HERBICIDAL ISOXAZOLINE DERIVATIVES

The present invention relates to isoxazoline-oxime derivatives, to processes and intermediates for making these compounds, to herbicidal compositions comprising these compounds and to methods of using these compounds to control plant growth.

Certain isoxazoline derivatives with herbicidal properties are disclosed in EP 1 203 768 B, EP 1 364 946 B, EP 1 405 853 B, WO 03/010165, WO 2006/024820 Al , WO 2006/037945 Al , WO 2007/003294 (and US 2007/1 61 513 Al), WO 2007/071900 Al , WO 2007/096576 Al , and WO 2008/074991 Al .

It has now surprisingly been found that isoxazoline-oxime derivatives have herbicidal properties. a first aspect, the present invention therefore provides a compound of formula (I)

wherein

R ¹ and R ² are independently hydrogen, Ci-C ₈ alkyl or C3-Ciocycloalkyl or R ¹ and R ² join to form, together with the carbon atom to which they are attached, a C3-Ci ₀ cycloalkyl ring; R ³ and R ⁴ are independently hydrogen, halogen or Ci-Csalkyl or R ³ and R ⁴ join to form, together with the carbon atom to which they are attached, a C3-Ciocycloalkyl ring;

R ⁵ and R ⁶ are independently hydrogen, halogen, CpC ₈ alkyl or, taken together with the carbon atom to which they are attached, form a C3-C 10 cycloalkyl ring; R ⁷ is selected from hydrogen, Ci-C ₈ alkyl optionally substituted by one to three groups R ⁹ , C| -Cjjhaloalkyl, C i-C ₈ alkoxy, formyl, amino, Ci -Cealkylamino, di(Ci-C ₆ )alkylamino, C _\ - C ₈ alkylcarbonyl-, Ci-C ₈ alkoxycarbonyl-, (C| -C8)alkoxy(C|-C ₈ )alkyl, C ₃ - C ₈ cycloalkoxycarbonyl-, C ₂ -C ₈ alkenyloxycarbonyl-, C ₂ -C ₈ alkynloxycarbonyl-, C ₃ - C ₈ cycloalkylcarbonyl-, Ci-C ₈ haloalkylcarbonyl-, C ₂ -C ₈ alkenyl optionally substituted by one to three groups R ⁹ , C2-C ₈ alkenylcarbonyl, C3-C ₈ cycloalkenyl optionally substituted by one to three groups R ⁹ , C3-C ₈ halocycloalkenyl, C2-C ₈ haloalkenyl, C ₂ -C ₈ alkynyl optionally substituted by one to three groups R ⁹ , C ₂ -C ₈ alkynylcarbonyl, C ₂ -C ₈ haloalkynyl, - CONR ¹⁴ R ¹⁵ , -S0 ₂ NR ^l4 R ¹⁵ , C ₃ -Ci ₀ cycloalkyl optionally substituted by one to three groups R ⁹ , (C ₃ -Ci ₀ )cycloalkyl(C| -C8)alkyl optionally substituted by one to three groups R ⁹ , (C ₃ - C 1 ₀ )cycloalkyl(C i -C ₈ )haloalkyl, (C ₃ -C 1 ₀ )halocycloalkyl(C , -C ₈ )alkyl, C ₃ -C , _O halocycloalkyl, cyano, C ₆ -Cioaryl optionally substituted by one to five groups R ¹⁰ , heterocyclyl optionally substituted by one to five groups R ¹⁰ , (C ₆ -Cio)aryl(C|-C ₄ )alkyl- where the alkyl moiety is optionally substituted one to three groups R ⁹ and the aryl moiety is optionally substituted by one to five groups R ¹⁰ , heterocyclyl(Ci-C ₄ )alkyl- where the alkyl moiety is optionally substituted one to three groups R ⁹ and the heterocyclyl moiety is optionally substituted by one to five groups R ¹⁰ ; and

R ⁸ is selected from hydrogen, Ci-C ₈ alkyl optionally substituted by one to three groups R ¹² , C,-C ₈ haloalkyl, formyl, Ci-C ₈ alkylcarbonyl-, (C C ₈ )alkoxy(C,-C ₈ )alkyl, d- Qalkoxycarbonyl-, C ₃ -C ₈ cycloalkoxycarbonyl-, C ₃ -C ₈ cyloalkylcarbonyl-, Ci- C ₈ haloalkylcarbonyl-, C ₂ -C ₈ alkenyl optionally substituted by one to three groups R ¹² , C ₂ - C ₈ alkenylcarbonyl. C ₃ -C ₈ cycloalkenyl optionally substituted by one to three groups R , C ₃ - Qhalocycloalkenyl, C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl optionally substituted by one to three groups R ¹² , C ₂ -C ₈ alkynylcarbonyl, C ₂ -C ₈ haloalkynyl, -CONR ¹⁴ R ¹⁵ , -S0 ₂ NR ^l4 R ¹⁵ , C,- C ₈ alkylsulfonyl, Ci-C ₈ haloalkylsulfonyl, C ₃ -C| ₀ cycloalkyl optionally substituted by one to three groups R ¹² , (C -Cio)cycloalkyl(Ci-C ₈ )alkyl optionally substituted by one to three groups R ¹² , (C ₃ -C ₁₀ )cycloalkyl(Ci-C ₈ )haloalkyl, (C ₃ -Ci ₀ )halocycloalkyl(C,-C ₈ )alkyl, C ₃ -C, ₀ halocycloalkyl, cyano, C ₆ -C| ₀ aryl optionally substituted by one to five groups R ¹³ , heterocyclyl optionally substituted by one to five groups R ¹³ , (C6-C| ₀ )aryl(Ci-C ₄ )alkyl- where the alkyl moiety is optionally substituted one to three groups R ¹² and the aryl moiety is optionally substituted by one to five groups R ¹³ , or heterocyclyl(Ci-C ₄ )alkyl- where the alkyl moiety is optionally substituted one to three groups R ¹² and the heterocyclyl moiety is optionally substituted by one to five groups R ¹³ ; wherein each R ¹² is independently halogen, nitro, cyano, C ₃ -C ₆ cycloalkyl, C|-C ₆ alkoxy, C ₃ - C ₆ cycloalkoxy, C _r C ₆ haloalkyl, C ₃ -C ₆ halocycloalkyl, C C ₆ haloalkoxy, Ci-C ₆ alkylthio, Ci- C ₆ haloalkylthio, C| -C ₆ alkylsulfinyl, Ci -C ₆ alkylsulfonyl, formyl, Ci-Cealkylcarbonyl, amino, C|-C ₆ alkylamino, di(C,-C ₆ )alkylamino, -CONR ^{l 4} R ^{1 5} or -S0 ₂ NR ¹⁴ R ¹⁵ ;

each R ⁹ is independently halogen, nitro, cyano, C ₃ -C ₆ cycloalkyl, d-Cealkoxy, C ₃ - C ₆ cycloalkoxy, Ci-C ₆ haloalkyl, C ₃ -C ₆ halocycloalkyl, Ci-C ₆ haloalkoxy, Ci-C ₆ alkylthio, Cp C6haloalkylthio, CpQalkylsulfinyl, Ci-C ₆ alkylsulfonyl, formyl, C|-C ₆ alkylcarbonyl-, amino, Ci-C ₆ alkylamino, di(Ci-C ₆ )alkylamino, -CONR ^{l 4} R ¹⁵ or -S0 ₂ NR ¹⁴ R ¹⁵ ;

each R ¹⁰ is independently cyano, nitro, halogen, C]-C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, Ci- C ₄ alkylsulfonyl, Ci-C haloalkyl, C _r C ₄ alkoxy, Ci-C ₄ haloalkoxy, Ci-C ₄ alkoxycarbonyl, aminocarbonyl, Ci-C ₆ alkylaminocarbonyl, di(C| -C6)alkylaminocarbonyl, aminosulfonyl, Ci- Caalkyl aminosulfonyl, or di(Ci-C ₆ )alkylaminosulfonyl;

each R ^{1 1} is independently halogen, Ci-C ₄ alkyl, Ci -C alkoxy, or C C ₄ haloalkyl;

each R ¹³ is independently cyano, nitro, halogen, C _r C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, C| - C ₄ alkylsulfonyl, C|-C haloalkyl, C _r C ₄ alkoxy, Ci-C ₄ alkoxycarbonyl, aminocarbonyl, Ci- C6alkylaminocarbonyl, di(Ci-C ₆ )alkylaminocarbonyl, aminosulfonyl, C|-C ₆ alkyl

aminosulfonyl, di(Ci-C ₆ )alkylaminosulfonyl, or C C ₄ haloalkoxy; and

R ¹⁴ and R ¹⁵ are independently of each other hydrogen, Ci-C alkyl, C| -C ₆ acyl, C ₃ - Qcycloalkyl, or R ¹⁴ and R ¹⁵ join to form, together with the nitrogen to which they are attached, a 3- to 8-membered non-aromatic heterocyclic ring optionally containing one further ring member which is oxygen, sulphur. NH or an NC _r C ₆ alkyl group; or R ⁶ and R ⁷ are joined to form, together with the carbon atoms through which they are connected, a a 4- to 8-membered non-aromatic cycloalkyl, cycloalkenyl or heterocyclic ring which can be optionally substituted by one to five groups R ^{1 1} ;

7 ii

or R and R are joined to form, together with the oxygen, nitrogen and carbon atoms through which they are connected, a 4- to 8-membered non-aromatic heterocyclic ring optionally substituted by one to five groups R ^{1 1} ; and X is S, SO or S0 ₂ ; or a salt or an N-oxide thereof. In a second aspect, the invention provides a herbicidal composition which comprises a herbicidally effective amount of a compound of formula (I) as defined above in addition to formulation adjuvants.

In a third aspect, the invention provides the use of a compound or a composition of the invention as a herbicide.

In a fourth aspect, the invention provides a method of controlling plants which comprises applying to the plants or to the locus thereof a herbicidally effective amount of a compound or a composition of the invention.

The compounds of formula (I) may exist in different geometric or optical isomers 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. For example, the compounds of formula (I) may contain one or more asymmetric carbon atoms, for example, at the -CR ⁵ R ⁶ - group, and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such. Furthermore, when X is SO, the compounds of the invention are sulfoxides, which can exist in two enantiomeric forms. Furthermore, the compounds of formula (I) contain at least one double bond, namely the C=N bond in the oxime moiety, and can thus be present as the (E)-isomer, the (Z)-isomer, or a mixture of the (E)-isomer and the (Z)-isomer. The reactions described herein occasionally yield a single isomer. More frequently, however, a mixture of the (E)-isomer and the (Z)-isomer is obtained. The ratio of the (E)- to the (Z)-isomers can vary depending on the nature of the R ⁵ , R ⁶ , R ⁷ and R ⁸ groups.

Alkyl groups (either alone or as part of a larger group, such as alkoxy- or

alkylcarbonyl-) can be in the form of a straight or branched chain and are, for example, methyl, ethyl, propyl, prop-2-yl, butyl, but-2-yl, 2-methyl-prop-l -yl or 2-methyl-prop-2-yl. Unless otherwise indicated, the alkyl groups are preferably Ci-C ₆ , more preferably C1 -C4, most preferably C _r C ₃ alkyl groups.

Alkenyl groups can be in the form of straight or branched chains, and can be, where appropriate, of either the (EJ- or (Z)-configuration. Examples are vinyl and allyl. Unless otherwise indicated, the alkenyl groups are preferably C ₂ -C ₆ , more preferably C ₂ -C ₄ , most preferably C ₂ -C ₃ alkenyl groups.

Alkynyl groups can be in the form of straight or branched chains. Examples are ethynyl and propargyl. Unless otherwise indicated, the alkynyl groups are preferably C ₂ -C ₆ , more preferably C ₂ -C ₄ , most preferably C ₂ -C ₃ alkynyl groups. Alkylcarbonyl refers to the group -(C=0)-alkyl, wherein alkyl is as defined above. Examples of alkylcarbonyl groups include ethanoyl, propanoyl, n-butanoyl, etc.

Amino refers to the group -NH ₂ .

Alkylamino refers to the group -NH-alkyl, wherein alkyl is as defined above. Examples of alkylamino groups include methylamino, ethylamino, prop-l-ylamino, prop-2- ylamino etc.

Dialkylamino refers to the group -N(alkyl)alkyl' wherein alkyl and alkyl' are independently selected alkyl as defined above. Examples of dialkylamino groups include dimethylamino, diethylamino, methyl(ethyl)amino, methyl(prop-2-yl)amino, etc.

Alkylthio refers to the group -S-alkyl, wherein alkyl is as defined above. Examples of alkylthio groups are methylthio, ethylthio, propylthio, prop-2-ylthio, butylthio etc.

Alkylsulfinyl refers to the group -S(0)-alkyl, and alkylsulfonyl to the group -S(0) ₂ -alkyl, wherein alkyl is as defined above.

Haloalkyl groups (either alone or as part of a larger group, such as haloalkoxy- or haloalkylcarbonyl-) are alkyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, difluoromethyl, trifluoromethyl,

chlorodifiuoromethyl or 2,2,2-trifluoro-ethyl.

Haloalkylthio refers to the group -S-haloalkyl, wherein haloalkyl is as defined above.

Examples of haloalkylthio groups are trifluoromethylthio, 2,2,2,-trifluoroethylthio, etc.

Haloalkylcarbonyl refers to the group -(C=0)-haloalkyl, wherein haloalkyl is as defined above. Examples of haloalkylcarbonyl groups include trifluoroethanoyl, 3,3,3 trichloropropanoyl, n-perfluorobutanoyl, etc.

Alkoxycarbonyl refers to the group -(C=0)-0-alkyl, wherein the alkyl group is as defined above. Examples of alkoxycarbonyl groups are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, but- 1 -oxycarbonyl and but-3-oxycarbonyl.

Cycloalkyl groups can be in mono- or bi-cyclic form and are, for example, cyclopropyl, cyclobutyl, cyclohexyl and bicyclo[2.2.1]heptan-2-yI. The cycloalkyl groups are preferably C ₃ -C ₈ , more preferably C ₃ -C ₆ cycloalkyl groups. Where a cycloalkyl moiety is said to be substituted, the cycloalkyl moiety is, unless otherwise indicated, preferably substituted by one to four substituents, most preferably by one to three

substituents. Cycloalkoxycarbonyl refers to the group -(C=0)-0-cycloalkyl, wherein the cycloalkyl group is as defined above. Examples of cycloalkoxycarbonyl groups are cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl and cyclohexyloxycarbonyl.

Cycloalkylcarbonyl refers to the group -(C=0)cycloalkyl wherein the cycloalkyl group is as defined above. Examples of cycloalkylcarbonyl groups include cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexylcarbonyl.

Cycloalkenyl refers to a cycloalkyl group as defined above having at least one carbon- carbon double bond in the ring. Examples of cycloalkenyl are cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl etc.

Halocycloalkyl refers to a cycloalkyl group as defined above, substituted with at least one halogen atom. Examples of halocycloalkyl groups are perfluorocyclopropyl, 2,2- difluorocyclobutyl, 3,4-dichlorocyclohexyl etc.

Halocycloalkenyl refers to a cycloalkenyl group as defined above having at least one halogen substituent. Examples of cycloalkenyl are 1 -fluorocyclopropenyl, perfluorocyclobutenyl, 3,3-dichlorocyclopentenyl, 2,3-dibromocyclohexenyl etc.

Formyl refers to the group -CHO.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkenyl groups are alkenyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, 2,2-difluoro-vinyl or 1 ,2-dichloro-2- fluoro-vinyl.

Haloalkynyl groups are alkynyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, l -chloro-prop-2-ynyl.

Aminocarbonyl refers to the group -(C=0)NH ₂ .

Alkylaminocarbonyl refers to the group -(C=0)NHalkyl, wherein alkyl is as defined above. Examples of alkylaminocarbonyl groups are methylaminocarbonyl,

ethylaminocarbonyl, prop-l-ylaminocarbonyl, prop-2-ylaminocarbonyl etc.

Dialkylaminocarbonyl refers to the group -(C=0)N(alkyl)alkyl', wherein alkyl and alkyl' are independently selected alkyl as defined above. Examples of dialkylaminocarbonyl groups are dimethylaminocarbonyl, methyl(ethyl)aminocarbonyl, etc.

Aminosulfonyl refers to the group -SO2NH2. Alkylaminosulfonyl refers to the group -S0 ₂ NHalkyl, herein alkyl is as defined above. Examples of alkylaminosulfonyl groups are methylaminosulfonyl, ethylamino sulfonyl, prop-l -ylaminosulfonyl, prop-2-ylaminosulfonyl etc.

Dialkylaminosulfonyl refers to the group -S0 ₂ NH(alkyl)alkyl', herein alkyl and alkyl' are independently selected alkyl as defined above. Examples of dialkylaminosulfonyl groups are dimethylaminosulfonyl, methyl(ethyl)aminosulfonyl, methyl(prop-l - yl)aminosulfonyl etc.

Cycloalkylalkyl refers to an alkyl group as defined above, substituted with a cycloalkyl group as defined above, and connected to the remainder of the molecule via the alkyl group. Examples of cycloalkylalkyl groups are cyclopropyl methyl, 1 -cyclobutylethyl, 2-cyclobutylethyl, etc.

Cycloalkylhaloalkyl refers to a haloalkyl group as defined above, substituted with a cycloalkyl group as defined above, and connected to the remainder of the molecule via the haloalkyl group. Examples of cycloalkylhaloalkyl groups are cyclopropyldifluoromethyl, 1 - cyclobutyl-2,2,2-trifluoroethyl, 2-cyclobutly-l -chloroethyl, etc.

Aryl groups (either alone or as part of a larger group, such as aryl-alkyl-) are aromatic ring systems which can be in mono-, bi- or tricyclic form. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyl and naphthyl, phenyl being most preferred. Where an aryl moiety is said to be substituted, the aryl moiety is, unless otherwise indicated, preferably substituted by one to four substituents, most preferably by one to three (e.g. one or two) substituents.

Heteroaryl groups (either alone or as part of a larger group, such as heteroaryl-alkyl-) are aromatic ring systems containing at least one ring heteroatom and consisting either of a single ring or of two or more fused rings, and having from 5 to 12 ring atoms. Preferably, single rings will contain up to three heteroatoms and bicyclic systems up to four heteroatoms which will preferably be independently chosen from nitrogen, oxygen and sulfur. Examples of monocyclic groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples of bicyclic groups include quinolinyl, cinnolinyl, quinoxalinyl, indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl. Where a heteroaryl moiety is said to be substituted, the heteroaryl moiety is, unless otherwise indicated, preferably substituted by one to four substituents, most preferably by one to three (e.g. one or two) substituents.

Heterocyclyl groups or heterocyclic rings (either alone or as part of a larger group, such as heterocyclyl-alkyl-) are defined to include heteroaryl groups and in addition their unsaturated or partially unsaturated analogues. The unsaturated or partially unsaturated analogues can also be referred to as non-aromatic heterocyclyl groups or as non-aromatic heterocyclic rings. Where the term non-aromatic is used in connection with the embodiment where R ⁷ and R ⁸ are joined to form a 4- to 8-membered non-aromatic heterocyclic ring, the ring contains at least one double bond, namely the C=N bond in the oxime moiety. Examples of monocyclic groups include pyrrolidinyl, tetrahydrofuranyl, [1 ,3]dioxolanyl, piperidinyl, piperazinyl, [l,4]dioxanyl, and morpholinyl. Examples of bicyclic groups include 2,3- dihydro-benzofuranyl, benzo[l ,3]dioxolanyl, and 2,3-dihydro-benzo[ l ,4]dioxinyl. Where a heterocyclyl moiety is said to be substituted, the heterocyclyl moiety is, unless otherwise indicated, preferably substituted by one to four substituents, most preferably by one to three (e.g. one or two) substituents.

Arylalkyl refers to an alkyl group as defined above, substituted with an aryl group as defined above, and connected to the remainder of the molecule via the alkyl group.

Examples of arylalkyl groups are benzyl (phenylmethyl), naphthylmethyl, 2-phenethyl, etc.

Heterocyclylalkyl refers to an alkyl group as defined above, substituted with a heterocyclyl group as defined above, and connected to the remainder of the molecule via the alkyl group. Examples of heterocyclylalkyl groups are furan-2-yl methyl, furan-3-yl methyl, pyridine-3- yl methyl, tetrahydrofuran-2-yl ethyl, and indol-2-yl propyl etc.

Preferred values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹ ', R ¹² , R ¹³ and X for the compounds of formula (I), are, in any combination, as set out below.

Preferably R ¹ is Ci-C ₈ alkyl, more preferably methyl.

Preferably R ² is Ci-C ₈ alkyl, more preferably methyl.

More preferably, R ¹ and R ² are methyl.

Preferably R ³ is hydrogen or fluorine. More preferably, R ³ is hydrogen.

Preferably R ⁴ is hydrogen or fluorine. More preferably, R ⁴ is hydrogen.

More preferably, R ³ and R ⁴ are hydrogen.

Preferably R ⁵ is hydrogen, halogen or Ci-Csalkyl, more preferably hydrogen, fluorine or methyl, still more preferably hydrogen or fluorine. Preferably R ⁶ is hydrogen, halogen or C _r C ₈ alkyl, more preferably hydrogen, fluorine or methyl, still more preferably hydrogen or fluorine.

More preferably, R ³ and R ⁶ are both hydrogen or fluorine. Still more preferably, R ⁵ and R ⁶ are both fluorine.

Preferably R ⁷ is hydrogen, Ci-Cgalkyl or Ci-C ₈ alkyl optionally substituted by one to three groups R ⁹ , C C ₈ haloaIkyl, Ci-C ₈ alkoxy, (Ci-Cg)alkoxy(Ci-C ₈ )alkyl, C ₃ - C ₈ cycloalkenyl, C ₂ -C ₈ haloalkenyl, C ₂ -C ₈ alkynyl, (C ₃ -Ci ₀ )cycloalkyl(Ci-C ₈ )alkyl, C ₃ - Ciohalocycloalkyl, cyano, C ₃ -C| ₀ cycloalkyl or C3-C| ₀ cycloalkyl optionally substituted by one to three groups R ⁹ , CrQalkoxycarbonyl-, C ₂ -C ₈ alkenyl or C ₂ -C ₈ alkenyl optionally substituted by one to three groups R ⁹ , -CONR ^l4 R ¹⁵ , (C ₆ -Ci ₀ )aryl(C|-C ₄ )alkyl- or (C ₆ -

Cio)aryl(Ci-C ₄ )alkyl- wherein the aryl (e.g. phenyl) moiety is optionally substituted by one to five groups R ¹⁰ , heterocyclyl(Ci-C ₄ )alkyl- or heterocyclyl(Ci-C4)alkyl- wherein the heterocyclyl moiety is optionally substituted by one to five groups R ¹⁰ , aryl (e.g. phenyl) or aryl (e.g. phenyl) substituted by one to five groups R ¹⁰ , or heterocyclyl or heterocyclyl substituted by one to five groups R ¹⁰ .

More preferably R ⁷ is hydrogen, Ci-C ₈ alkyl or Ci-C ₈ alkyl optionally substituted by one to three groups R ⁹ , Ci-C ₈ haloalkyl, C ₃ -Ciocycloalkyl or C ₃ -Ci ₀ cycloalkyl optionally substituted by one to three groups R ⁹ , aryl (e.g. phenyl) or aryl (e.g. phenyl) substituted by one to five groups R ¹⁰ , or heterocyclyl or heterocyclyl substituted by one to five groups R ¹⁰ .

Still more preferably, R ⁷ is hydrogen, C|-C ₈ alkyl, C|-C ₈ haloalkyl, C ₃ -Ci ₀ cycloalkyl, aryl (e.g. phenyl) or aryl (e.g. phenyl) substituted by one to three (e.g. one or two) groups R ¹⁰ , or heterocyclyl or heterocyclyl substituted by one to three (e.g. one or two) groups R ¹⁰ .

Still more preferably, R ⁷ is hydrogen, C _r Cgalkyl, C _r Cgalkoxy, Ci-C ₈ haloalkyl, C ₃ - Ciocycloalkyl, phenyl or phenyl substituted by from one to three (e.g. one or two) R ¹⁰ , or heteroaryl or heteroaryl substituted by one to three (e.g. one or two) R ¹⁰ .

Yet more preferably, R ⁷ is hydrogen, methyl-, ethyl-, 2-methyl-prop-2-yl-,

trifluoromethyl-, cyclopropyl-, phenyl-, 4-chloro-phenyl-, 2,4-difluoro-phenyl-, 2,5-difluoro- phenyl-, 2-fluoro-phenyl-, 3-fluoro-phenyl-, 4-fluoro-phenyl-, 4-methyl-phenyl-, thiophen-2- yl-, 5-bromo-thiophen-2-yl-, 3,4-dibromo-thiophen-2-yl-, thiophen-3-yl-, 2,5-dichloro- thiophen-3-yl-, 2-chlorophenyl-, fur-2-yl-, ethoxycarbonyl-, thiazol-2-yl, or 4-methoxy- phenyl-. Most preferably, R ⁷ is methyl-, ethyl-, 2-methyl-prop-2-yl-, trifluoromethyl-, or cyclopropyl-.

Preferably R ⁸ is hydrogen, Ci-C ₈ alkyl or Ci-C ₈ alkyl optionally substituted by one to three groups R ¹² , (Ci-C ₈ )alkoxy(Ci-C ₈ )alkyl, Ci-C ₈ alkoxycarbonyl-, C ₃ -C ₈ cycloalkenyl, C ₂ - Cshaloalkenyl, C ₂ -C ₈ alkynyl or C ₂ -Cgalkynyl optionally substituted by one to three groups R ¹² , Ci-Cghaloalkyl, Ci-C ₈ alkylcarbonyl-, C2-C ₈ alkenyl or C ₂ -C ₈ alkenyl optionally substituted by one to three groups R ¹² , C ₃ -Ci ₀ cycloalkyl optionally substituted by one to three groups R ¹² , (C3-C|o)cycloalkyl(C| -C8)alkyl optionally substituted by one to three groups R ¹² , or a group -CONR ¹⁴ R ¹⁵ or -S0 ₂ NR ¹⁴ R ¹⁵ , aryl (e.g. phenyl) or aryl (e.g. phenyl) substituted by one to five groups R ¹³ , or aryl-C|-C ₄ alkyl- or aryl-Ci-C ₄ alkyl- wherein the aryl (e.g. phenyl) moiety is substituted by one to five groups R ¹³ , heterocyclyl or heterocyclyl optionally substituted by one to five groups R ¹³ , or heterocyclyl(Ci-C ₄ )alkyl- wherein the heterocyclyl moiety is optionally substituted by one to five groups R ¹³ .

More preferably R ⁸ is hydrogen, C|-C ₈ alkyl or C|-C ₈ alkyl optionally substituted by one to three groups R ¹² , C C ₈ haloalkyl, Ci-C ₈ alkylcarbonyl-, C ₂ -Qalkenyl or C ₂ -C ₈ alkenyl optionally substituted by one to three groups R ¹² , aryl (e.g. phenyl) or aryl (e.g. phenyl) substituted by one to five groups R ¹³ , or aryl-Ci-C ₄ alkyl- or aryl-C C ₄ alkyl- wherein the aryl moiety is substituted by one to five groups R ¹³ , heterocyclyl or heterocyclyl optionally substituted by one to five groups R ¹³ , heterocyclyl(Ci-C ₄ )alkyl- wherein the heterocyclyl moiety is optionally substituted by one to five groups R ¹³ .

Still more preferably, R ⁸ is C _r C ₈ alkyl, C,-C ₈ haloalkyl, C ₂ -C ₈ alkenyl, aryl (e.g.

phenyl) or aryl (e.g. phenyl) substituted by one or three (e.g. one or two) R ¹³ , or benzyl or

1 3 benzyl wherein the phenyl moiety is substituted by one or three (e.g. one or two) R .

Yet more preferably, R ⁸ is hydrogen, methyl-, ethyl-, prop-2-yl-, prop-l -yl-, 2-methyl- propyl-, 2-methyl-prop-2-yl-, 2,2,2-trifluoro-ethyl-, 2,2-difluoro-ethyl-, difluoromethyl-, methylcarbonyl-, prop-2-en-l -yl-, phenyl-, 4-cyano-phenyl-, phenylmethyl-, 3-fluoro- phenylmethyl-, 4-nitro-phenylmethyl- or 4-trifluoromethyl-phenylmethyl-.

Most preferably, R ⁸ is methyl-, ethyl-, prop-2-yl-, prop-l -yl-, 2-methyl-propyl-, 2- methyl-prop-2-yl-, 2,2,2-trifluoro-ethyl-, 2,2-difluoro-ethyl-, or difluoromethyl-.

In an alternative, preferred embodiment, R ⁷ and R ⁸ are joined to form, together with the oxygen, nitrogen and carbon atoms through which they are connected, a 4- to 8- membered non-aromatic heterocyclic ring which can be optionally substituted by one to five groups R ^{1 1} .

7 8

In embodiments where R and R are joined to form, together with the oxygen, nitrogen and carbon atoms through which they are connected, a 4- to 8-membered non- aromatic heterocyclic ring, this is preferably a 5,6-Dihydro-[ 1 ,4,2]dioxazine group or R ⁷ and R ⁸ are joined to form a 5,5 dimethyl-4,5-dihydroisoxazole group.

Preferably each R ⁹ is independently halogen, cyano, C ₃ -C ₆ cycloalkyl, C|-C ₆ alkoxy, C ₃ -C cycloalkoxy, Ci-Cehaloalkyl, C3-C ₆ halocycloalkyl, Ci-C ₆ haloalkoxy, C|-C ₆ alkylthio, Ci-C ₆ haloalkylthio, Ci-C ₆ alkylsulfinyl, C _r C ₆ alkylsulfonyl, or Ci-C ₆ alkylcarbonyl-. More preferably, each R ⁹ is independently C ₃ -C6cycloalkyl or Ci-C ₆ alkoxy.

Preferably each R ¹⁰ is independently cyano, nitro, halogen, Ci-C ₄ alkyl, Ci- C ₄ haloalkyl, Ci-C ₄ alkoxy, C ₂ -C ₄ alkenyl, C -C ₄ alkynyl, Ci-C ₄ alkylsulfonyl, or C|- C ₄ haloalkoxy, more preferably cyano, nitro, halogen, Ci-C ₄ alkyl C|-C ₄ haloalkyl, or Q- C ₄ alkoxy. More preferably, each R ¹⁰ is independently cyano, nitro, bromine, chlorine, fluorine, methyl, methoxy or trifluoromethyl.

Preferably each R ^{1 1} is independently halogen, Ci-C ₄ alkyl or Ci-C ₆ alkoxy, more preferably Ci-C ₄ alkyl , most preferably methyl.

Preferably each R ¹² is independently halogen, cyano, C ₃ -C ₆ cycloalkyl, C|-C ₆ alkoxy, C ₃ -C ₆ cycloalkoxy, C _r C ₆ haloalkyl. C ₃ -C ₆ halocycloalkyl, Ci-Cahaloalkoxy, C _r C ₆ alkylthio, Ci-C ₆ haloalkylthio, Ci-C ₆ alkylsulfinyl, C _r C ₆ alkylsulfonyl, or C _r C ₆ alkylcarbonyl-. More preferably, each R ¹² is independently C3-C ₆ cycloalkyl or Ci-C ₆ alkoxy.

Preferably each R ¹³ is independently cyano, nitro, halogen, Ci-C ₄ alkyl, Ci- C ₄ haloalkyl, Ci-C ₄ alkoxy, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, Ci-C ₄ alkylsulfonyl, or Ci- C4haloalkoxy, more preferably cyano, nitro, halogen, or Ci-C ₄ haloalkyl, still more preferably cyano, nitro, bromine, chlorine, fluorine, or trifluoromethyl.

Preferably X is SO or S0 ₂ , more preferably S0 ₂ .

Certain intermediates are novel and thus form another embodiment of this invention. Thus, in one embodiment there is provided a compound of formula (II)

where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are as defined for a compound of formula (I); or a salt or N-oxide thereof. The preferred values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X are as defined for a compound of formula (I).

In a further embodiment, there is provided a compound of formula (la)

where R', R% R R\ R , R°, R' and R ^s are as defined for a compound of formula (I); or a salt or N-oxide thereof The preferred values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined for a compound of formula (I). Compounds of formula (la) were found to have good biological activity and are also useful as intermediates for making further compounds of formula (la).

In a further embodiment, there is provided a compound of formula (Ila)

where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined for a compound of formula (I); or a salt or N-oxide thereof. The preferred values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R' are as defined for a compound of formula (I). Compounds of formula (Ila) are useful as intennediates for making compounds of formula (la).

In a further embodiment, there is provided a compound of formula (lb)

where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined for a compound of formula (I); or a salt or N-oxide thereof. The preferred values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined for a compound of formula (I). Compounds of formula (lb) are useful as

intermediates for making compounds of formula (la).

In a further embodiment, there is provided a compound of formula (lib)

where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined for a compound of formula (I); or a salt or N-oxide thereof. The preferred values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined for a compound of fonnula (I). Compounds of formula (lib) are useful as intermediates for making compounds of formula (la).

The compounds of the invention may be made by a variety of methods, for example by the methods described in Schemes 1 to 4.

Scheme 1

(Ha) 1 ) An oxime of formula (la) can be made by reacting a ketone of formula (Ila) where R', R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined for a compound of formula (I) with an appropriate hydroxylamine of formula NH ₂ OR ⁸ such as O-mefhyl hydroxylamine

hydrochloride, in the presence of a base, for example, an organic base, such as pyridine, or a inorganic base, such as potassium hydroxide, in the presence of a solvent, for example, a polar solvent, such as ethanoi. The reaction is preferably carried out at a temperature of from -20°C to +100°C, more preferably from 0°C to 60°C, most preferably at ambient

temperature.

2) A sulfone of formula (Ila) as defined in 1) can be made by reacting a sulfide of formula (lib) where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are as defined for a compound of formula

(I) with two equivalents of an oxidising agent, for example, a peracid, such as peracetic acid or 3-chloroperoxybenzoic acid ("MCPBA"), in the presence of a solvent, for example, a non- polar solvent, such as dichloromethane. The reaction is preferably carried out at a

temperature of from -20°C to +60°C, more preferably from -10°C to +30°C, most preferably at ambient temperature.

3) Alternatively, a sulfone of formula (la) can be made by reacting a sulfide of formula (lb) where R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined for a compound of formula (I) with an oxidising agent as defined in 2), in the presence of a solvent as defined in 2), and at a temperature as defined in 2).

4) An oxime of formula (lb) can be made by reacting a ketone of formula (lib) as defined in 2) with a hydroxylamine as defined in 1 ), in the presence of a base as defined in 1), in the presence of a solvent as defined in 1), and at a temperature as defined in 1 ).

5) Similarly, a compound of formula (I) where X is SO (i.e. a sulfoxide)

can be made using the method described in 2) but using one equivalent of an oxidising agent followed by the method described in 1), or alternatively can be made using the method described in 4) followed by the method described in 3) but using one equivalent of an oxidising agent. Scheme 3

(la") da'")

9) An oxime of formula (la) can be made by reacting a hydroxy oxime of formula (la') (i.e., compound of formula (la) where R ⁸ is hydrogen) with a compound of formula LG- R ⁸ where R ⁸ is as defined for a compound of formula (1) and LG is a leaving group, for example, a halide, such as bromide or chloride, or a sulfonate, such as methanesulfonate ("mesylate") or trifluoromethanesulfonate ("triflate"), in the presence of a base, for example, an inorganic base, such as caesium carbonate, in the presence of a solvent, for example, a polar solvent, such as dimethylformamide. The reaction is preferably carried out at a temperature of from -20°C to +100°C, more preferably from 0°C to 60°C, most preferably at ambient temperature.

10) When R ⁵ and/or R ⁶ is halogen, a sulfone of formula (la'") can be made by reacting a sulfone of formula (la") (i.e. a compound of formula (la) where R ⁵ is hydrogen) with an halogenating agent, in the presence of a base, in the presence of a solvent, for example, a polar solvent, such as tetrahydrofuran. Suitable halogenating agents are, for example, 4-iodotoluene difluoride (CAS RN 371 -1 1 -9) or N-fluorobenzenesulfonimide ("NFSI"), N-chlorosuccinimide ("NCS"), N-bromosuccinimide ("NBS"), and N- iodosuccinimide ("NIS"), for making a compound where R ⁵ and/or R ⁶ is F, CI, Br, or I, respectively. Suitable bases are, for example, a phosphazene base, such as N'-/e/7-butyl- NN,N',N',N'',N'-hexamethyIphosphorirnidic triamide ("Pi-'Bu"), 1 -ethyl-2,2,4,4,4- pentakis(dimethylamino)-2-lambda ⁵ -5,4-lambda ^: '-5-catenadi(phosphazene) ("P ₂ -Et"), 1 butyl-2,2,4,4,4-pentakis(dimethylarnino)-2-larnbda ⁵ -5,4-lambda ⁵ -5-catenadi(phosphazene) ('TV'Bu"), 2-fer butylimino-2-diethylan^ino-l,3-dirnethyl-perhydro-l ,3,2-diazaphosphorine C'BEMP") or 2,8,9-triisobutyl-2,5,8,9-tetraaza-l -phosphabicyclo[3.3.3]undecane

("Verkade's base"), or a strong non-nucleophilic base, such as lithium

bis(trimethylsilyl)amide ("LiHMDS"). The reaction is preferably carried out at a temperature of from -80°C to +100°C, more preferably from 0°C to 60°C, most preferably at ambient temperature. The skilled person will appreciate that dihalomethylene compounds (i.e.

compounds of formula (1 a) wherein R ⁵ and R ⁶ are both halogen) may be prepared from compounds of formula (la") wherein R ⁶ is hydrogen.

1 1 ) Similarly, a compound of formula (I) where X is SO (i.e. a sulfoxide) can be made using the method described in 9),

and a compound of formula (1) where X is SO (i.e. a sulfoxide) and R ⁵ and/or R ⁶ is halogen can be made using the method described in 10).

Sche

(III) (lib)

12) Alternatively, a sulfide of formula (lb) as defined in 3) can be made by reacting an isothiouronium-isoxazoline of formula (HI) where R ¹ , R ² , R ³ and R ⁴ are as defined for a compound of formula (I) with an oxime of formula (IV) where R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined for a compound of formula (I) and X ^B is a leaving group as defined in 9), in the presence of a base, such as potassium carbonate, in the presence of a solvent, for example, a polar solvent, such as acetonitrile. The reaction is preferably carried out at a temperature of from -20°C to +100°C, more preferably from 0°C to 60°C, most preferably at ambient temperature. The preparation of isothiouronium-isoxazolines of formula (III) is described, for example, in EP 1 ,829,868. The isothiouronium-isoxazoline is usually isolated as a salt, for example the hydrochloric acid salt. Oximes of fonnula (IV) are commercially available or can be made by methods known to a person skilled in the art.

13) Alternatively, a sulfide of formula (lib) as defined in 2) can be made by reacting an isothiouronium-isoxazoline of formula (HI) as defined in 12), with a ketone of formula (V) where R ⁵ , R ⁶ and R ⁷ are as defined for a compound of formula (I) and X ^B is a leaving group as defined in 9), in the presence of a base, such as potassium carbonate, in a solvent, for example a polar solvent such as acetonitrile. The reaction is preferably carried out at a temperature of from -20°C to +100°C, more preferably from 0°C to 60°C, most preferably at ambient temperature. Ketones of formula (V) are commercially available or can be made by methods known to a person skilled in the art.

The compounds of the invention may optionally be converted into a salt form. For those compounds capable of forming an anion (such as, for example, compounds comprising a carboxylic acid or sulfonic acid group), 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 aminium cations of the formula :

R i 6 _R i 7 _R i 8 _NH + _wherein R ¹⁶ , R ¹⁷ , and R ¹⁸ each, independently represents hydrogen or C _r Ci ₂ alkyl, C ₃ -C _]2 alkenyl or C ₃ -C] ₂ alkynyl, each of which is optionally substituted by one or more hydroxy, C1 -C4 alkoxy, C _r C ₄ alkylthio or phenyl groups. 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.

For those compounds capable of forming a cation , suitable acid addition salts include salts with inorganic acids, for example hydrochlorides, sulfates, phosphates and nitrates and salts with organic acids, for example acetates.

The compounds of formula (I) according to the invention can be used as herbicides in unmodified form, as obtained in the synthesis, but they are generally formulated into herb- icidal 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 (I) 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 approximately 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, polyure hane 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, N,N-dimethylformamide, 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, N-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 180.910 and 180.920.

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 dodecyl- benzenesulfonate; alkylphenol/alkyl oxide addition products, such as nonylphenol ethoxylate; alcohol/alkyl oxide addition products, such as tridecylalcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, 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 C ₈ -C ₂₂ fatty acids, especially the methyl derivatives of C _{] 2} -Ci 8 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 Ci ₂ -C ₂₂ 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 heptamefhyltriloxanes 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 alkyl- pyrrolidones (e.g. Agrimax®) to be added to the spray mixture. Formulations of synthetic lattices, e.g. polyacrylamide, polyvinyl compounds or poly-l -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 (I) 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 (I) 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 (I) 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 (I) (% = % bv weight)

Fl . 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. CaC0 ₃ or Si0 ₂

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 granules 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. CaC0 ₃ or Si0 ₂

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 granules a) b) c) d)

active ingredient 0.1 % 3 % 5 % 15 %

sodium lignosulfonate 1.5 % 2 % 3 % 4 %

carboxymethylcellulose 1.4 % 2 % 2 % 2 %

kaolin 97.0 % 93 % 90 % 79 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is 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 and grinding the mixture in a suitable mill.

F8. Suspension concentrates 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 %

carboxymethylcellulose 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 (I).

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 (I).

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 (1).

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 bum, 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.

Crops of useful plants in which the composition according to the invention can be used include 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 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 Xan hium.

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 N ® (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).

Areas under cultivation include land on which the crop plants are already growing and land intended for cultivation with those crop plants. The compounds of the invention can be applied before weeds emerge (pre-emergence application) or after weeds emerge (post- emergence application), and are particularly effective when applied post-emergence.

The compounds of formula (I) according to the invention can also be used in combination with one or more further herbicides. In particular, the following mixtures of the compound of formula (I) are important:

Mixtures of a compound of formula (I) with an acetanilide (e.g. compound of formula (I) + acetochlor (5), compound of formula (I) + dimethenamid (268), compound of formula (I) + metolachlor (567), compound of formula (1) + S-metolachlor (568), or compound of formula (I) + pretilachlor (677)).

Mixtures of a compound of formula (I) with an HPPD inhibitor (e.g. compound of formula (I) + isoxaflutole (495), compound of formula (I) + mesotrione (533), compound of formula (I) + pyrasulfotole (CAS RN 365400- 1 1 -9), compound of formula (I) + sulcotrione (767), compound of formula (I) + tembotrione (CAS RN 335104-84-2), compound of formula (I) + topramezone (831 ), compound of formula (I) + 4-hydroxy-3-[[2-[(2- methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbon yl]-bicyclo[3.2.1 ]oct-3-en-2- one (CAS RN 352010-68-5), or compound of formula (I) + 4-hydroxy-3-[[2-(3- methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicy clo[3.2.1 ]oct-3-en-2-one (CAS RN 894355-80-7)).

Mixtures of a compound of formula (I) with a triazine (e.g. compound of formula (I) + atrazine (38), or compound of formula (I) + terbuthylazine (795)).

Mixtures of a compound of formula (I) with a triazine and an HPPD inhibitor (e.g. compound of formula (I) + triazine + isoxaflutole, compound of formula (I) + triazine + mesotrione, compound of formula (I) + triazine + pyrasulfotole, compound of formula (1) + triazine + sulcotrione, compound of formula (I) + triazine + tembotrione, compound of formula (I) + triazine + topramezone, compound of formula (I) + triazine + 4-hydroxy-3-[[2- [(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]ca rbonyl]-bicyclo[3.2.1]oct-3- en-2-one, or compound of formula (1) + triazine + 4-hydroxy-3-[[2-(3-methoxypropyl)-6- (difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2-one).

Mixtures of a compound of formula (I) with glyphosate (431 ).

Mixtures of a compound of formula (I) with glyphosate and an HPPD inhibitor (e.g. compound of formula (I) + glyphosate + isoxaflutole, compound of formula (I) + glyphosate + mesotrione, compound of formula (I) + glyphosate + pyrasulfotole, compound of formula (I) + glyphosate + sulcotrione, compound of formula (I) + glyphosate + tembotrione, compound of formula (I) + glyphosate + topramezone, compound of formula (I) + glyphosate + 4-hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl )-3-pyridinyl]carbonyl]- bicyclo[3.2.1]oct-3-en-2-one, or compound of formula (I) + glyphosate + 4-hydroxy-3-[[2-(3- methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicy clo[3.2.1]oct-3-en-2-one).

Mixtures of a compound of formula (I) with glufosinate-ammonium (430).

Mixtures of a compound of formula (I) with glufosinate-ammonium and an HPPD inhibitor (e.g. compound of formula (I) + glufosinate-ammonium + isoxaflutole, compound of formula (1) + glufosinate-ammonium + mesotrione, compound of formula (1) +

glufosinate-ammonium + pyrasulfotole, compound of formula (I) + glufosinate-ammonium + sulcotrione, compound of formula (I) + glufosinate-ammonium + tembotrione, compound of formula (I) + glufosinate-ammonium + topramezone, compound of formula (I) + glufosinate- ammonium + 4-hydroxy-3-[[2-[(2-methoxyethox}')methyl]-6-(trifluoromethy l)-3- pyridinyl]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2-one, or compound of formula (I) + glufosinate- ammonium + 4-hydroxy-3-[[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyrid inyl]carbonyl]- bicyclo[3.2.1 ]oct-3-en-2-one).

Mixtures of a compound of formula (I) with a PPO inhibitor (e.g. compound of formula (1) + acifluorfen-sodium (8), compound of formula (I) + butafenacil (103), compound of formula (I) + carfentrazone-ethyl (123), compound of formula (I) + cinidon- ethyl (156), compound of formula (I) + flumioxazin (388), compound of formula (I) + fomesafen (413), compound of formula (I) + lactofen (503), or compound of formula (I) + SYN 523 ([3-[2-chloro-4-fluoro-5-(l -methyl-6-trifluoromethyl-2,4-dioxo-l , 2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetic acid ethyl ester) (CAS RN 353292- 31 -6)). The mixing partners of the compound of formula (1) 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 acifiuorfen-sodium also applies to acifluorfen, the reference to dimethenamid also applies to dimethenamid-P, and the reference to glufosinate-ammonium also applies to glufosinate, etc.

The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 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 (I) with the mixing partner).

Additionally, one or more of the following herbicides or plant growth regulators can be used in combination with a compound of formula (I) according to the invention or in combination with a mixture as described above: N-acetylthiazolidine-4-carboxylic acid (6), aclonifen (9), acrolein (1 1), alachlor (14), alloxydim (18), ametryn (20), amicarbazone (21 ), amidosulfuron (22), aminocyclopyrachlor (CAS RN 858956-08-8), aminopyralid (23), amitrole (aminotriazole) (26), ammonium sulfamate (27), ancymidol (31 ), anilofos (32), asulam (37), aviglycine (40), azafenidin (CAS RN 68049-83-2), azimsulfuron (43), beflubutaraid (55), benazolin (58), bencarbazone (CAS RN 173980-17-1 ), benfluralin (60), benfuresate (62), bensulfuron-mefhyl (65), bensulide (66), bentazone (68), benzfendizone (70), benzobicyclon (71 ), benzofenap (72), 6-benzylaminopurine (74), bifenox (77), bilanafos (bialaphos) (78), bispyribac-sodium (85), borax (88), bromacil (92), bromobutide (95), bromoxynil (97), bromofenoxim (CAS RN 13181 -17-4), butachlor (102), butamifos ( 104), butralin (107), butroxydim (108), butylate (1 10), cafenstrole (1 12), carbaryl (1 17), carbetamide (1 19), carvone ( 1 26), chlorbromuron (CAS RN 13360-45-7), chlorflurenol- methyl (136), chloridazon ( 137), chlorimuron-ethyl (138), chlormequat chloride ( 140), chloroacetic acid (141 ), 2-chloro-6'-ethyl-N-isopropoxy-methylaceto-o-toluidide

(propisochlor) (142), chlorotoluron (147), chlorphthalim ( 148), chlorpropham ( 149), chlorsulfuron (152), chlorthal-dimethyl (153), cinmethylin ( 157), cinosulfuron (158), clethodim ( 159), clodinafop-propargyl (160), clomazone ( 162), clomeprop (163), cloprop ( 164), clopyralid (165), cloransulam-methyl (1 7), cloxyfonac ( 1 9), 4-CPA (179), cumyluron ( 1 83), cyanamide ( 1 85), cyanazine ( 186), cyclanilide ( 1 89), cycloate ( 190), cyclosulfamuron ( 192), cycloxydim ( 193), cyhalofop-butyl ( 198), cytokinins (2 1 3), 2,4-D (214), daimuron (216), dalapon (217), daminozide (218), dazomet (219), 2,4-DB (220), n- decanol (224), desmedipham (228), desmetryn (CAS RN 1014-69-3), dicamba (232), dichlobenil (233), dichlorprop (239), dichlorprop-P (240), diclofop-methyl (243), diclofop-P-. methyl (244), diclosulam (247), difenzoquat metilsulfate (254), diflufenican (258), diflufenzopyr (259), 2,6-diisopropylnaphthalene (262), dikegulac (263), dimefuron (264), dimepiperate (265), dimethachlor (266), dimethametryn (267), dimethipin (269),

dimethylarsinic acid (272), dinitramine (277), dinoterb (281), diphenamid (284), dipropetryn (CAS RN 4147-51-7), diquat dibromide (286), dithiopyr (290), diuron (291 ), DNOC (292), DSMA (CAS RN 144-21 -8), endothal (307), EPTC (31 1 ), esprocarb (315), ethalfluralin (317), ethametsulfuron-mefhyl (318), ethephon (319), ethofumesate (323), ethoxyfen (CAS RN 188634-90-4), ethoxyfen-ethyl (CAS RN 131086-42-5), ethoxysulfuron (326), ethychlozate (327), etobenzanid (330), fenoxaprop-P-ethyl (351), fentrazamide (359), ferrous sulfate (364), flamprop-M (366), flazasulfuron (367), florasulam (370), fluazolate

(isopropazol) (CAS RN 174514-07-9), fluazifop-butyl (372), fluazifop-P-butyl (373), flucarbazone-sodium (376), flucetosulfuron (377), fluchloralin (CAS RN 33245-39-5), flufenacet (BAY FOE 5043) (381), flufenpyr-ethyl (383), flumetralin (385), flumetsulam (386), flumiclorac-pentyl (387), flumipropyn (flumipropin) (CAS RN 84478-52-4), fluometuron (390), fluoroglycofen-ethyl (393), flupoxam (CAS RN 1 19126-15-7), flupropacil (CAS RN 120890-70-2), flupropanate (396), flupyrsulfuron-methyl-sodium (397), flurenol (399), fluridone (400), flurochloridone (401), fluroxypyr (402), flu rimidol (403), flurtamone (404), fluthiacet-methyl (407), foramsulfuron (414), forchlorfenuron (415), fosamine (418), gibberellic acid (427), gibberellin A ₄ with gibberellin A ₇ (428),

halosulfuron-methyl (438), haloxyfop (439), haloxyfop-P (440), HC-252 (441), hexazinone (453), imazamethabenz-methyl (463), imazamox (464), imazapic (465), imazapyr (466), imazaquin (467), imazethapyr (468), imazosulfuron (469), inabentide (474), indanofan (475), indaziflam (CAS RN 950782-86-2), indol-3-ylacetic acid (476), 4-indol-3-ylbutyric acid (477), iodosulfuron-methyl-sodium (480), ioxynil (481 ), isoprothiolane (490), isoproturon (491 ), isouron (492), isoxaben (493), isoxachlortole (CAS RN 141 1 12-06-3), isoxapyrifop (CAS RN 87757-18-4), karbutilate (499), lenacil (504), linuron (506), maleic hydrazide (510), CPA (517), MCPA-thioethyl ( 18), MCPB (519), mecoprop (521), mecoprop-P (522), mefenacet (523), mefluidide (525), mepiquat chloride (527), mesosulfuron-methyl (532), metam (538), metamifop (mefluoxafop) (539), metamitron (540), metazachlor (543), methabenzthiazuron (545), methasulfocarb (547), methazole (CAS RN 20354-26-1), methylarsonic acid (555), 1 -methylcyclopropene (558), methyldymron (559), methyl isothiocyanate (562), metobenzuron (CAS RN 1 11578-32-6), metobromuron (CAS RN 3060-89-7), metosulam (570), metoxuron (571), metribuzin (573), metsulfuron-methyl (574), molinate (578), monolinuron (580), MSMA (CAS RN 2163-80-6), 2-(l-naphthyl)acetamide (586), 1-naphthylacetic acid (587), 2-naphthyloxyacetic acid (588), naproanilide (CAS RN 52570-16-8), napropamide (589), naptalam (590), neburon (591), nicosulfuron (594), nipyraclofen (CAS RN 99662-1 1-0), nitrophenolate mixture (598), /i-methyl-glyphosate, nonanoic acid (600), norflurazon (601 ), oleic acid (fatty acids) (610), orbencarb (612), orthosulfamuron (614), oryzalin (615), oxadiargyl (617), oxadiazon (618), oxasulfuron (621), oxaziclomefone (622), oxyfluorfen (628), paclobutrazol (630), paraquat dichloride (633), pebulate (636), pendimethalin (640), penoxsulam (641), pentachlorophenol (642), pentanochlor (643), pentoxazone (645), pethoxamid (647), petrolium oils (648),

phenmedipham (649), N-phenylphthalamic acid (654), picloram (665), picolinafen (666), pinoxaden (668), piperophos (671), primisulfuron-methyl (678), prodiamine (682), profluazol (CAS RN 190314-43-3), profoxydim (684), prohexadione calcium (685), prometon (686), prometryn (687), propachlor (688), propanil (690), propaquizafop (691), propazine (693), propham (695), propoxycarbazone-sodium (procarbazone-sodium) (699), n- propyl dihydrojasmonate (700), propyzamide (701 ), prosulfocarb (703), prosulfuron (704), pyraclonil (pyrazogyl) (CAS RN 158353-15-2), pyraflufen-ethyl (71 1 ), pyrazolynate (712), pyrazosulfuron-ethyl (714), pyrazoxyfen (715), pyribenzoxim (717), pyributicarb (718), pyridafol (CAS RN 40020-01 -7), pyridate (722), pyriftalid (724), pyriminobac-methyl (727), pyrimisulfan (CAS RN 221205-90-9), pyrithiobac-sodium (729), pyroxasulfone (CAS RN 447399-55-5), pyroxsulam (triflosulam) (CAS RN 422556-08-9), quinclorac (732), quinmerac (733), quinoclamine (734), quizalofop (737), quizalofop-P (738), rimsulfuron (741), saflufenacil (BAS 800H) (CAS RN 372137-35-4), sethoxydim (746), siduron (747), simazine (750), simetryn (752), sintofen (753), sodium chlorate (754), sulfentrazone (769), sulfometuron-methyl (771), sulfosate (CAS RN 81591-81 -3), sulfosulfuron (772), sulfuric acid (775), tar oils (778), 2,3,6-TBA (779), TCA-sodium (780), tebutam (CAS RN 35256- 85-0), tebuthiuron (785), tecnazene (787), tefuryltrione (CAS RN 473278-76-1),

tepraloxydim (791 ), terbacil (792), terbumeton (794), terbutryn (796), TH 547 (l -(2-chloro- 6-propylimidazo[ 1 ,2-b]pyridazin-3-ylsulfonyl)-3-(4,6-dimethoxypyrimidin-2-yl) urea) (CAS RN 570415-88-2), thenylchlor (809), thidiazimin (CAS RN 123249-43-4), thiazafluron (CAS RN 25366-23-8), thiazopyr (813), thidiazuron (814), thiencarbazone-methyl (CAS RN 317815-83-1 ), thifensulfuron-methyl (thiameturon-methyl) (815), thiobencarb (817), tiocarbazil (CAS RN 36756-79-3), tralkoxydim (832), triacontanol (835), tri-ailate (838), triasulfuron (839), triaziflam (841 ), tribenuron-methyl (844), tribufos (845), triclopyr (849), trietazine (853), trifloxysulfuron-sodium (855), trifluralin (858), triflusulfuron-methyl (859), trihydroxytriazine (CAS RN 108-80-5), trinexapac-ethyl (863), tritosulfuron (865), uniconazole (867), urea sulfate (868), and 5-(2,6-difluoro-benzyloxymethyl)-5-methyl-3-(3- methyl-thiophen-2-yl)-4,5-dihydro-isoxazole (CAS RN 403640-27-7).

The mixing partners of the compound of formula (I) 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 bensulfuron-methyl also applies to bensulfuron, the reference to cloransulam- methyl also applies to cloransulam, the reference to flamprop-M also applies to flamprop, and the reference to pyrithiobac-sodium also applies to pyrithiobac, etc.

The mixing ratio of the compound of formula (I) to the mixing partner is preferably from 1 : 100 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 (I) with the mixing partner).

The compounds of formula (I) according to the invention can also be used in combination with one or more safeners. Likewise, mixtures of a compound of formula (I) according to the invention 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. The safeners can be benoxacor (64), cloquintocet-mexyl (166), cyometrinil (CAS RN 78370-21 -5),

cyprosulfamide (CAS RN 221667-31-8), dichlormid (236), dicyclonon (CAS RN 79260-71 - 2), dietholate (CAS RN 32345-29-2), fenchlorazole-ethyl (343), fenclorim (344), flurazole (CAS RN 72850-64-7), fluxofenim (41 1 ), furilazole (425), isoxadifen-ethyl (494), mefenpyr- diethyl (524), mephenate (CAS RN 2620-53-3), 2-methoxy-N-[[4-[[(methylamino)carbonyl]- amino]phenyl]sulfonyl]-benzamide (CAS RN 129531 -12-0), naphthalic anhydride (CAS RN 81-84-5), oxabetrinil (616), and TI-35 (826). Particularly preferred are mixtures of a compound of formula (I) with benoxacor and a compound of formula (I) with cloquintocet- mexyl.

The safeners of the compound of formula (I) 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 the reference to fenchlorazole-ethyl also applies to fenchlorazole, etc.

Preferably the mixing ratio of compound of formula (I) 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 fomiula (I) with the safener). It is possible that the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously. For example, the safener, a compound of formula (I) 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 (I) 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 (I) 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.

Preferred mixtures of a compound of formula (I) with further herbicides and safeners include:

Mixtures of a compound of formula (1) with S-metolachlor and a safener, particularly benoxacor.

Mixtures of a compound of formula (I) with isoxaflutole and a safener.

Mixtures of a compound of formula (I) with mesotrione and a safener.

Mixtures of a compound of formula (I) with sulcotrione and a safener.

Mixtures of a compound of formula (I) with tembotrione and a safener.

Mixtures of a compound of formula (I) with topramezone and a safener.

Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-[(2-rnethoxyethoxy)- methyl]-6-(trifluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3. 2.1]oct-3-en-2-one and a safener. Mixtures of a compound of formula (I) with 4-hydroxy-3-[[2-(3-methoxypropyl)-6- (difluoromethyl)-3-pyridinyl]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2-one) and a safener.

Mixtures of a compound of formula (I) with a triazine and a safener.

Mixtures of a compound of formula (I) with a triazine and isoxaflutole and a safener. Mixtures of a compound of formula (I) with a triazine and mesotrione and a safener.

Mixtures of a compound of formula (I) with a triazine and sulcotrione and a safener. Mixtures of a compound of formula (I) with a triazine and tembotrione and a safener. Mixtures of a compound of formula (I) with a triazine and topramezone and a safener. Mixtures of a compound of formula (I) with a triazine and 4-hydroxy-3-[[2-[(2- methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbon yl]-bicyclo[3.2.1 ]oct-3-en-2- one and a safener.

Mixtures of a compound of formula (I) with a triazine and 4-hydroxy-3-[[2-(3- methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicy clo[3.2.1]oct-3-en-2-one) and a safener.

Mixtures of a compound of formula (I) with glyphosate and a safener.

Mixtures of a compound of formula (I) with glyphosate and isoxaflutole and a safener.

Mixtures of a compound of formula (I) with glyphosate and mesotrione and a safener. Mixtures of a compound of formula (I) with glyphosate and sulcotrione and a safener. Mixtures of a compound of formula (I) with glyphosate and tembotrione and a safener.

Mixtures of a compound of formula (I) with glyphosate and topramezone and a safener.

Mixtures of a compound of formula (I) with glyphosate and 4-hydroxy-3-[[2-[(2- methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridinyl]carbon yl]-bicyclo[3.2.1]oct-3-en-2- one and a safener.

Mixtures of a compound of formula (I) with glyphosate and 4-hydroxy-3-[[2-(3- methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbonyl]-bicy clo[3.2.1 ]oct-3-en-2-one) and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and isoxaflutole and a safener. Mixtures of a compound of formula (I) with glufosinate-ammonium and mesotrione and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and sulcotrione and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and tembotrione and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and topramezone and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and 4-hydroxy-3- [[2-[(2-methoxyethoxy)methyl]-6-(trifluoromethyl)-3-pyridiny l]carbonyl]-bicyclo[3.2.1 ]oct- 3-en-2-one and a safener.

Mixtures of a compound of formula (I) with glufosinate-ammonium and 4-hydroxy-3- [[2-(3-methoxypropyl)-6-(difluoromethyl)-3-pyridinyl]carbony l]-bicyclo[3.2.1 ]oct-3-en-2- one) and a safener.

The following Examples further illustrate, but do not limit, the invention. Preparation Examples The following abbreviations were used in this section: s = singlet; bs = broad singlet; d = doublet; dd = double doublet; dt = double triplet; t = triplet, tt = triple triplet, q = quartet, sept = septet; m = multiplet; RT = retention time, MH ⁺ = molecular mass of the molecular cation. 1H NMR spectra were recorded at 400MHz on a Varian Unity Inova instrument. LC-

MS data was obtained using the following two methods:

Method A: the compounds were analyzed using a Waters 2777 injector, 2996 photodiode array, 2420 ELSD and Micromass ZQ2000 equipped with a Waters Atlantis dCl 8 column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron). Solvent A: 0.05% trifluoroacetic acid in water (v/v); Solvent B: 0.05% trifluoroacetic acid in acetonitrile (v/v). The analysis was conducted using a three minute run time, according to the following gradient table:

Method B: the compounds were analyzed using a Waters 2795 HPLC equipped with a Waters Atlantis dCl 8 column (column length 20 mm, internal diameter of column 3 mm, particle size 3 micron, temperature 40°C), Waters photodiode array ESI Corona CAD detector and Micromass ZQ2000 MS. Standard MS conditions are ES+/- switching over mass range 130-950. Solvent A: 0.1 % formic acid in water (v/v); Solvent B: 0.1 % formic acid in acetonitrile (v/v). The analysis was conducted using a three minute run time, according to the following gradient table:

Time (min) Solvent A (%) Solvent B (%) Flow (ml/min)

0.00 90.0 10.0 2.00

0.25 90.0 10.0 2.00

2.00 10.0 90.0 2.00

2.50 10.0 90.0 2.00

2.60 90.0 10.0 2.00

3.0 90.0 10.0 2.00

1. Reactions to prepare the compounds of the invention

Example 1.1 Preparation of l -(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-4-methyl- pent-3-en-2-one oxime (Compound No. Al 5 of Table A)

To a stirred solution of 3-methanesulfonyl-5,5-dimethyl-4,5-dihydro-isoxazole [made as described in WO 2001/012613] ( 177 mg, 1.0 mmol) in tetrahydrofuran (2 ml) was added dropwise under nitrogen at 0°C a solution of potassium bis(trimethylsilyl)amide ("KHMDS") (1 M in tetrahydrofuran) (1 .2 ml). The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 3 hours. The reaction was quenched by addition of aqueous potassium dihydrogen phosphate (saturated) (2 ml) and the mixture neutralized by dropwise addition of aqueous hydrochloric acid (1 M). The layers were separated and the aqueous layer extracted with ethyl acetate. The combined organic extracts were filtered through magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting with an wohexane to ethyl acetate gradient) to give the title compound as a yellow solid (1 10 mg, 80% yield). 1 H NMR (CDC1 ₃ ) 1.40 (s, 6H), 1.76 (s, 3H), 1.96 (s, 3H), 2.95 (s, 2H), 4.29 (s, 2H), 5.69 (s, 1 H), 9.54, (bs, 1H) ppm. Example 1.2 Preparation of 3-(5,5-dimethyl-4,5-dihydro-isoxazol-3-ylmethanesulfonyl)-5, 5- dimethyl-4,5-dihydro-isoxazole (Compound No. A18 of Table A)

To a stirred solution of 3-methanesulfonyl-5,5-dimethyl-4,5-dihydro-isoxazole [made as described in WO 2001/012613] (1.94 g, 10.95 mmol) in tetrahydrofuran (35 ml) was added dropwise over a 10 minute period under nitrogen at -35°C a solution of potassium bis(trimethylsilyl)amide (" HMDS") (0.91 M in tetrahydrofuran) (5.0 ml). The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 2.5 hours. The reaction was quenched by addition of aqueous potassium dihydrogen phosphate (saturated) (5 ml) and the mixture concentrated. The residue was taken up in dichloromethane, the solution filtered through magnesium sulfate and the filtrate

concentrated. The residue was purified by HPLC on silica gel (eluting with dichloromethane / 5 -hexane / ethyl acetate 5:4: 1) to give the title compound as a white solid (260 mg, 20% yield). 1 H NMR (CDC1 ₃ ) 1.43 (s, 6H), 1.51 (s, 6H), 2.94 (s, 2H), 3.10 (s, 2H), 4.32 (s, 2H) ppm.

Example 1.3 Preparation of 2-(5.5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-l -phenyl- ethanone ( -(2,2-difluoro-ethyl)-oxime (Compound No. A129 of Table A)

To a stirred suspension of caesium carbonate (490 mg, 1.5 mmol) and 2,2- difluoroethyl trifluoromethanesulfonate (236 mg, 1.1 mmol) in dimethylformamide (3 ml) was added dropwise over a period of 5 minutes at 0°C a solution of Compound No. A 128 of Table A (296 mg, 1.0 mmol) in dimethylformamide (2 ml). The reaction mixture was allowed to warm to ambient temperature and stirred at ambient temperature for 4 hours. The reaction was quenched by addition of aqueous potassium dihydrogen phosphate (saturated). The mixture was extracted with diethyl ether, the extract filtered through magnesium sulfate and the filtrate concentrated. The residue was purified by chromatography on silica gel (eluting with an wo-hexane to ethyl acetate gradient) to give the title compound as a white solid (190 mg, 53% yield). 1H NM (CDC1 ₃ ) 1.43 (s, 6H), 2.98 (s, 2H), 4.47 (dt, 2H), 4.99 (s, 2H), 6.08 (tt, 1 H), 7.4-7.5 (m, 3H), 7.7-7.75 (m, 2H) ppm.

Example 1.4 Preparation of 2-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-l -(4-fluoro- phenyl )-ethanone -mefhyloxime (Compound No. A22 of Table A)

To a stirred solution of Compound No. B6 of Table B (1.0 g, 3.3 mmol) in ethanol (20 ml) was added at ambient temperature O-methyl hydroxylamine hydrochloride (0.41 g, 4.95 mmol) and pyridine (0.53 ml, 4.95 mmol). The reaction mixture was stirred at ambient temperature for 72 hours. Additional O-methyl hydroxylamine hydrochloride (0.2 g, 2.4 mmol) and pyridine (0.25 ml, 2.33 mmol) were added and the reaction mixture stirred for a further 24 hours. The reaction mixture was concentrated and the residue partitioned between water (50 ml) and ethyl acetate (3x 50 ml). The combined organic extracts were dried over magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting first with wo-hexane and then with wo-hexane / ethyl acetate 7:3) to give the title compound as a white solid (0.89 g, 82% yield). LC-MS: MH ⁺ = 329, RT = 1.5 minutes. Example 1.5 Preparation of 3-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)- 1 , 1,1 - trifluoro-propan-2-one O-methyl-oxime (Compound No. A10 of Table A)

To a stirred solution of Compound No. CI of Table C (0.150 g, 0.55 mmol) in dichloromethane (10 ml) was added 3-chloroperoxybenzoic acid ("MCPBA") (0.400 g, 1.39 mmol). The reaction mixture was stirred at ambient temperature for 18 hours. The reaction was quenched by addition of aqueous sodium metabisulfite (saturated) (5 ml) and aqueous sodium hydrogen carbonate (saturated) (50 ml). The mixture was extracted with

dichloromethane (3x 100 ml). The combined organic extracts were washed with brine (100 ml), dried over magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting first with wohexane and then with «Ό-hexane / ethyl acetate 4:1 ) to give the title compound as a colorless oil (0.163 g, 96% yield). 1H NMR (CDC1 ₃ ) 1.50 (s, 6H); 3.08 (s, 2H); 4.14 (s, 3H); 4.66 (s, 2H) ppm. Example 1.6 Preparation of 2-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-2,2-difluo ro- l -(4-fluoro-phenyl)-ethanone O-methyl-oxime (Compound No. A96 of Table A)

To a stirred solution of Compound No. A22 of Table A (0.5 g, 1.53 mmol) in tetrahydrofuran (10 ml) was added N-fluorobenzenesulfonimide ("NFSI") (1.06 g, 3.37 mmol) and a solution of l -/er/-butyl-2,2,4,4,4-pentakis(dimethylamino)-2-lambda ⁵ -5,4- lambda ⁵ -5-catenadi(phosphazene) ("Pa-'Bu") (2M in tetrahydrofuran) ( 1 .65 ml) at ambient temperature. The reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was absorbed onto silica gel and purified by chromatography on silica gel (eluting first with hexane and then with hexane / ethyl acetate 6:4) to give the title compound as a white solid (0.25 g, 45% yield). LC-MS: MH ⁺ = 365, RT = 1.7 minutes. Example 1.7 Preparation of 2-(5,5-dimethyl-4,5-dihydro-isoxazole-3-sulfonyl)-2,2-di luoro- HphenyD-ethanone O-methyl-oxime (Compound No. A20 of Table A)

To a stirred solution of Compound No. A17 of Table A (0.12 g, 0.39 mmol) in tetrahydrofuran (10 ml) was added at 0°C N-fluorobenzenesulfonimide ("NFSI") (0.27 g, 0.85 mmol) in a single portion followed by dropwise addition of a solution of lithium bis(trimethylsilyl)amide ("LiHMDS") ( 1 M in tetrahydrofuran) (0.85 ml). The reaction mixture was allowed to warm to ambient temperature and then stirred at ambient temperature for 72 hours. The reaction mixture was heated to reflux for 6 hours, then allowed to cool to ambient temperature and stored at ambient temperature for 16 hours. The reaction mixture was concentrated. The residue was partitioned between water (30 ml) and ethyl acetate (3x 50 ml). The combined organic extracts were dried over magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting first with hexane and then with hexane / ethyl acetate 9: 1 ) to give the title compound as a white solid (0.06 g, 45% yield). LC-MS: MH ⁺ = 347, RT = 1.7 minutes.

Compound Nos. A 15 and A 18 of Table A were made by the methods described in Example 1 .1 and Example 1.2, respectively. The compounds where R ⁸ is 2,2-difluoroethyl were made by the method described in Example 1.3. The remaining compounds of Table A where R ⁵ and R ⁶ are both hydrogen were made by the method described in Example 1.4, except where R ⁷ is trifluoromethyl in which case the method described in Example 1.5 was used. The compounds of Table A where R ³ and/or R ⁶ is fluorine were made by the methods described above followed by either the method described in Example 1 .6 or the method described in Example 1.7. Table A:

lists compounds of fomiula (la) where R ¹ and R ² are both methyl, R ³ and R ⁴ are both hydrogen, and R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined in the table.

Comp. R ⁵ R ⁶ R ⁷ R ⁸ LC-MS 1 H NMR (measured No. (MH ⁺ , in CDCI3 unless

RT in otherwise indicated) minutes) ³

A193 F H trifluoro- prop-2-yl- 349, 1 .8 ^b

rnethyl-

A194 F F trifluoro- prop-2-yl- 366, 1 .9 ^b

m ethyl -

A195 H H -OCH2-CH2-O- 263, 0.5 ^b

A196 F -CH ₂ -CH ₂ -CH ₂ - prop-2-yl- 321 , 1.7 ^b

A197 H -CH ₂ -CH ₂ -CH ₂ - prop-2-yl- 335, 1 .8 ^b

CH ₂ - a - Method A used for analysis unless otherwise indicated,

b - Method B used for analysis.

2. Reactions to prepare intennediates

Example 2.1 Preparation of 2-(5,5-dimethyl-4,5-dihvdro-isoxazole-3-sulfonyl)-l-(4-fluor o- phenyD-ethanone (Compound No. B6 of Table B)

To a stirred solution of Compound No. D8 of Table D (3.9 g, 14 mmol) in dichloromethane (50 ml) was added peracetic acid (32% w/v in acetic acid) (8.8 ml) dropwise at ambient temperature. The reaction mixture was stirred for 48 hours at ambient temperature. The reaction was quenched by addition of aqueous sodium metabisulfite (40% w/v) (5 ml) and the mixture stirred at ambient temperature for 30 minutes. The mixture was made basic by the addition of aqueous sodium carbonate (2M) until gas evolution ceased. The phases were separated and the aqueous phase was extracted with dichloromethane (2x 50ml). The combined organic extracts were dried over magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting first with hexane and then with hexane / ethyl acetate 1 : 1 ) to give the title compound as a colorless oil (2.9 g, 69% yield). LC-MS: MH ⁺ = 300, RT = 1.4 minutes.

The compounds of Table B were made by the method described in Example 2.1.

Table B:

lists compounds of formula (Ila) where R ¹ and R ² are both methyl, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen, and R ⁷ is as defined in the table.

B23 napthalen-2-yl 332, l .6 ^b

a - Method A used for analysis unless otherwise indicated,

b - Method B used for analysis.

Example 2.2 Preparation of 3-(5,5-dimethyl-4,5-dihydro-isoxazol-3-ylsulfanyl)-l ,l T- trifluoro-propan-2-one O-methyl-oxime (Compound No. CI of Table C)

To a stirred solution of O-methyl hydroxylamine hydrochloride (0.215 g, 2.58 mmol) in a mixture of ethanol and water (l :1 ) (15 ml) was added potassium hydroxide (0.162 g, 2.79 mmol) at ambient temperature. Compound No. D2 of Table D (0.385 g, 1.60 mmol) (which was partly present in hydrated form) was added at ambient temperature and the reaction mixture stirred at ambient temperature for 18 hours. Additional O-methyl hydroxylamine hydrochloride (0.215 g, 2.58 mmol) and potassium hydroxide (0.180 g, 3.21 mmol) were added and the reaction mixture stirred at ambient temperature for a further 24 hours. The reaction was quenched by addition of water (50 ml) and aqueous ammonium chloride (saturated) (50 ml). The mixture was extracted with dichloromethane (3x 100ml). The combined organic extracts were washed with brine (100 ml), dried over magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting first with z ^' so-hexane and then with wo-hexane / ethyl acetate 85: 15) to give the title compound as a colorless oil (0.361 g, 84% yield). 1 H NMR (CDC1 ₃ ) 1.40 (s, 6H); 2.77 (s, 2H); 4.02 (s, 2H); 4.06 (s, 3H) ppm.

Example 2.3 Preparation of chloroacetaldehyde 0-iert-buty\ oxime

To a stirred suspension of 0-/£r/-butyl-hydroxylamine hydrochloride (1.16 g, 9.24 mmol) and sodium hydrogen carbonate (0.7 g, 8.3 mmol) in tetrahydrofuran (15 ml) was added dropwise at ambient temperature a solution of chloroacetaldehyde (50% in water)

(1.88 g, 12mmol). The reaction mixture was stirred at ambient temperature for 20 hours. The reaction mixture was neutralized by addition of sodium hydrogen carbonate (solid). The mixture was diluted with diethyl ether, the solution filtered through magnesium sulfate and concentrated to give the title compound as a colorless oil (1.28 g, 83% yield, 90% purity as determined by NMR). 1H NMR (CDC1 ₃ ) 1.28 (s, 9H, major and minor isomers); 4.12 (d, major isomer), 4.23 (d, minor isomer, together 2H); 6.80 (t, minor isomer), 7.38 (t, major isomer, together 1 H) ppm.

Example 2.4 Preparation of (5,5-dimethyl-4,5-dihydro-isoxazol-3-ylsulfanyl)-acetaldehyd e O-fe/V-butyl-oxime (Compound No. C4 of Table Q

To a stirred suspension of 2-(5,5-dimethyl-4,5-dihydro-isoxazol-3-yl)-isothiouronium hydrochloride [made as described in WO 2005/095352] (1 .62 g, 9.3 mmol) and

chloroacetaldehyde O-/ert-butyl-oxime (Example 2.3) (1.19 g, 7.2 mmol) in acetonitrile (15 ml) was added potassium carbonate (5 g, 36 mmol). The reaction mixture was stirred at ambient temperature for 48 hours. The reaction mixture was concentrated, the residue taken up in dichloromethane, the solution filtered through cellulose (Celite®) and the filtrate concentrated. The residue was purified by chromatography on silica gel (eluting with an iso- hexane to ethyl acetate gradient) to give the title compound as a pale yellow oil (1.25 g, 71 % yield). IH NMR (CDC1 ₃ ) major isomer 1.27 (s, 9H), 1.41 (s, 6H), 2.80 (s, 2H), 3.77 (d, 2H), 7.49 (t, IH); minor isomer 1.28 (s, 9H), 1 .42, (s, 6H), 2.79 (s, 2H), 3.83 (d, 2H), 6.91 (t, I H) ppm.

The compounds of Table C were made by the method described in Example 2.2, except where R ⁷ is H in which case the compounds were made by the method described in Example 2.3 followed by the method described in Example 2.4.

Table C:

lists compounds of formula (lb) where R ¹ and R ² are both methyl, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen, and R ⁷ and R ⁸ are as defined in the table.

Comp. R ⁷ R ⁸ LC-MS (MH ⁺ , 1 H NMR (measured in

No. RT in CDCI3 unless otherwise

minutes) ³ indicated)

CI trifluoro- methyl - 271 , 1.5 - methyl-

C2 H 2-methyl- 245, 1.6 ^b - propyl-

C3 H 3-fluoro- 297, 1.6 ^b - phenyl-methyl-

Comp. R ⁷ R ⁸ LC-MS (MH ⁺ , 1 H NMR (measured in

No. RT in CDC1 ₃ unless otherwise

minutes) ³ indicated)

C25 -OCH ₂ CH ₂ 0- 231 , 0.7 ^b

C26 2,4- methyl- Signals observed for major

dicholoro isomer: 1.39 (s, 6H); 2.75 thiophen- (s, 2H); 4.05 (s, 3H); 4.27 2-yl (s, 2H); 6.97 (s, 1H).

Signals observed for minor isomer only: 1.4 2(s, 6H);

2.78 (s, 2H); 3.9 (s, 3H);

4.5 (s, 2H); 6.8 (s, 1H).

a - Method A used for analysis unless otherwise indicated,

b - Method B used for analysis.

Example 2.5 Preparation of 2-(5,5-dimethyl-4,5-dihvdro-isoxazol-3-ylsulfanvn- l-(4-fluoro- phenyD-ethanone (Compound No. D8 of Table D)

To a stirred solution of 2-chloro-4'-fluoroacetophenone (commercially available) (3.0 g, 17.0 mmol) in acetonitrile (50 ml) was added 2-(5,5-dimethyl-4,5-dihydro-isoxazol-3-yl)- isothiouronium hydrochloride [made as described in WO 2005/095352] (4.0 g, 19 mmol) followed by potassium carbonate (4.7 g, 27 mmol) at ambient temperature. The reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was concentrated and the residue partitioned between water (200 ml) and ethyl acetate (3x 100 ml). The combined organic extracts were dried over magnesium sulfate and concentrated. The residue was purified by chromatography on silica gel (eluting with hexane / ethyl acetate 7:3) to give the title compound as a white solid (3.91 g, 88% yield). LC-MS: MH ⁺ = 268, RT = 1.4 minutes. Example 2.6 Preparation of 3-(5,5-dimethyl-4,5-dihydro-isoxazol-3-ylsulfanyl)- 1 , 1 ,1 - trifluoro-propan-2-one (Compound No. D2 of Table D)

To a solution of 2,2,2-trifluoro-l-bromoacetone (commercially available) (2 ml, 19.3 mmol) and 2-(5,5-dimethyl-4,5-dihydro-isoxazol-3-yl)-isothiouronium hydrochloride [made as described in WO 2005/095352] (4.44 g, 21.2 mmol) in acetonitrile (100 ml) under nitrogen at ambient temperature was added potassium carbonate (5.32 g, 38.5 mmol). The reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was concentrated and the residue partitioned between water (100 ml) and ethyl acetate (3x 100 ml). The combined organic extracts were concentrated. The residue was purified by chromatography on silica gel (eluting first with wo-hexane and then with /.so-hexane / ethyl acetate 85: 15) to give the title compound as a white solid (1.953 g, 39% yield). The title compound was obtained as a mixture of the ketone and its hydrated form (85: 15). 1 H NMR (CDC1 ₃ ) 1.42 (s, 6H); 2.87 (s, 2H); 3.39 (s, 2H) ppm.

The compounds of Table D were made by the methods described in Example 2.5 and Example 2.6.

Table D:

lists compounds of formula (lib) where R ¹ and R ² are both methyl, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen, and R ⁷ is as defined in the table.

Comp. R ⁷ LC-MS (MH ⁺ , 1H NMR (measured in No. RT in CDCI ₃ unless otherwise

minutes) ³ indicated)

D24 2-methoxyphenyl 280, 1.5 ^b

D25 naphthalen-2-yl 300, 1.6 ^b

D26 2,5-dichloro- 322, 1.6 ^b

thiophen-3-yl a - Method A used for analysis unless otherwise indicated,

b - Method B used for analysis. Table E:

lists compounds of formula (Ie) where R ¹ and R ² are both methyl, R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen, and R ⁷ is ethoxycarbonyl and R ^s is as defined in the table.

Comp. R ⁷ R ⁸ LC-MS (MH ⁺ , 1 H NMR (measured in No. RT in CDCI ₃ unless otherwise minutes) ³ indicated)

El ethoxy- ethyl- 305, 1.3 ^b

carbonyl-

E2 ethoxy- prop-2-yl- 319, 1.4 ^b

carbonyl-

E3 ethoxy- 2-methyl- 333, 1.6 ^b

carbonyl- prop-2-yl-

E4 ethoxy- phenyl-methyl- 367, 1.6 ^b

carbonyl-

E5 ethoxy- 4-trifluoro- 435, 1.7 ^b

carbonyl- methyl-phenyl- methyl-

E6 ethoxy- 3-fluoro- 385, 1.6 ^b

carbonyl- phenyl -methyl -

E7 ethoxy- prop-2-en-l-yl- 317, 1.4 ^b

carbonyl- a - Method A used for analysis unless otherwise indicated,

b - Method B used for analysis.

Biological examples

Example Bl : Herbicidal action

Seeds of a variety of test species were sown in standard soil in pots. After cultivation for one day (pre-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity) and watered twice daily. After 13 days, the test was evaluated (10 = total damage to plant; 0 = no damage to plant).

Table Bl : Application pre-emergence

Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY EC

No. (g/ha)

A2 1000 - 0 0 8 2 9

A3 1000 - 3 8 9 9 9

A6 1000 - 6 10 9 9 9

A7 1000 - 2 9 8 4 8

A8 1000 - 2 10 10 6 9

A9 1000 - 2 10 9 5 9

A 10 1000 - 3 6 9 10 10

Al l 1000 - 1 3 8 5 9

A12 1000 - 4 9 10 9 10

A13 1000 - 5 10 9 9 9

A14 1000 - 3 10 10 9 9

A16 1000 - 0 - 9 8 9

A17 1000 - 2 _ 9 7 9 W 201

- 67 -

Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY ECHCG No. (g ha)

A18 1000 4 2 0 4

A19 1000 6 10 9 7 9

A20 1000 8 10 10 6 9

A21 1000 10 10 10 6 9

A22 1000 7 10 9 6 9

A23 1000 3 10 9 7 9

A24 1000 10 10 9 7 10

A25 1000 2 1 1 2

All 1000 0 0 0 4

A29 1000 0 9 7 9

A30 1000 4 9 8 9

A31 1000 0 9 7 9

A32 1000 0 9 7 9

A33 1000 0 9 2 9

A36 1000 - 9 8 9

A37 1000 0 9 8 9

A38 1000 0 9 8 9

A39 1000 0 9 9 9

A40 1000 0 0 9 3 9

A42 1000 0 9 7 9

A43 1000 0 9 7 9

A44 1000 0 9 6 9

A45 1000 0 9 8 9

A46 1000 0 9 8 9

A48 1000 - 9 6 9

A49 1000 - 9 6 9

A50 1000 0 9 4 8

A51 1000 0 0 6 2 8 Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY E

No. (g/ha)

A53 1000 - 0 0 7 3 7

A60 1000 - 10 10 9 6 9

A61 1000 - 0 - 2 0 4

A62 1000 - 0 9 9 3 9

A63 1000 - 3 9 9 9 9

A64 1000 - 4 10 9 9 9

A65 1000 - 3 10 9 9 9

A66 1000 - 0 10 9 7 9

A67 1000 - 2 10 7 2 9

A68 1000 - 0 0 9 3 9

A69 1000 - 0 10 9 9 9

A70 1000 - 0 2 0 0 4

A71 1000 - 3 9 9 6 9

A72 1000 - 2 7 9 7 9

A73 1000 - 1 5 9 5 9

A74 1000 - 0 0 8 1 9

A75 1000 - 0 0 7 1 4

A78 1000 - 0 0 7 0 5

A79 1000 - 2 4 6 1 5

A80 1000 - 0 4 2 0 4

A81 1000 - 2 9 7 2 9

A82 1000 - 0 0 7 1 5

A83 1000 - 0 6 4 0 5

A84 1000 - 0 2 5 1 6

A86 1000 - 6 10 10 6 9

A88 1000 - 0 5 5 0 6

A89 1000 - 6 10 9 7 9

A91 1000 0 1 9 2 9 Comp. Rate ABUTH sc AMARE SETFA ALOMY ECHCG

No. (gha)

A92 1000 5 - 10 9 9 9

A93 1000 - 10 9 9 9

A94 1000 - 5 10 9 5 8

A95 1000 - 5 7 10 6 9

A96 1000 - 3 7 9 4 8

A97 1000 - 2 3 9 3 6

A98 1000 - 1 10 9 2 7

A100 1000 - 5 9 9 2 7

A101 1000 - 2 3 5 1 5

A102 1000 - 3 0 7 0 6

A103 1000 - 1 7 9 7 9

A104 1000 - 10 10 10 7 9

A105 1000 - 5 10 10 6 8

A106 1000 - 2 4 9 4 7

A107 1000 - 0 10 9 1 5

A108 1000 - 3 5 9 5 8

A109 1000 - 0 0 9 1 7

A110 1000 - 5 9 9 6 8

Alll 1000 - 5 10 10 7 9

Al 12 1000 - 4 6 9 4 9

Al 13 1000 - 1 3 3 1 1

A114 1000 2 - - 8 6 9

Al 15 1000 2 - 10 9 8 9

A116 1000 0 - 10 9 7 9

A117 1000 0 - 10 9 5 9

Al 18 1000 0 - 10 9 9 9

Al 19 1000 1 - 10 9 9 9

A120 1000 0 _ 10 8 6 9 Comp. Rate ABUTH SOLN1 AMARE SETFA ALOMY ECHCG

No. (g/ha)

A121 1000 1 7 9 8 9

A123 1000 0 - 9 4 9

A124 1000 1 0 9 8 9

A125 1000 1 10 9 8 9

A126 1000 1 - 8 6 9

A127 1000 0 10 9 6 9

A129 1000 3 10 9 5 8

A130 1000 2 10 9 5 9

A131 1000 0 9 9 4 9

A 132 1000 4 10 10 9 10

A133 1000 7 10 10 8 9

A134 1000 8 10 10 9 10

A135 1000 3 8 10 5 9

A136 1000 0 7 9 7 10

A137 1000 7 10 10 9 10

A 138 1000 4 9 10 5 10

A139 1000 5 10 10 8 10

A140 1000 4 10 8 6 9

A141 875 1 10 9 3 9

A 142 1000 6 10 9 6 10

A143 1000 3 7 9 5 9

A144 1000 5 10 9 7 9

A 145 1000 3 10 10 7 9

A148 1000 2 10 9 5 7

A149 1000 2 10 10 5 10

A 150 1000 3 10 9 5 9

A151 1000 0 10 9 5 9

A152 1000 5 10 9 6 9 Comp. Rate ABUTH SOLN1 AMARE SETFA ALOMY ECHCG

No. (g/ha)

A153 1000 2 7 8 3 9

A154 1000 3 10 9 3 10

A 1 56 1000 6 9 9 7 9

A157 1000 4 10 9 9 9

A 158 1000 7 10 9 9 10

A 167 1000 6 9 9 7 9

A168 1000 7 10 9 5 9

A174 1000 1 7 9 5 9

A181 1000 0 10 9 7 9

A182 1000 6 10 9 7 9

A1 83 1000 0 0 9 5 9

A184 1000 0 0 9 5 9

A185 1000 0 10 9 3 9

ABUTH = Abutilon theophrasti; SOLNI = Solanum nigrum; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi; ALOMY = Alopecurus myosuroides; ECHCG = Echinochloa crus-galli Example B2: Herbicidal action

Seeds of a variety of test species were sown in standard soil in pots. After 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity), the plants were sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone / water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). The test plants were then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65% humidity) and watered twice daily. After 1 3 days, the test was evaluated (10 = total damage to plant; 0 = no damage to plant). Table B2: Application post-emergence

Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY E

No. (g/ha)

A2 1000 - 2 0 7 4 6

A3 1000 - 3 0 7 4 5

A6 1000 - 3 1 7 4 5

A7 1000 - 0 0 8 5 7

A8 1000 - 2 0 6 4 6

A9 1000 - 1 0 6 3 6

A 10 1000 - 2 2 6 4 6

A l l 1000 - 2 0 5 2 4

A12 1000 - 1 0 6 2 6

A 13 1000 - 2 3 6 4 5

A14 1000 - 2 3 6 3 3

A 16 1000 - 0 - 7 6 5

A 17 1000 - 2 0 8 7 7

A 18 1000 - 2 0 4 2 4

A19 1000 - 2 0 6 4 3

A20 1000 - 2 3 7 3 4

A21 1000 - 5 3 7 4 4

A22 1000 - 3 3 6 4 4

A23 1000 4 4 7 4 5

A24 1000 - 6 4 7 4 5

A25 1000 - 0 0 5 0 4

A26 1000 2 0 3 2 4

A27 1000 0 - 5 0 4

A29 1000 - 0 0 7 6 7

A30 1000 - 2 0 8 6 7

A3 1 1000 - 0 - 7 7 7

A32 1000 - 2 0 7 6 7 Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY E

No. (g/ha)

A33 1000 0 0 7 7 6

A36 1000 0 - 7 5 6

A37 1000 0 2 7 6 7

A38 1000 0 3 7 6 6

A39 1000 0 0 7 5 6

A40 1000 0 0 7 5 7

A42 1000 0 0 7 6 7

A43 1000 0 0 7 5 6

A44 1000 0 - 7 6 7

A45 1000 0 0 7 6 6

A46 1000 0 0 7 5 5

A47 1000 - - 6 4 3

A48 1000 0 0 6 3 3

A49 1000 - 0 6 3 4

A50 1000 0 0 6 4 3

A51 1000 2 0 6 1 2

A53 1000 2 5 6 2 4

A56 1000 9 0 0 0 0

A60 1000 2 1 6 3 5

A61 1000 2 0 4 1 1

A62 1000 3 1 6 2 2

A63 1000 1 0 6 2 3

A64 1000 2 1 7 3 5

A65 1000 2 0 7 5 3

A66 1000 4 3 7 3 4

A67 1000 3 4 4 2 3

A68 1000 0 0 7 2 5

A69 1000 10 10 6 2 5 Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY ECHCG

No. (g/ha)

A71 1000 1 0 6 2 4

A72 1000 - 2 0 6 2 3

A73 1000 - 1 0 6 2 4

A74 1000 - 0 0 6 1 5

A75 1000 - 3 2 5 1 1

A78 1000 - 0 0 6 1 1

A79 1000 - 1 0 5 1

A81 1000 - 1 0 6 1

A82 1000 - 3 0 7 1 3

A83 1000 - 0 0 4 0 1

A84 1000 - 3 0 6 1 2

A86 1000 - 2 0 6 2 4

A88 1000 - 2 0 4 0 2

A89 1000 - 2 0 6 2 4

A91 1000 1 - 2 9 4 5

A92 1000 1 - 0 6 4 4

A93 1000 1 - 0 6 6 5

A94 1000 - 4 0 6 2 4

A95 1000 - 1 0 6 3 5

A96 1000 - 1 0 7 2 3

A97 1000 - 0 0 6 2 3

A98 1000 - 0 0 6 3 3

A99 125 1 - 0 6 2 4

A 100 1000 - 2 1 6 2 5

A101 1000 - 1 0 6 1 1

A 102 1000 - 0 0 5 1 2

A103 1000 - 2 0 6 2 3

A104 1000 2 0 6 3 3 Comp. Rate ABUTH SOLNI AMARE SETFA ALOMY E No. (gha)

A105 1000 - 2 2 7 4 3

A106 1000 - 1 3 6 2 2

A107 1000 - 1 1 5 2 3

A108 1000 - 0 0 5 2 1

A109 1000 - 3 0 5 1 1

A110 1000 - 2 0 5 3 3

Atll 1000 - 0 0 5 1 2

A112 1000 - 2 0 5 1 3

Al 13 1000 - 2 0 5 0 0

A114 1000 1 - 0 6 4 5

Al 15 1000 1 - 0 6 4 6

A116 1000 3 - 0 6 4 4

Al 17 1000 0 - 0 6 4 5

A118 1000 0 - 0 6 5 5

A119 1000 0 - 0 6 4 5

A120 1000 0 - 0 6 4 4

A121 1000 0 - 0 6 4 4

A123 1000 0 - 0 6 3 5

A124 1000 0 - 0 6 4 5

A125 1000 1 - 0 6 4 5

A126 1000 1 - 0 6 4 5

A127 1000 0 - 0 6 5 5

A128 1000 1 - 0 2 3 4

A129 1000 1 - 1 6 4 4

A130 1000 1 - 1 6 4 3

A131 1000 1 - 3 6 4 4

A132 1000 2 - 4 6 6 5

A133 1000 6 3 7 4 6 Comp. Rate ABUTH SOLN1 AMARE SETFA ALOMY ECHCG No. (g/ha)

A134 1000 7 0 7 5 6

A135 1000 2 0 6 5 3

A 136 1000 2 2 7 2 5

A137 1000 6 4 7 3 6

A138 1000 3 2 7 3 5

A 139 1000 2 0 7 3 5

A 140 1000 2 0 6 5 5

A141 875 3 1 6 2 5

A142 1000 3 4 7 4 4

A143 1000 3 2 7 5 5

A144 1000 7 4 7 6 6

A145 1000 1 3 7 5 5

A 148 1000 0 3 7 4 5

A149 1000 3 2 7 4 6

A150 1000 3 3 7 4 5

A151 1000 0 0 6 4 5

A152 1000 0 2 7 6 7

A153 1000 2 0 7 4 6

A154 1000 3 1 7 3 6

A1 56 1000 1 0 7 5 6

A157 1000 0 0 7 5 6

A158 1000 1 0 6 5 6

A164 1000 4 0 0 0 0

A 167 1000 2 0 6 4 6

A168 1000 0 0 6 3 6

A174 1000 0 1 5 3 4

A181 1000 0 0 5 4 3

A182 1000 1 0 5 3 5 Comp. Rate ABUTH SOLNI AMARE SET FA ALOMY ECHCG

No. (g/ha)

A183 1000 0 0 5 2 5

A184 1000 1 3 6 4 5

A185 1000 0 0 5 2 3

ABUTH = Abutilon theophrasti; SOLNI = Solanum nigrum; AMARE = Amaranthus retroflexus; SETFA = Setaria faberi; ALOMY = Alopecurus myosuroides; ECHCG = Echinochloa crus-galli.