO02/34048 and the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

Preferably the mixing ratio of compound of formula (A) to safener is from 100:1 to 1 :10, especially from 20:1 to 1 :1.

The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of formula (A) and any further active ingredient, in particular a further herbicide, with the safener).

It is possible that the safener and a compound of formula (A) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (A) and one or more additional herbicide(s), if any, might be applied to the locus pre-emergence or might be applied to the crop post-emergence. It is also possible that the safener and a compound of formula (A) and one or more additional herbicide(s), if any, are applied sequentially. For example, the safener might be applied before sowing the seeds as a seed treatment and a compound of formula (A) and one or more additional herbicides, if any, might be applied to the locus pre- emergence or might be applied to the crop post-emergence.

Various aspects and embodiments of the present invention will now be illustrated in more detail by way of example. It will be appreciated that modification of detail may be made without departing from the scope of the invention.

For the avoidance of doubt, where a literary reference, patent application, or patent, is cited within the text of this application, the entire text of said citation is herein incorporated by reference. Examples

Compound Formula (I) wherein W is O, R2 is H, R3 and R5 are H.

Compound A1 A2 A3 A4 R4 R6 R7

number

A1 C-H N C-Br C-H H H H

C-

A2 C-H OCH2CH3 C-CI C-H H H CH3

A3 C-H C-H C-CF3 C-H H H CH2CCH

A4 C-H C-H C-CN C-H H H CH2CH3

A5 C-H N C-Br C-H H H CH2CH2SCH3

A6 C-H C-H C-CF3 C-H H H CH2CH2SCH3

A7 C-H C-H C-CN C-H H H H

A8 C-H C-H C-CN C-H H H CH2Ph

A9 C-H C-H C-CI C-H H H CH2CH2CHCH2

A10 C-H N C-Br C-H H H CH2CHCH2

C-

A1 1 C-H OCH2CH3 C-Br C-H H H H

A12 C-H CH C-CF3 C-H H H CH2CHCI2

A13 C-H N C-CI C-H H H CH3

A14 C-H N C-Br C-H H H CH2CH2CH2CH3

A15 C-H N C-CI C-H H H H

A16 C-H N C-Br C-H H H CH2CH2CHCH2

A17 C-H C-H C-Br C-H H H H

A18 C-H C-H C-CN C-H H H CH3

A19 C-H C-H C-CF3 C-H H H CH3

A20 C-H C-H C-CI C-H H H CH2CH20CH3

A21 C-H N C-Br C-H H H CH2(CH2)3CH3 A22 C-H N C-Br C-H H H CH2CH(CH3)CH2CH3

A23 C-H C-H C-F C-H H H CH3

A24 C-H C-H C-SCH3 C-H H H CH3

C-

A25 C-H N CF(CF3)2 C-H H H H

A26 C-H C-H C-CF3 C-H H H H

A27 C-H N C-Br C-H H H CH2CH(CH2)4

A28 C-H N C-Br C-H H H CH(CH3)CH2CH2CH3

A29 C-H N C-CI C-H H H CH2CH2CHCH2

A30 C-H C-CI C-CI C-H H H CH3

A31 C-H N C-Br C-H H H CH2CF3

A32 C-H N C-Br C-H H H CH2CCH

A33 C-H N C-CF3 C-H H H CH3

A34 C-H N C-Br C-H H H CH3

A35 C-H C-H C-CF3 C-H H H CH2CHCH2

A36 C-H C-H C-CF3 C-H H H CH2CH2CHCH2

A37 C-H C-0CH3 C-CI C-H H H CH3

A38 C-H C-H C-Br C-H H H CH2(CH2)2CF3

A39 C-H N C-CI C-H H H CH2CHCH2

A40 C-H C-H C-CF3 C-H H H CH2CF3

A41 C-H C-H C-Br C-H H H CH2(CH2)2CH3

A42 C-H N C-CI C-H H H CH2(CH2)2CH3

A43 C-H C-0CH3 C-Br C-H H H CH3

A44 C-H N C-Br C-H H H CH2CH20CH3

A45 C-H C-H C-CF3 C-H H H CH2(CH2)2CH3

A46 C-H C-H C-Br C-H H H CH2CCH

A47 C-H C-H C-Br C-H H H CH2CHCH2

C-

A48 C-H OCH2CH3 C-Br C-H H H CH3

A49 C-H C-H C-Br C-H H H CH2CH2CHCH2

A50 C-H C-H C-Br C-H H H CH2CH2SCH3

C-

A51 C-H N CF2CF3 C-H H H CH3

C-

A52 Cl N C-CI C-H H H H

A53 C-H C-H C-Br C-H H H CH2CF3

A54 C-H C-H C-CI C-H H H CH3

A55 C-H C-H C-CHF2 C-H H H CH3

A56 C-H C-H C-Br C-H H H CH2CHCI2

A57 C-H C-H C-Br C-H H H CH2CH20CH3

A58 C-H C-H C-l C-H H H H

A59 C-H C-H C-CF3 C-H H H H

A60 C-H C-H C-CI C-H H H H

A61 C-H C-H C-Br C-H H H H

A62 C-H C-H C-l C-H H H CH2CH3

A63 C-H C-H C-Br C-H H CH3 H

A64 C-H C-H C-Br C-H H CH4 CH3

A65 C-H C-CF3 C-CF3 C-H H H CH3

A66 C-H C-CF3 C-CF3 C-H H H H Compound Formula (II) wherein W is O, R3 and R5 are H.

Example 1

Herbicidal action Example 1 a: Pre-emergence herbicidal activity

Seeds of a variety of test species were sown in unsterilised compost in small pots. After cultivation for one day (pre-emergence) in controlled conditions in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) the plants were sprayed with 1 mg of the active ingredient, formulated in 466 μΙ of an acetone / water / Tween 20 (49.75:49.75:0.5) solution, which is equivalent to 1000 g/ha. Once the foliage was dry, the pots were kept in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), and were watered twice daily. After 12 days the test was evaluated and scored (100 = total damage to plant, 0 = no damage to plant). Results shown in Table 1.

Table 1 : Application pre-emerqence

Example 1 b: Post-emergence herbicidal activity

Seeds of a variety of test species were sown in unsterilised compost in small pots. After cultivation for seven days (post-emergence) in controlled conditions in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) the plants were sprayed with 1 mg of the active ingredient, formulated in 466 μΙ of an acetone / water / Tween 20 (49.75:49.75:0.5) solution, which is equivalent to 1000 g/ha. Once the foliage was dry, the pots were kept in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), and were watered twice daily. After 12 days the test was evaluated and scored (100 = total damage to plant, 0 = no damage to plant). Results are shown in Table 2.

Table 2: Application post-emergence

Compound Rate

AMARE STEME LOLPE DIGSA

Number (g/ha)

A1 1000 50 40 20 60

A2 1000 70 30 10 20

A3 1000 40 60 0 0

A4 1000 40 40 0 60

A5 1000 60 50 0 60

A6 1000 20 40 0 0

A7 1000 20 40 20 40

A8 1000 20 40 0 50

A9 1000 0 0 30 40

A10 1000 60 50 0 40

A1 1 1000 50 0 0 0

A12 1000 40 50 0 50

A13 1000 50 50 0 70

A14 1000 60 60 0 50

A15 1000 40 50 0 70

A16 1000 60 50 0 70

A17 1000 30 60 20 60

A18 1000 30 60 20 60

A19 1000 40 50 0 40

A20 1000 30 40 0 40

A21 1000 50 50 0 80

A22 1000 60 80 0 80

A23 1000 40 20 0 0

A24 1000 0 40 0 0

A25 1000 40 40 0 0

A26 1000 40 0 0 0

A27 1000 50 40 0 70

A28 1000 40 70 0 70

A29 1000 0 0 60 40 A30 1000 50 0 0 40

A31 1000 60 40 0 50

A32 1000 40 60 0 70

A33 1000 0 40 0 60

A34 1000 70 50 30 60

A35 1000 30 60 0 40

A36 1000 50 60 0 70

A37 1000 70 60 0 70

A38 1000 30 50 0 50

A39 1000 0 0 50 40

A40 1000 50 50 0 40

A41 1000 40 50 0 30

A42 1000 40 50 0 70

A43 1000 70 40 0 60

A44 1000 0 0 60 40

A45 1000 40 40 0 0

A46 1000 60 60 0 50

A47 1000 50 50 0 40

A48 1000 60 40 10 40

A49 1000 60 60 0 30

A50 1000 30 40 0 0

A51 1000 10 60 0 0

A52 1000 0 40 0 0

A53 1000 60 60 0 70

A54 1000 50 50 0 30

A55 1000 20 40 0 20

A56 1000 40 50 0 30

A57 1000 50 50 0 40

A58 1000 40 60 10 60

A59 1000 0 0 0 0

A60 1000 0 50 0 0

A61 1000 50 40 50 30

A62 1000 40 30 0 0

A63 1000 40 40 0 0 A64 1000 50 50 10 0

A65 1000 80 80 0 60

A66 1000 80 60 0 70

B1 1000 40 40 10 60

B2 1000 0 0 0 0

B3 1000 40 30 0 20

B4 1000 90 60 20 0

B5 1000 30 30 0 70

B6 1000 40 20 10 10

B7 1000 70 50 30 20

B8 1000 80 60 60 80

B9 1000 60 50 0 70

B10 1000 0 50 0 70

B1 1 1000 70 20 10 70

AMARE = Amaranthus retroflexus; STEME = Stellaria media; LOLPE = Lolium perenne; DIGSA = Digitaria sanguinalis,

Example 1 c: Post-emergence herbicidal activity

Seeds of a variety of test species were sown in unsterilised compost in small pots. After cultivation for seven days (post-emergence) in controlled conditions in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) the plants were sprayed with 1 mg of the active ingredient, formulated in 466 μΙ of an acetone / water / Tween 20 (49.75:49.75:0.5) solution, which is equivalent to 1000 g/ha. Once the foliage was dry, the pots were kept in the glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), and were watered twice daily. After 12 days the test was evaluated and scored (100 = total damage to plant, 0 = no damage to plant). Results are shown in Table 3. Table 3: Application post-emergence

ABUTH = Abutilon theothrasti; BIDPI = Bidens pilosa; CHEAL = Chenopodium album; KCHSC = Koschia scoparia, ECHCG = Echinochloa crus-galli; SETFA = Setaria faberi; ELEIN = Eleusine indica; SORHA = Sorghum halepense

Claims

1. Use of a compound of the formula (A):

wherein A1 , A2 and A4 are each independently C-R1 or nitrogen, wherein each R1 may be the same or different;

A3 is C-X; R1 is H, CrC₆haloalkyl, cyano, halogen, CrC₆alkoxy, CrC₆alkyl or d-C₆alkyl substituted by one or more cyano, hydroxyl, amine, carbonylamine;

X is halogen, d-C₆haloalkyl, cyano, thiocyanate, nitro, d-C₆alkoxy, d-C₆halo- alkoxy, C Cealkylthio, Crdhaloalkylthio, d-C₆alkylsulfinyl, d-C₆haloalkylsulfinyl, d- C₆alkylsulfonyl, Ci-C₆haloalkylsulfonyl, C₂-C₆alkenyl, C₂-C₆alkynyl, amine, N-CrC₆alkyl amine, N,N-di-CrC₆alkyl amine, CrC₆alkylcarbonyl, Ci-C₆alkoxycarbonyl, d- C₆haloalkoxycarbonyl,Ci-C₆haloalkylcarbonyl, C₃-C₈cycloalkyl, formyl or mercapto; or X is heteroaryl or heteroaryl subtituted by one or more halogen, cyano, C Csalkyl, d- C₃haloalkyl;

R2 is H, Ci-C₆alkyl, d-C₆haloalkyl, d-C₄alkylcarbonyl, d-C₆alkoxycarbonyl; or R2 is CrC₆alkyl substituted by one or more cyano, amine, carbonylamine;

Q is a group according to formula (i)

or R2 and Q form a cyclic group (ii)

wherein W are independently O or S;

R3, R4, R5 and R6 are independently hydrogen, halogen, nitro, cyano, C

C₃alkyl, d-C₃haloalkyl, C1-C3 alkoxy, hydroxyl, -OC(0)R9, amine, N-CrC₃alkyl amine or N,N-di-Ci-C₃alkyl amine; R7 is hydrogen, CrC₉alkyl, CrC₆haloalkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-

C₆alkynyl, C₂-C₆haloalkynyl, C₄-C₆alkylcycloalkyl, aryl or aryl substituted by one to five substituents R10, heterocyclyl or heterocyclyl substituted by one to ten substituents R10, C₃-C₇cycloalkyl or C₃-C₇cycloalkyl substituted by one to five substituents R10; or R7 is Ci-C₉alkyl substituted by one or more cyano, nitro, amine, hydroxyl, C

C₆alkoxy, CrC₆haloalkoxy, CrC₆alkylthio, CrC₆haloalkylthio, CrC₆alkylsulfinyl, CrC₆haloalkylsulfinyl, Ci-C₆alkylsulfonyl, Ci-C₆haloalkylsulfonyl, C₂-C₆alkenyl, C₂- C₆haloalkenyl, C₂-C₆alkynyl, C₂-C₆haloalkynyl, C₃-C₇cycloalkyl, C₄-C₆alkylcycloalkyl, N- C-|-C₆alkyl amine, N,N-di-C-|-C₆alkyl amine, aryl or aryl substituted by one to five substituents R10, heterocyclyl or heterocyclyl substituted by one to ten substituents R10; R9 is hydrogen, CrC₆alkyl, CrC₆alkoxy, or Ci-C₆haloalkyl; and each R10 is independently cyano, nitro, amino, hydroxy, halogen, CrC₆alkyl, d- C₆haloalkyl, Ci-C₄alkoxy-Ci-C₄alkyl, C₂-C₆alkenyl, C₂-C₆haloalkenyl, C₂-C₆alkynyl, C₂- C₆haloalkynyl, C₃-C₆cycloalkyl, C₃-C₆halocycloalkyl, Ci-C₆alkoxy, CrC₆haloalkoxy, C C alkoxy-Ci-C alkoxy, CrC₆alkylthio, CrC₆haloalkylthio, CrC₆alkylsulfinyl, Ci- C₆haloalkylsulfinyl, CrC₆alkylsulfonyl, Ci-C₆haloalkylsulfonyl, N-Ci-C₆alkylamino, N,N- di-(Ci-C₆alkyl)amino, N,N-di-(Ci-C₆alkyl)aminocarbonyl, N,N-di-(C C₆alkyl)- aminosulfonyl, CrC₆alkylcarbonyl, Ci-C₆alkylcarbonyloxy, CrC₆alkoxycarbonyl, Ci- C₆alkylcarbonylamino; or salts or N-oxides thereof, as a herbicide.

2. The use according to claim 1 , wherein in the compound of Formula A:

Q is (i);

both W are O;

A1 and A4 are C-R1 ;

A2 is C-R1 or N;

R1 is H, trifluoromethyl, cyano, halogen or methyl;

X is halogen, CrC₆haloalkyl or cyano;

R2 is H or C C₆alkyl;

R3, R4, R5 and R6 are independently hydrogen or methyl; and

R7 is hydrogen, CrC₆alkyl, CrC₆haloalkyl, C₂-C₆ alkenyl, C₂-C₆alkynyl, C₃- C₆cycloalkyl, benzyl, or R7 is C C₆ alkyl substituted by one or more C Cealkoxy, C^ C₆alkylthio.

3. The use according to claim 1 or 2, wherein in the compound of Formula (A), R2 is hydrogen.

4. The use according to any one of claims 1 to 3, wherein in the compound of Formula (A), R7 is hydrogen, methyl, ethyl, n-propyl or iso-propyl.

5. The use according to claim 1 , wherein in the compound of Formula (A):

Q and R2 form cyclic group (ii); both W are O;

A1 and A4 are C-R1 ;

A2 is C-R1 or N;

R1 is H, trifluoromethyl, cyano, halogen or methyl;

X is halogen, CrC₆haloalkyl or cyano; and

R3, R4, R5 and R6 are independently hydrogen or methyl.

6. The use according to any one of claims 1 to 5, wherein in the compound of Formula (A), X is bromine, chlorine, trifluoromethyl or cyano.

7. The use according to any one of claims 1 to 6, wherein in the compound of Formula (A), A2 is N.

8. The use according to any one of claims 1 to 7, wherein in the compound of Formula (A), A1 and A4 are C-H.

9. The use according to any one of claims 1 to 6 or claim 8, wherein in the compound of Formula (A), A2 is C-H.

10. The use according to any one of claims 1 to 9, wherein in the compound of Formula (A), R3, R4, R5 and R6 are hydrogen.

1 1. A herbicide composition, comprising a compound of Formula (A) defined according to any one of the preceding claims, and an agriculturally acceptable formulation adjuvant.

12. A method for killing weeds and unwanted vegetation, wherein the method comprises applying to said weeds or unwanted vegetation an amount of a compound of Formula (A) defined according to any one of claims 1 to 10, or the composition according to claim 1 1.

13. A method for controlling weeds comprising applying to said weeds post- emergence an effective amount of a compound of Formula (A) defined according to any one of claims 1 to 10, or the composition according to claim 1 1.

14. A method for controlling weeds comprising applying to the soil before said weeds emerge an effective amount of a compound of Formula (A) defined according to any one of claims 1 to 10, or the composition according to claim 1 1 .