WO2010057880A1 - Nouveaux herbicides - Google Patents

Nouveaux herbicides Download PDF

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Publication number
WO2010057880A1
WO2010057880A1 PCT/EP2009/065297 EP2009065297W WO2010057880A1 WO 2010057880 A1 WO2010057880 A1 WO 2010057880A1 EP 2009065297 W EP2009065297 W EP 2009065297W WO 2010057880 A1 WO2010057880 A1 WO 2010057880A1
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formula
compound
alkyl
optionally substituted
crc
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PCT/EP2009/065297
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English (en)
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Christopher John Mathews
James Nicholas Scutt
Louisa Robinson
Melloney Tyte
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Syngenta Limited
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Publication of WO2010057880A1 publication Critical patent/WO2010057880A1/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
    • C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems
    • 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
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • C07D413/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/10—Spiro-condensed systems

Definitions

  • the present invention relates to novel, herbicidally active isoxazolidine and isoxazoline compounds, and derivatives thereof, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting undesired plant growth.
  • Cyclopentanedione compounds having herbicidal action are described, for example, in WO 01/74770 and WO 96/03366.
  • the present invention accordingly relates to compounds of formula I
  • G is hydrogen or an agriculturally acceptable metal, sulfonium, ammonium or latentiating group
  • R 1 is methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, ethynyl, halogen,
  • R 2 and R 3 are independently of each other hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, Ci-C 2 alkoxy,
  • R 4 is hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, halomethyl, haloethyl, vinyl, propenyl, ethynyl, propynyl, halogen, CrC 2 alkoxy or CrC 2 haloalkoxy,
  • R 5 and R 9 are independently of each other hydrogen or methyl
  • R 6 is hydrogen optionally substituted CrC 6 alkyl, optionally substituted C 3 -C 7 cycloalkyl, optionally substituted aryl, optionally substituted heteroaryl or a group COR 10 , CO 2 R 11 , R 7 and R 8 are independently of each other, hydrogen, optionally substituted C-i-C ⁇ alkyl, optionally substituted C 3 -C 7 cycloalkyl, optionally substituted C 4 -C 7 heterocyclyl, optionally substituted aryl or optionally substituted heteroaryl, or any two of R 6 , R 7 and R 8 may be joined to form a 4-7 membered carbocyclic ring optionally substituted by one to four C 1 -C 3 alkyl groups or a C 4 -C 7 heterocyclyl containing a heteroatom selected from oxygen or sulfur and optionally substituted by one to four CrC 3 alkyl groups, or R 6 and R 7 form a bond,
  • R 10 is optionally substituted CrC 6 alkyl or optionally substituted phenyl
  • R 11 is optionally substituted C-i-C ⁇ alkyl or optionally substituted phenyl.
  • each alkyl moiety either alone or as part of a larger group is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, n-butyl, sec-butyl, isobutyl, fert-butyl or neopentyl.
  • the alkyl groups are suitably CrC ⁇ alkyl groups, but are preferably CrC 4 alkyl or CrC 3 alkyl groups, and, more preferably, CrC 2 alkyl groups.
  • the optional substituents on an alkyl moiety include one or more of halogen, nitro, cyano, C 3- C 7 cycloalkyl (itself optionally substituted with Ci-C ⁇ alkyl or halogen), C 5 -C 7 cycloalkenyl (itself optionally substituted with Ci-C 4 alkyl or halogen), hydroxy, Ci-Ci 0 alkoxy, Ci-Ci 0 alkoxy(Ci-Ci 0 )alkoxy, tri(Ci-C 4 )alkylsilyl(CrC 6 )alkoxy, CrC 6 alkoxy- carbonyl(Ci-Cio)alkoxy, CrCiohaloalkoxy, aryl(Ci-C 4 )alkoxy (where the halogen, nitro, cyano, C 3- C 7 cycloalkyl (itself optionally substituted with Ci-C ⁇ alkyl or halogen), C 5 -C 7 cycloalken
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, CF 3 , CF 2 CI, CF 2 H, CCI 2 H, FCH 2 , CICH 2 , BrCH 2 , CH 3 CHF, (CHs) 2 CF, CF 3 CH 2 or CHF 2 CH 2 .
  • aryl refers to aromatic ring systems which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
  • heteroaryl preferably refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulphur.
  • Examples of such groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1 ,2,4-oxadiazolyl, 1 ,3,4-oxadiazolyl, 1 ,2,5-oxadiazolyl, 1 ,2,3-thiadiazolyl, 1 ,2,4-thiadiazolyl, 1 ,3,4-thiadiazolyl, 1 ,2,5-thiadiazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1 ,2,3-triazinyl, 1 ,2,4-triazinyl, 1 ,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl,
  • heteroaromatic radicals include pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, oxazolyl, isoxazolyl, 2,1 ,3-benzoxadiazolyl and thiazolyl.
  • Another group of preferred heteroaryls comprises pyrazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl or quinoxalinyl.
  • pyrazolyl 1 ,2,3-triazolyl, 1 ,2,4-triazolyl
  • pyridazinyl pyrazinyl
  • quinolinyl isoquinolinyl
  • cinnolinyl quinazolinyl or quinoxalinyl.
  • heterocyclyl preferably refers to a non-aromatic preferably monocyclic or bicyclic ring systems containing up to 7 atoms including one or more (preferably one or two) heteroatoms selected from O, S and N.
  • heteroatoms selected from O, S and N.
  • examples of such rings include 1 ,3-dioxolane, oxetane, tetrahydrofuran, morpholine, thiomorpholin and piperazine.
  • the optional substituents on heterocyclyl include CrC ⁇ alkyl and d-C ⁇ haloalkyl as well as those optional substituents given above for an alkyl moiety.
  • Cycloalkyl includes preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.
  • the optional substituents on cycloalkyl include Ci-C 3 alkyl as well as those optional substituents given above for an alkyl moiety.
  • Carbocyclic rings include aryl, cycloalkyl or carbocyclic groups, and cycloalkenyl groups.
  • the optional substituents on aryl, heteroaryl and carbocycles are preferably selected independently, from halogen, nitro, cyano, rhodano, isothiocyanato, C-i-C ⁇ alkyl, Ci-C 6 haloalkyl, Ci-C 6 alkoxy(Ci-C 6 ) alkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 - C 7 cycloalkyl (itself optionally substituted with d-C ⁇ alkyl or halogen), C 5-7 cycloalkenyl (itself optionally substituted with CrC 6 alkyl or halogen), hydroxy, Ci-Ci 0 alkoxy, Ci-Ci 0 alkoxy(Cr Cio)alkoxy, tri(Ci-C 4 )alkylsilyl(CrC6)alkoxy, Ci-C6alk
  • aryl or heteroaryl include arylcarbonylamino (where the aryl group is substituted by d-C ⁇ alkyl or halogen), (d-C ⁇ Jalkoxycarbonylamino, (Ci-C6)alkoxycarbonyl- ⁇ /-(CrC6)alkylamino, aryloxycarbonylamino (where the aryl group is substituted by d-C ⁇ alkyl or halogen), aryloxycarbonyl- ⁇ /-(Ci-C6)alkylamino, (where the aryl group is substituted by d-C ⁇ alkyl or halogen), arylsulphonylamino (where the aryl group is substituted by d-C ⁇ alkyl or halogen), arylsulphonyl- ⁇ /-(Ci-C6)alkylamino (where the aryl group is substituted by d-C ⁇ alkyl or halogen), aryl-N-(
  • substituents are independently selected from halogen, C-i-C ⁇ alkyl, d-C ⁇ haloalkyl, d-C ⁇ alkoxy, d-C ⁇ haloalkoxy, d-
  • dialkylamino substituents include those where the dialkyl groups together with the N atom to which they are attached form a five, six or seven-membered heterocyclic ring which may contain one or two further heteroatoms selected from O, N or S and which is optionally substituted by one or two independently selected d-C ⁇ alkyl groups.
  • heterocyclic rings are formed by joining two groups on an N atom
  • the resulting rings are suitably pyrrolidine, piperidine, thiomorpholine and morpholine each of which may be substituted by one or two independently selected d- C ⁇ alkyl groups.
  • the invention relates also to the agriculturally acceptable salts which the compounds of formula I are able to form with transition metal, alkali metal and alkaline earth metal bases, amines, quaternary ammonium bases or tertiary sulfonium bases.
  • transition metal alkali metal and alkaline earth metal salt formers
  • hydroxides of copper, iron, lithium, sodium, potassium, magnesium and calcium
  • hydroxides, bicarbonates and carbonates of sodium and potassium are preferably the hydroxides, bicarbonates and carbonates of sodium and potassium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Ci-Cisalkylamines, Ci-C 4 hydroxyalkylamines and C 2 -C 4 alkoxyalkyl- amines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbut
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R 3 R b R c R d )]OH, wherein R 3 , R b , R c and R d are each independently of the others hydrogen, Ci-C 4 alkyl. Further suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • Preferred tertiary sulfonium bases suitable for salt formation correspond, for example, to the formula [SR e R f R g ]OH, wherein R e , R f and R 9 are each independently of the others C 1 -C 4 alkyl.
  • Trimethylsulfonium hydroxide is especially preferred.
  • Suitable sulfonium bases may be obtained from the reaction of thioethers, in particular dialkylsulfides, with alkylhalides, followed by conversion to a suitable base, for example a hydroxide, by anion exchange reactions.
  • the compounds of formula I according to the invention also include hydrates which may be formed during the salt formation.
  • the latentiating groups G are selected to allow its removal by one or a combination of biochemical, chemical or physical processes to afford compounds of formula I where G is H before, during or following application to the treated area or plants. Examples of these processes include enzymatic cleavage, chemical hydrolysis and photoloysis. Compounds bearing such groups G may offer certain advantages, such as improved penetration of the cuticula of the plants treated, increased tolerance of crops, improved compatibility or stability in formulated mixtures containing other herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides, or reduced leaching in soils.
  • the latentiating group G is preferably selected from the groups CrC 8 alkyl, C 2 -C 8 haloalkyl, phenylC-i-Csalkyl (wherein the phenyl may optionally be substituted by CrC 3 alkyl, Ci-C 3 haloalkyl, CrC 3 alkoxy, CrC 3 haloalkoxy, CrC 3 alkylthio, CrC 3 alkylsulfinyl, Ci-C 3 alkylsulfonyl, halogen, cyano or by nitro), heteroaryld-Csalkyl (wherein the heteroaryl may optionally be substituted by Ci-C 3 alkyl, C r C 3 haloalkyl, C r C 3 alkoxy, C r C 3 haloalkoxy, C r C 3 alkylthio, C r C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, halogen
  • R a is H, CrCi 8 alkyl, C 2 -Ci 8 alkenyl, C 2 -Ci 8 alkynyl, C r Ci 0 haloalkyl, C r Ci 0 cyanoalkyl, C r C-ionitroalkyl, Ci-C-ioaminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 -(Cr C 5 )oxyalkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5
  • R b is CrCi 8 alkyl, C 3 -Ci 8 alkenyl, C 3 -Ci 8 alkynyl, C 2 -Ci 0 haloalkyl, Ci-Ciocyanoalkyl, C r Cionitroalkyl, C 2 -Cioaminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 - C 5 alkynyloxy(CrC 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(C
  • R c and R d are each independently of each other hydrogen, Ci-Ci O alkyl, C 3 -Ci 0 alkenyl, C 3 - Cioalkynyl, C 2 -Ciohaloalkyl, Ci-Ciocyanoalkyl, Ci-Cionitroalkyl, Ci-Cioaminoalkyl, Cr C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 -C 7 cycloalkyl(CrC 5 )alkyl, C r C 5 alkoxy(CrC 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 -C 5 alkynyloxy(CrC 5 )alkyl, C r C 5 alkylthio(CrC 5 )alkyl, Ci-C 5 alkyls
  • R f and R 9 are are each independently of each other d-Ci O alkyl, C 2 -Ci 0 alkenyl, C 2 -Ci 0 alkynyl, d- Cioalkoxy, CrCiohaloalkyl, d-Ciocyanoalkyl, d-donitroalkyl, Ci-Cioaminoalkyl, Cr C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 -C 7 cycloalkyl(Ci-C 5 )alkyl, C r C 5 alkoxy(CrC 5 )alkyl, C3-C 5 alkenyloxy(Ci-C 5 )alkyl, C3-C 5 alkynyloxy(Ci-C 5 )alkyl, d- C 5 alkylthio(CrC 5 )alkyl
  • R h is CrCioalkyl, C 3 -Cioalkenyl, C 3 -Cioalkynyl, Ci-Ciohaloalkyl, Ci-Ciocyanoalkyl, d- Cionitroalkyl, C 2 -Ci 0 aminoalkyl, Ci-C 5 alkylamino(Ci-C 5 )alkyl, C 2 -C 8 dialkylamino(Ci-C 5 )alkyl, C 3 - C 7 cycloalkyl(CrC 5 )alkyl, Ci-C 5 alkoxy(Ci-C 5 )alkyl, C 3 -C 5 alkenyloxy(CrC 5 )alkyl, C 3 - C 5 alkynyloxy(Ci-C 5 )alkyl, Ci-C 5 alkylthio(Ci-C 5 )alkyl, Ci-C 5 alkylsulfinyl(Ci-C 5
  • the latentiating group G is a group -C(X a )-R a or -C(X b )-X c -R b , and the meanings of X a , R a , X b , X c and R b are as defined above.
  • G is hydrogen, an alkali metal or alkaline earth metal, where hydrogen is especially preferred.
  • compounds of formula I may exist in different isomeric forms.
  • G is hydrogen, for example, compounds of formula I may exist in different tautomeric forms:
  • R 5 I is, methyl, ethyl, n-propyl, cyclopropyl, vinyl, ethynyl, halogen, Ci-C 2 alkoxy or Ci-C 2 haloalkoxy. More preferably, R 1 is methyl or ethyl.
  • R 2 is methyl, ethyl, halogen, Ci-C 2 alkoxy, CrC 2 haloalkoxy, optionally substituted phenyl, optinally substituted naphthyl or optionally substituted pyridyl.
  • R 2 is methyl, optionally substituted phenyl, optionally substituted naphthyl or optionally substituted pyridyl.
  • R 2 are CrC 2 alkyl, d- C 2 haloalkyl, C r C 2 alkoxy, C r C 2 haloalkoxy, C r C 2 alkylthio, C r C 2 haloalkylthio, C r C 2 alkylsulfinyl, CrC 2 haloalkylsulfinyl, Ci-C 2 alkylsulfonyl, Ci-C 2 haloakylsulfonyl, amino, Ci-C 2 alkylamino, di-Cr C 2 alkylamino, d-C ⁇ lkylcarbonylamino, CrC 2 alkoxycarbonylamino, Ci-C 2 alkylsulfonylamino, Cr C 2 haloalkylsulfonylamino, CrC 2 alkylcarbonyl, Ci-C 2 alk
  • these phenyl rings R 2 are substituted on two adjacent carbons by -O- CH 2 -O-, -0-CH 2 -CH 2 -O- and 0-CF 2 -O- to form annellated rings.
  • R 2 is phenyl subsitituted one to three times by fluorine, chlorine, bromine, methyl, methoxy, trifluorom ethyl, trifluoromethoxy, nitro or cyano.
  • R 2 is methyl
  • R 2 is hydrogen
  • R 3 is preferably optionally substituted phenyl, optionally substituted naphthyl or optionally substituted pyridyl.
  • R 3 Preferred substituents on these phenyl, naphthyl or pyridyl rings R 3 are CrC 2 alkyl, Cr C 2 haloalkyl, C r C 2 alkoxy, C r C 2 haloalkoxy, C r C 2 alkylthio, C r C 2 haloalkylthio, C r C 2 alkylsulfinyl, CrC 2 haloalkylsulfinyl, Ci-C 2 alkylsulfonyl, Ci-C 2 haloakylsulfonyl, amino, Ci-C 2 alkylamino, di-Cr C 2 alkylamino, Ci-C 2 alkylcarbonylamino, Ci-C 2 alkoxycarbonylamino, Ci-C 2 alkylsulfonylamino, Cr C 2 haloalkylsulfonylamino, CrC 2 alkylcarbonyl, Ci-C 2 al
  • R 3 are substituted on two adjacent carbons by -O- CH 2 -O-, -0-CH 2 -CH 2 -O- and 0-CF 2 -O- to form annellated rings. More preferably, R 3 is phenyl subsitituted one to three times by fluorine, chlorine, bromine, methyl, methoxy, trifluorom ethyl, trifluoromethoxy, nitro or cyano.
  • R 3 is hydrogen
  • R 4 is methyl, ethyl, n-propyl, vinyl or ethynyl, in particular methyl or ethyl.
  • R 4 is hydrogen
  • R 5 and R 9 in the compounds of formula I are preferably hydrogen
  • R 6 is C 1 -C 4 alkyl, and, more preferably, methyl.
  • R 6 and R 7 together with the atoms to which they are joined form a 5- or 6-membered carbocyclic ring optionally substituted by one to four methyl groups.
  • R 7 and R 8 are independently hydrogen, Ci-C 4 alkyl, a 5- or 6-membered carbocylic ring optionally substituted once or twice by CrC 2 alkyl or Ci-C 2 alkoxy, a 5- or 6-membered heterocyclyl containing one oxygen atom, or R 7 and R 8 together with the atom to which they are attached form a 5- or 6-membered carbocyclic ring optionally substituted once or twice by d- C 2 alkyl or R 7 and R 8 together with the atom to which they are attached form a 5- or 6-membered heterocyclyl containing one oxygen atom.
  • R 7 and R 8 are independently hydrogen, methyl, a 5- or 6-membered heterocyclyl containing one oxygen atom, or R 7 and R 8 together form a 5- or 6-membered heterocyclyl containing one oxygen atom.
  • R 10 and R 11 are independently C 1 -C 4 alkyl.
  • the compounds of formula (I) can be present in the form of two isomeric compounds, of formula (IA) and (IB).
  • formula (IA) formula (1B) This invention covers both a compound of formula (IA) and a compound of formula (IB), together with mixtures of these compounds in any ratio.
  • the O-acylation of cyclic 1 ,3-diones may be effected by procedures similar to those described, for example, by R. Haines, US4175135, and by T. Wheeler, US4422870, US4659372 and US4436666.
  • diones of formula (A) may be treated with an acylating agent preferably in the presence of at least one equivalent of a suitable base, and optionally in the presence of a suitable solvent.
  • the base may be inorganic, such as an alkali metal carbonate or hydroxide, or a metal hydride, or an organic base such as a tertiary amine or metal alkoxide.
  • suitable inorganic bases include sodium carbonate, sodium or potassium hydroxide, sodium hydride
  • suitable organic bases include trialkylamines, such as trimethylamine and triethylamine, pyridines or other amine bases such as 1 ,4-diazobicyclo[2.2.2]octane and 1 ,8- diazabicyclo[5.4.0]undec-7-ene.
  • Preferred bases include triethylamine and pyridine.
  • Suitable solvents for this reaction are selected to be compatible with the reagents and include ethers such as tetrahydrofuran and 1 ,2-dimethoxyethane and halogenated solvents such as dichloromethane and chloroform.
  • acylating agent is a carboxylic acid
  • acylation is preferably effected in the presence of a known coupling agent such as 2-chloro-1- methylpyridinium iodide, ⁇ /, ⁇ /-dicyclohexylcarbodiimide, 1-(3-dimethylaminopropyl)-3- ethylcarbodiimide and ⁇ /, ⁇ /-carbodiimidazole, and optionally in the presence of a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile.
  • a base such as triethylamine or pyridine in a suitable solvent such as tetrahydrofuran, dichloromethane or acetonitrile.
  • Phosphorylation of cyclic 1 ,3-diones may be effected using a phosphoryl halide or thiophosphoryl halide and a base by procedures analogous to those described by L. Hodakowski, US4409153.
  • Sulfonylation of a compound of formula (A) may be achieved using an alkyl or aryl sulfonyl halide, preferably in the presence of at least one equivalent of base, for example by the procedure of C. Kowalski and K. Fields, J. Org. Chem., (1981 ), 46, 197-201.
  • a compound of formula (A), wherein R 6 and R 7 form a bond may be prepared by the reaction of a compound of formula (B) with a nitrile oxide of formula (C) in a suitable solvent such as dichloromethane, chloroform or toluene.
  • a nitrile oxide of formula (C) may be prepared by the dehydration of a nitroalkane of formula (D), in the presence of a dehydrating agent such as phenylisocyanate or 1 ,4-phenylene diisocyanate, or by the dehydrohalogenation of a hydroximoyl halide of formula (E), wherein Hal is a halogen (preferably chlorine or bromine) by contact with a suitable base (such as triethylamine or potassium carbonate), according to known procedures (see, for example, V. Jager and I. M ⁇ ller, Tetrahedron (1985), 41 (17), 3519-3528; E. Kantorowski et al., J. Org. Chem., (1998), 63, 5272- 5274; L. Deng and Y. Hu, Synth. Commun. (2007), 37, 157-163).
  • a dehydrating agent such as phenylisocyanate or 1 ,4-pheny
  • the nitrile oxide of formula (C) is not isolated, but instead is prepared in the presence of a compound of formula (B), at a suitable temperature (preferably -20 0 C to 100 0 C), and in a suitable solvent such as dichloromethane, chloroform or toluene, according to known procedures.
  • a suitable temperature preferably -20 0 C to 100 0 C
  • a suitable solvent such as dichloromethane, chloroform or toluene
  • additional compounds of formula (A) may be prepared from a compound of formula (B) by reaction with a nitrone of formula (F), optionally in the presence of a suitable solvent (such as dichloromethane, chloroform, acetonitrile and toluene), and optionally in the presence of a Lewis acid catalyst such as aluminium chloride, bismuth(lll) chloride, bismuth(lll) trifluoromethanesulfonate, boron trifluoride, cerium(lll) chloride, copper(l) trifluoromethanesulfonate, diethylaluminium chloride, hafnium(IV) chloride, iron(lll) chloride, lithium perchlorate, lithium trifluoromethanesulfonate, magnesium bromide, magnesium iodide, scandium(lll) trifluoromethanesulfonate, tin(IV) chloride, titanium(IV) chloride, titanium(IV) iso
  • Nitrones of formula (F) are known compounds, or may be made by known methods from known compounds (see, for example, N. Langlois and F. Rakotondradany, Tetrahedron, (2000), 56, 2437-2448; S. Kang and W. Kim, Synlett., (1991 ), 520; J. Hwu et al., J. Chem. So ⁇ , Perkin. Trans.1 (1989), 1823-1831 ; O. Exner, Coll. Czech. Chem., (1951 ), 16, 258-267).
  • a compound of formula (A) wherein R 6 is H may be converted into additional compounds of formula (A) by known transformations (for example, acylation according to the procedure of S. Kang and W. Kim, Synlett., (1991 ), 520).
  • a compound of formula (B) may be prepared from a compound of formula (G), wherein Hal is bromine or iodine, and a compound of formula (H) according to the procedure of K. Saito and H. Yamachika, US4371711.
  • Compounds of formula (G) are known compounds, (see, for example, M. Muehlebach et al., WO08/071405; M. Muehlebach et ai, WO08/1 10308; M. Muehlebach et ai, WO08/110307; M. Feuerstein et ai., Synthesis, (2004), 8, 1281-1289; T. Maetzke et ai., WO01/017972, R. Fischer et al., WO99/43649), or may be made by known methods from known compounds.
  • the compounds of formula I according to the invention can be used as crop protection agents in unmodified form, as obtained in the synthesis, but they are generally formulated into crop protection compositions in a variety of ways using formulation adjuvants, such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, for example in the form of dusting powders, gels, wettable powders, coated or impregnated granules for manual or mechanical distribution on target sites, water-dispersible granules, water-soluble granules, emulsifiable granules, water-dispersible tablets, effervescent compressed tablets, water-soluble tapes, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water (EW) or water-in-oil (WO) emulsions, other multiphase systems such as oil/water/oil or water/oil/water products, oil flowables, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), impregnated polymer films or in other forms known, for example, from the Manual on Development and Use of FAO Specific
  • Such formulations can either be used directly or are diluted prior to use. They can then be applied through suitable ground or aerial application spray equipment or other ground application equipment such as central pivot irrigation systems or drip/trickle irrigation means.
  • Diluted formulations can be prepared, for example, with water, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
  • the formulations can be prepared, for example, by mixing the active ingredient with 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 contained in fine microcapsules consisting of a core and a polymeric shell. Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredients in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be present in the form of liquid technical material, in the form of a suitable solution, in the form of fine particles in solid or liquid dispersion or as a monolithic solid.
  • the encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers or other similar suitable membrane forming material, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane, aminoplast resins or chemically modified starch or other polymers that are known to the person skilled in the art in this connection.
  • microcapsules it is possible for fine so called “microcapsules” to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated with a diffusion limiting membrane as outlined in the preceding paragraph.
  • the active ingredients may be adsorbed on a porous carrier. This may enable the active ingredients to be released into their surroundings in controlled amounts (e.g. slow release).
  • Other forms of controlled release formulations are granules or powders in which the active ingredient is dispersed or dissolved in a solid matrix consisting of a polymer, a wax or a suitable solid substance of lower molecular weight.
  • Suitable polymers are polyvinyl acetates, polystyrenes, polyolefins, polyvinyl alcohols, polyvinyl pyrrolidones, alkylated polyvinyl pyrrolidones, copolymers of polyvinyl pyrrolidones and maleic anhydride and esters and half- esters thereof, chemically modified cellulose esters like carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, examples of suitable waxes are polyethylene wax, oxidized polyethylene wax, ester waxes like montan waxes, waxes of natural origin like camauba wax, candelilla wax, bees wax etc. Other suitable matrix materials for slow release formulations are starch, stearin, lignin.
  • composition adjuvants suitable for the preparation of the compositions according to the invention are known per se.
  • liquid carriers there may be used: water, aromatic solvents such as toluene, m-xylene, o- xylene, p-xylene and mixtures thereof, cumene, aromatic hydrocarbon blends with boiling ranges between 140 and 320 0 C known under various trademarks like Solvesso ® , Shellsol A ® , Caromax ® , Hydrosol ® , paraffinic and isoparaffinic carriers such as paraffin oils, mineral oils, de- aromatized hydrocarbon solvents with boiling ranges between 50 and 320 0 C known for instance under the trademark Exxsol ® , non-dearomatized hydrocarbon solvents with boiling ranges between 100 and 320 0 C known under the tradename Varsol ® , isoparaffinic solvents with boiling ranges between 100 and 320 0 C known under tradenames like Isopar ® or Shellsol T ® , hydrocarbons such as cyclohexane, tetrahydronaphthalene (tetral
  • Water is generally the carrier of choice for the dilution of the concentrates.
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica (fumed or precipated silica and optionally functionalised or treated, for instance silanised), attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montomorillonite, cottonseed husks, wheatmeal, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials, as described, for example, in the EPA CFR 180.1001. (c) & (d).
  • a large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those formulations which can be diluted with a carrier prior to use.
  • Surface-active substances may be anionic, cationic, amphoteric, non-ionic or polymeric and they may be used as emulsifiying, wetting, dispersing or suspending agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulphate; Sodium lauryl sulphate, salts of alkylarylsulfonates, such as calcium or sodium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products, such as nonylphenol ethoxylates; alcohol-alkylene oxide addition products, such as tridecyl alcohol 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 lauryl trimethylammonium chlor
  • Further adjuvants which can usually be used in pesticidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspending agents, dyes, anti-oxidants, foaming agents, light absorbers, mixing aids, anti-foams, complexing agents, neutralising or pH-modifying substances and buffers, corrosion-inhibitors, fragrances, wetting agents, absorption improvers, micronutrients, plasticisers, glidants, lubricants, dispersants, thickeners, anti-freezes, microbiocides, compatibility agents and solubilisers and also liquid and solid fertilisers.
  • the formulations may also comprise additional active substances, for example further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
  • compositions according to the invention can additionally include an additive (commonly referred to as an adjuvant), comprising a mineral oil, an oil of vegetable or animal origin, alkyl esters of such oils or mixtures of such oils and oil derivatives.
  • an additive commonly referred to as an adjuvant
  • the amount of oil additive used 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, emulsifiable vegetable oil, such as AMIGO® (Loveland Products Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • a preferred additive contains, for example, as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters of C8-C 22 fatty acids, especially the methyl derivatives of C 12 -C 1 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being important.
  • Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS- 112-39-0) and methyl oleate (CAS-112-62-9).
  • a preferred fatty acid methyl ester derivative is AGNIQUE ME 18 RD-F® (Cognis).
  • 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 combining them with surface-active substances, such as non-ionic, anionic, cationic or amphoteric surfactants.
  • surface-active substances such as non-ionic, anionic, cationic or amphoteric surfactants.
  • suitable anionic, non-ionic, cationic or amphoteric surfactants are listed on pages 7 and 8 of WO97/34485.
  • 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 C 12 -C 22 fatty alcohols having a degree of ethoxylation of from 5 to 40.
  • surfactants examples include the Genapol types (Clariant). Also preferred are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available e.g. as SILWET L-77®, and also perfluorinated surfactants.
  • concentration of surface-active substances in relation to the total additive is generally from 1 to 50 % by weight.
  • oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are TURBOCHARGE®, ADIGOR® (both (Syngenta Crop Protection AG), ACTIPRON® (BP Oil UK Limited), AGRI-DEX® (Helena Chemical Company).
  • the said surface-active substances may also be used in the formulations alone, that is to say without oil additives.
  • an organic solvent to the oil additive/surfactant mixture can contribute to a further enhancement of action.
  • Suitable solvents are, for example, SOLVESSO® and AROMATIC® solvents (Exxon Corporation). The concentration of such solvents can be from 10 to 80 % by weight of the total weight.
  • Such oil additives which may be in admixture with solvents, are described, for example, in US 4 834 908.
  • a commercially available oil additive disclosed therein is known by the name MERGE® (BASF).
  • Further oil additives that are preferred according to the invention are SCORE® and ADIGOR® (both Syngenta Crop Protection AG).
  • alkylpyrrolidones e.g. AGRIMAX® from ISP
  • formulations of synthetic latices such as, for example, polyacrylamide, polyvinyl compounds or poly-1-p-menthene (e.g. BOND®, COURIER® or EMERALD®) can also be used.
  • Such adjuvant oils as described in the preceding paragraphs may be employed as the carrier liquid in which an active compound is dissolved, emulsified or dispersed as appropriate to the physical form of the active compound.
  • the pesticidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound 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 rate of application of the compounds of formula I may vary within wide limits and depends upon 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 weed or grass 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 1- 2000 g/ha, preferably 1- 1000 g / ha and most preferably at 1- 500 g / ha.
  • Emulsifiable concentrates active ingredient: 1 to 95 %, preferably 60 to 90 % surface-active agents: 1 to 30 %, preferably 5 to 20 % solvents as liquid carrier: 1 to 80 %, preferably 1 to 35 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 5 % solid carriers: 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 agents: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agents: 0.5 to 20 %, preferably 1 to 15 % solid carriers: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carriers: 99.5 to 70 %,
  • Waterdispersible granules active ingredient: 1 to 90 %, preferably 10 to 80 % surface-active agents: 0.5 to 80 %, preferably 5 to 30 % solid carriers: 90 to 10 %, preferably 70 to 30 %
  • Emulsifiable concentrates a) b) c) d) active ingredient 5 % 10 % 25 % 50 % calcium dodecylbenzene- sulfonate 6% 8% 6% 8% castor oil polyglycol ether 4 % - 4 % 4 %
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • the solutions are suitable for application undiluted or after dilution with water.
  • 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% -
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding 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 silica 0.9 % 2% 2 % inorg. carrier 99. 0% 93% 83 %
  • the active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier and the solvent is subsequently evaporated off in vacuo.
  • the finely ground active ingredient is applied uniformly, 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 resulting mixture is extruded and then dried in a stream of air.
  • the active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water.
  • the resulting mixture is extruded and then dried in a stream of air.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates a) b) c) d) active ingredient 3 % 10 % 25 % 50 % propylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
  • the finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.
  • Crops of useful plants in which the compositions according to the invention can be used include especially cereals, in particular wheat and barley, rice, corn, rape, sugarbeet, sugarcane, soybean, cotton, sunflower, peanut and plantation crops.
  • crops is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides or classes of herbicides for example ALS, GS, EPSPS, PPO and HPPD inhibitors
  • An example of a crop that has been rendered tolerant e.g. to imidazolinones, such as 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®.
  • the weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. Control of monocotyledonous weeds, in particular Agrostis, Avena, Setaria, Lolium, Echinochloa, Bromus, Alopecurus and Sorghum is very extensive.
  • 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 NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins and transgenic plants able to synthesise 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 that contain one or more genes which 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 and their seed material can be resistant to herbicides and at the same time also to insect feeding ("stacked" transgenic events). Seed can, for example, have the ability to express an insecticidally active Cry3 protein and at the same time be glyphosate-tolerant.
  • the term "crops" is to be understood as also including crops obtained as a result of conventional methods of breeding or genetic engineering which contain so-called output traits (e.g. improved flavour, storage stability, nutritional content).
  • Areas under cultivation are to be understood as including land where the crop plants are already growing as well as land intended for the cultivation of those crop plants.
  • the compounds of formula I according to the invention can also be used in combination with further herbicides.
  • the compound of the formula I is one of those compounds listed in Tables 1 to 30 below.
  • the following mixtures of the compound of formula I are especially important: compound of formula I + acetochlor, compound of formula I + acifluorfen, compound of formula I + acifluorfen-sodium, compound of formula I + aclonifen, compound of formula I + acrolein, compound of formula I + alachlor, compound of formula I + alloxydim, compound of formula I + allyl alcohol, compound of formula I + ametryn, compound of formula I + amicarbazone, compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + amitrole, compound of formula I + ammonium sulfamate, compound of formula I + anilofos, compound of formula I + asulam, compound of formula I + atraton, compound of formula I +
  • the mixing partners for the compound of formula I may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 12th Edition (BCPC) 2000.
  • compound of formula I + aclonifen compound of formula I + amidosulfuron, compound of formula I + aminopyralid, compound of formula I + beflubutamid, compound of formula I + benfluralin, compound of formula I + bifenox, compound of formula I + bromoxynil, compound of formula I + butafenacil, compound of formula I + carbetamide, compound of formula I + carfentrazone, compound of formula I + carfentrazone-ethyl, compound of formula I + chlorotoluron, compound of formula I + chlorpropham, compound of formula I + chlorsulfuron, compound of formula I + cinidon-ethyl, compound of formula I + clodinafop, compound of formula I + clodinafop-propargyl, compound of formula I + clopyralid, compound of formula I + 2,4-D, compound of formula I + dicamba, compound of formula I + dichlobenil
  • the compounds of formula I according to the invention can also be used in combination with safeners.
  • the compound of the formula I is one of those compounds listed in Tables 1 to 30 below.
  • the following mixtures with safeners especially, come into consideration: compound of formula I + cloquintocet-mexyl, compound of formula I + cloquintocet acid and salts thereof, compound of formula I + fenchlorazole-ethyl, compound of formula I + fenchlorazole acid and salts thereof, compound of formula I + mefenpyr-diethyl, compound of formula I + mefenpyr diacid, compound of formula I + isoxad if en-ethyl, compound of formula I + isoxadifen acid, compound of formula I + furilazole, compound of formula I + furilazole R isomer, compound of formula (I) + N-(2-methoxybenzoyl)-4-[(methylaminocarbonyl)amino]
  • Benoxacor, cloquintocet-mexyl, cyprosulfamide, mefenpyr-diethyl and N-(2-methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide are especially preferred, where cloquintocet- mexyl is particularly valuable.
  • the rate of application of safener relative to the herbicide is largely dependent upon the mode of application.
  • the herbicidal compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing.
  • the safeners can be used for pretreating the seed material of the crop plant (dressing the seed or seedlings) or introduced into the soil before or after sowing, followed by the application of the (unsafened) compound of the formula (I), optionally in combination with a co-herbicide. It can, however, also be applied alone or together with the herbicide before or after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide.
  • the treatment of the plant by simultaneous application of herbicide and safener is generally preferred.
  • the rate of application of safener relative to herbicide is largely dependent upon the mode of application.
  • In the case of field treatment generally from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied.
  • seed dressing generally from 0.001 to 10 g of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied.
  • safener solutions which contain the active ingredient in a concentration of from 1 to 10 000 ppm, preferably from 100 to 1000 ppm.
  • Example 1 Preparation of (3aS * ,6aR * )-5-(4'-chloro-4-ethylbiphen-3-yl)-2,3,3-trimethyl-3a,6a- tetrahvdrocvclopentard1isoxazole-4,6-dione.
  • Step 1 Preparation of (4'-chloro-4-ethylbiphen-3-yl)furan-2-ylmethanol.
  • a second batch of material is prepared in the same way, using identical quantities of reagents and solvents, before the two batches are treated according to the procedure below.
  • aqueous phase is extracted into ethyl acetate and the organic solutions are combined, washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure.
  • the residue is purified by column chromatography on silica gel to give 5-(4'-chloro-4-ethylbiphen-3-yl)-4-hydroxy-cyclopent-2-enone (59.84 g) as a brown oil.
  • Step 3 Preparation of 2-(4'-chloro-4-ethylbiphen-3-yl)cyclopent-4-ene-1 ,3-dione.
  • a 1.67 molar solution of Jones' reagent is prepared by adding chromium trioxide (72 g, 720 mmol) to an ice-cold mixture of concentrated sulphuric acid (72 ml) and water (360 ml) and stirring until dissolution is complete.
  • Ste p 4 P re pa ration of (3aS * ,6aR * )-5-(4'-chloro-4-ethylbiphen-3-yl)-2,3,3-trimethyl-3a,6a- tetrahydrocyclopenta[d]isoxazole-4,6-dione.
  • Anhydrous potassium carbonate (400 mg, 2.9 mmol) is added to a solution of N- methylhydroxylamine hydrochloride (120 mg, 3.6 mmol) and 2-(4'-chloro-4-ethylbiphen-3- yl)cyclopent-4-ene-1 ,3-dione (300 mg, 0.97 mmol) in acetone at 4O 0 C.
  • the mixture is stirred and heated at 4O 0 C for 18 hours, then cooled to room temperature.
  • the mixture is partitioned between dichloromethane and dilute aqueous potassium carbonate solution. The organic phase is discarded.
  • the aqueous phase is acidified to pH 1 by addition of 2M aqueous hydrochloric acid, and extracted into dichloromethane.
  • the organic extract is washed with brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is evaporated under reduced pressure.
  • the residue is purified by column chromatography on silica gel to give (3aS*,6aR*)-5-(4'-chloro-4- ethylbiphen-S-yl ⁇ .S.S-trimethyl-Sa. ⁇ a-tetrahydrocyclo-penta ⁇ lisoxazole ⁇ . ⁇ -dione.
  • Example 2 Preparation of (3aS * ,6aR * )-2,3,3-trimethyl-5-(2,4,6-trimethylphenyl)-3a,6a- tetrahydrocvclopentard1isoxazole-4,6-dione.
  • Step 1 Preparation of (2,4, 6-trimethylphenyl)furan-2-ylmethanol.
  • Step 2 Preparation of 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone.
  • aqueous phase is extracted into ethyl acetate and the organic solutions are combined, washed with saturated aqueous sodium bicarbonate solution and brine, dried over anhydrous magnesium sulfate, filtered and the filtrate is concentrated under reduced pressure.
  • the residue is purified by column chromatography on silica gel to give 5-(2,4,6-trimethylphenyl)-4-hydroxycyclopent-2-enone.
  • Step 3 Preparation of 2-(2,4,6-trimethylphenyl)cyclopent-4-ene-1 ,3-dione.
  • Step 4 Preparation of (3aS * ,6aR * )-2,3,3-trimethyl-5-(2,4,6-trimethylphenyl)-3a,6a- tetrahydrocyclopenta[d]isoxazole-4,6-dione.
  • Example 3 Preparation of (3aS * ,6aR * )-5-(4'-chloro-4-ethylbiphen-3-v)-3-ethyl-3a,6a- dihvdrocvclopentard1isoxazole-4,6-dione.
  • Triethylamine (4 drops, excess) is added to a mixture of 1 ,4-phenylene diisocyanate (320 mg, 2.0 mmol), 1-nitropropane (0.06 ml, 0.66 mmol) and 2-(4'-chloro-4-ethylbiphen-3-yl)cyclopent-4-ene- 1 ,3-dione (200 mg, 0.64 mmol) in tetrahydrofuran (7 ml) under an atmosphere of nitrogen.
  • the reaction mixture is heated to reflux for 22 hours then cooled to room temperature and diluted with dichloromethane. The mixture is stirred for 1 hour, then water (1 ml) is added and the mixture stirred for an additional 1 hour.
  • Solvent A H 2 O containing 0.1 % HCOOH
  • Solvent B CH 3 CN containing 0.1 % HCOOH
  • the characteristic values obtained for each compound were the retention time (rt, recorded in minutes) and the molecular ion (typically the cation MH + ), as listed in Table T1.
  • Table 1 covers compounds of the following type
  • Table 2 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 3 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 4 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 5 covers compounds of the following type wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 6 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 8 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 9 covers compounds of the following type
  • Table 10 covers compounds of the following type
  • Table 1 1 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 12 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 13 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 14 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 15 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 16 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 17 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 18 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 19 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 20 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 21 covers compounds of the following type
  • Table 22 covers compounds of the following type
  • Table 23 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 24 covers compounds of the following type
  • Table 25 covers compounds of the following type wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 26 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 27 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 28 covers compounds of the following type
  • R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • Table 29 covers compounds of the following type
  • Table 30 covers compounds of the following type wherein R 1 , R 2 , R 3 and R 4 are as defined in Table 1.
  • AMARE Amaranthus retroflexus
  • SETFA Setaria faberi
  • Alopecurus myosuroides Alopecurus myosuroides
  • EHCG Echinochloa crus-galli
  • AVEFA Avena fatua

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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention porte sur des composés de formule (I), dans laquelle les substituants sont tels que définis dans la revendication 1, qui sont appropriés pour être utilisés comme herbicides.
PCT/EP2009/065297 2008-11-19 2009-11-17 Nouveaux herbicides WO2010057880A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0821167.4 2008-11-19
GB0821167A GB0821167D0 (en) 2008-11-19 2008-11-19 Novel herbicides

Publications (1)

Publication Number Publication Date
WO2010057880A1 true WO2010057880A1 (fr) 2010-05-27

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PCT/EP2009/065297 WO2010057880A1 (fr) 2008-11-19 2009-11-17 Nouveaux herbicides

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Country Link
GB (1) GB0821167D0 (fr)
WO (1) WO2010057880A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011098433A1 (fr) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft Cétoénols cycliques pour thérapie
CN111253231A (zh) * 2020-02-03 2020-06-09 厦门大学 一种4-环戊烯-1,3-二酮的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001017972A2 (fr) * 1999-09-07 2001-03-15 Syngenta Participations Ag Nouveaux herbicides
DE102006000971A1 (de) * 2006-01-07 2007-07-12 Bayer Cropscience Ag 2,4,6-Trialkylphenylsubstituierte Cyclopentan-1,3-dione

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001017972A2 (fr) * 1999-09-07 2001-03-15 Syngenta Participations Ag Nouveaux herbicides
DE102006000971A1 (de) * 2006-01-07 2007-07-12 Bayer Cropscience Ag 2,4,6-Trialkylphenylsubstituierte Cyclopentan-1,3-dione

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011098433A1 (fr) 2010-02-15 2011-08-18 Bayer Schering Pharma Aktiengesellschaft Cétoénols cycliques pour thérapie
CN111253231A (zh) * 2020-02-03 2020-06-09 厦门大学 一种4-环戊烯-1,3-二酮的制备方法
CN111253231B (zh) * 2020-02-03 2021-08-03 厦门大学 一种4-环戊烯-1,3-二酮的制备方法

Also Published As

Publication number Publication date
GB0821167D0 (en) 2008-12-24

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