WO2011033251A1 - Dérivés d'isoxazoline herbicides - Google Patents

Dérivés d'isoxazoline herbicides Download PDF

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Publication number
WO2011033251A1
WO2011033251A1 PCT/GB2010/001712 GB2010001712W WO2011033251A1 WO 2011033251 A1 WO2011033251 A1 WO 2011033251A1 GB 2010001712 W GB2010001712 W GB 2010001712W WO 2011033251 A1 WO2011033251 A1 WO 2011033251A1
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alkyl
groups
optionally substituted
compound
formula
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PCT/GB2010/001712
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English (en)
Inventor
Jonathan Wesley Paul Dallimore
Myriem El Qacemi
Anthony Marian Kozakiewicz
Adrian Longstaff
Matthew Murdoch Woodhead Mclachlan
James Edward Peace
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Syngenta Limited
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Publication of WO2011033251A1 publication Critical patent/WO2011033251A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • 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.
  • 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 .
  • the present invention therefore provides a compound of formula (I)
  • 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
  • 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.
  • 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
  • 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
  • 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
  • R 14 and R 15 are independently of each other hydrogen, Ci-C alkyl, C
  • 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.
  • the invention provides the use of a compound or a composition of the invention as a herbicide.
  • 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.
  • 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.
  • X is SO
  • the compounds of the invention are sulfoxides, which can exist in two enantiomeric forms.
  • 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.
  • 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.
  • Amino refers to the group -NH 2 .
  • Alkylamino refers to the group -NH-alkyl, wherein alkyl is as defined above.
  • 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 are alkyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, difluoromethyl, trifluoromethyl,
  • Haloalkylthio refers to the group -S-haloalkyl, wherein haloalkyl is as defined above.
  • haloalkylthio groups are trifluoromethylthio, 2,2,2,-trifluoroethylthio, etc.
  • Examples of haloalkylcarbonyl groups include trifluoroethanoyl, 3,3,3 trichloropropanoyl, n-perfluorobutanoyl, etc.
  • 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.
  • the cycloalkyl moiety is, unless otherwise indicated, preferably substituted by one to four substituents, most preferably by one to three
  • Examples of cycloalkoxycarbonyl groups are cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl and cyclohexyloxycarbonyl.
  • 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.
  • 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.
  • alkylaminocarbonyl groups are methylaminocarbonyl,
  • 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 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 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.
  • 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 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.
  • 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.
  • 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.
  • arylalkyl groups examples include 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.
  • 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.
  • 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.
  • R 1 is Ci-C 8 alkyl, more preferably methyl.
  • R 2 is Ci-C 8 alkyl, more preferably methyl.
  • R 1 and R 2 are methyl.
  • R 3 is hydrogen or fluorine. More preferably, R 3 is hydrogen.
  • R 4 is hydrogen or fluorine. More preferably, R 4 is hydrogen.
  • R 3 and R 4 are hydrogen.
  • R 5 is hydrogen, halogen or Ci-Csalkyl, more preferably hydrogen, fluorine or methyl, still more preferably hydrogen or fluorine.
  • R 6 is hydrogen, halogen or C r C 8 alkyl, more preferably hydrogen, fluorine or methyl, still more preferably hydrogen or fluorine.
  • R 3 and R 6 are both hydrogen or fluorine. Still more preferably, R 5 and R 6 are both fluorine.
  • 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
  • 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 .
  • 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 .
  • R 7 is hydrogen, C
  • 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 .
  • R 7 is hydrogen, methyl-, ethyl-, 2-methyl-prop-2-yl-,
  • R 7 is methyl-, ethyl-, 2-methyl-prop-2-yl-, trifluoromethyl-, or 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-.
  • R 7 is methyl-, ethyl
  • 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
  • phenyl or aryl (e.g. phenyl) substituted by one to five groups R 13 , or aryl-C
  • R 8 is hydrogen, C
  • 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 .
  • 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
  • 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-.
  • 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-.
  • 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 .
  • 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.
  • each R 9 is independently halogen, cyano, C 3 -C 6 cycloalkyl, C
  • 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
  • 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.
  • each R 12 is independently halogen, cyano, C 3 -C 6 cycloalkyl, C
  • each R 12 is independently C3-C 6 cycloalkyl or Ci-C 6 alkoxy.
  • 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.
  • X is SO or S0 2 , more preferably S0 2 .
  • 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).
  • 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
  • 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).
  • 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).
  • 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
  • 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.
  • 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.
  • a base for example, an organic base, such as pyridine, or a inorganic base, such as potassium hydroxide
  • 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
  • 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
  • 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).
  • 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 ).
  • 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.
  • 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.
  • 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-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,
  • LiHMDS bis(trimethylsilyl)amide
  • 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.
  • dihalomethylene compounds i.e.
  • 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.
  • a base such as potassium carbonate
  • 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.
  • 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.
  • 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 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,
  • 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.
  • 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.
  • the active ingredients 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.
  • 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.
  • compositions according to the invention are known per se.
  • 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,
  • 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.
  • 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.
  • 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.
  • non-ionic, anionic or cationic surfactants examples include surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • 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).
  • silicone surfactants especially polyalkyl -oxide-modified heptamefhyltriloxanes which are commercially available e.g. as Silwet L-77®, and also perfluorinated surfactants.
  • concentration of the surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
  • 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).
  • an organic solvent 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
  • a further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
  • alkyl- pyrrolidones e.g. Agrimax®
  • formulations of alkyl- pyrrolidones e.g. Agrimax®
  • synthetic lattices e.g. polyacrylamide, polyvinyl compounds or poly-l -p-menthene (e.g. Bond®, Courier® or Emerald®)
  • propionic acid for example Eurogkem Pen-e-trate®
  • 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.
  • a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance.
  • 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.
  • Emulsifiable concentrates are:
  • 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 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 5 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surface-active agent 1 to 40 %, preferably 2 to 30 %
  • 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 %
  • active ingredient 0.1 to 30 %, preferably 0.1 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • 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 %
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the solutions are suitable for use in the form of microdrops.
  • 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)
  • the active ingredient is dissolved in methylene chloride and applied to the carrier by spraying, and the solvent is then evaporated off in vacuo.
  • 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.
  • 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)
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates active ingredient 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 %
  • 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).
  • herbicide as used herein means a compound that controls or modifies the growth of plants.
  • 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.
  • plants refers to all physical parts of a plant, including seeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, and fruits.
  • 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,
  • monocotyledonous species for example Abutilon, Amaranthus, Chenopodium, Chrysanthemum, Euphorbia, Galium, Ipomoea, Kochia, Nasturtium,
  • 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.
  • herbicides or classes of herbicides e.g. auxins or ALS-, EPSPS-, PPO- and HPPD-inhibitors
  • 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).
  • 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).
  • 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.
  • 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).
  • 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.
  • the following mixtures of the compound of formula (I) are important:
  • 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-(trifluoromethyl)-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-pyridinyl]carbonyl]- bicyclo[3.2.1 ]oct-3-en-2-one).
  • 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)).
  • a PPO inhibitor e.g. compound of formula (1) +
  • 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
  • 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.
  • 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).
  • 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 ), be
  • 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
  • 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.
  • 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.
  • 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.
  • 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),
  • 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.
  • 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).
  • active ingredient relates to the respective mixture of compound of fomiula (I) with the safener.
  • the safener and a compound of formula (I) and one or more additional herbicide(s), if any, are applied simultaneously.
  • 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.
  • the safener and a compound of formula (I) and one or more additional herbicide(s), if any are applied sequentially.
  • 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 (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]carbonyl]-bicyclo[3.2.1 ]oct-3-en-2- one 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 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.
  • 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:
  • 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).
  • N-fluorobenzenesulfonimide N-fluorobenzenesulfonimide
  • Pa-'Bu l -/er/-butyl-2,2,4,4,4-pentakis(dimethylamino)-2-lambda 5 -5,4- lambda 5 -5-catenadi(phosphazene)
  • R 1 and R 2 are both methyl
  • R 3 , R 4 , R 5 and R 6 are hydrogen
  • R 7 and R 8 are as defined in the table.
  • 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).
  • R 1 and R 2 are both methyl
  • R 3 , R 4 , R 5 and R 6 are hydrogen
  • R 7 is ethoxycarbonyl and R s is as defined in the table.
  • ABUTH Abutilon theophrasti
  • SOLNI Solanum nigrum
  • AMARE Amaranthus retroflexus
  • SETFA Setaria faberi
  • ALOMY Alopecurus myosuroides
  • ECHCG Echinochloa crus-galli
  • ABUTH Abutilon theophrasti
  • SOLNI Solanum nigrum
  • AMARE Amaranthus retroflexus
  • SETFA Setaria faberi
  • ALOMY Alopecurus myosuroides
  • ECHCG Echinochloa crus-galli.

Abstract

La présente invention concerne des dérivés isoxazoline-oximes de formule (I) dans laquelle R2, R3, R4, R5, R6, R7, R8 et X sont tels que définis dans la revendication 1; ou un sel ou N-oxyde de ceux-ci. L'invention concerne également des procédés et des intermédiaires pour la préparation des composés de formule (I), des compositions herbicides comprenant ces composés et des procédés d'utilisation de ces composés pour réguler la croissance des plantes.
PCT/GB2010/001712 2009-09-16 2010-09-10 Dérivés d'isoxazoline herbicides WO2011033251A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109721563A (zh) * 2018-12-29 2019-05-07 西南大学 磺酰噻唑化合物及其制备方法和应用
CN110294747A (zh) * 2018-03-23 2019-10-01 东莞东阳光科研发有限公司 异噁唑啉衍生物及其在农业中的应用

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CN110294747A (zh) * 2018-03-23 2019-10-01 东莞东阳光科研发有限公司 异噁唑啉衍生物及其在农业中的应用
CN110294747B (zh) * 2018-03-23 2020-07-24 东莞市东阳光农药研发有限公司 异噁唑啉衍生物及其在农业中的应用
CN109721563A (zh) * 2018-12-29 2019-05-07 西南大学 磺酰噻唑化合物及其制备方法和应用

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