WO1999024409A1 - Derives d'isoxazole et leur utilisation comme herbicides - Google Patents

Derives d'isoxazole et leur utilisation comme herbicides Download PDF

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WO1999024409A1
WO1999024409A1 PCT/EP1998/007177 EP9807177W WO9924409A1 WO 1999024409 A1 WO1999024409 A1 WO 1999024409A1 EP 9807177 W EP9807177 W EP 9807177W WO 9924409 A1 WO9924409 A1 WO 9924409A1
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alkyl
phenyl
alkoxy
alkenyl
alkynyl
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Jürgen Schaetzer
Walter Kunz
Alain De Mesmaeker
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Novartis Pharma GmbH Austria
Novartis AG
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Novartis Erfindungen Verwaltungs GmbH
Novartis AG
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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
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • 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
    • 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
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen
    • 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

Definitions

  • the present invention relates to novel herbicidally active isoxazole derivatives, 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 plant growth.
  • Isoxazole derivatives having herbicidal action are described, for example, in
  • Z is S, SO or SO 2 ;
  • Ri is hydrogen, d-C 8 alkyl or C ⁇ -C 8 alkyl substituted by halogen, C ⁇ -C 4 alkoxy, CrC 4 alkylthio, d-dalkylsulfonyl, C C 4 alkylsulfinyl, hydroxy, cyano, nitro, -CHO, -CO 2 R 2 , -COR 3 , -COSR 4 , -NR 5 R 6 , CONR 36 R37 or by phenyl which in turn may be substituted by C ⁇ -C 4 alkyl, C C 6 halo- alkyl, d-dalkoxy, C ⁇ -C 4 haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 - alkynyioxy, halogen, nitro, cyano, -COOH, COOC C 4 alkyl, COOpheny
  • NHSO 2 -d-C 4 alkyl NHSO 2 -phenyl, N(d-C 6 alkyl)SO 2 -C ⁇ -C 4 - alkyl, N(C ⁇ -C 6 alkyl)SO 2 -phenyl, N(C 2 -C 6 alkenyl)SO 2 -Ci-C 4 alkyl, N(C 2 -C 6 alkenyl)SO 2 -phenyl, N(C 3 -C 6 alkynyl)SO 2 -Ci-C 4 alkyl, N(C 3 -C 6 alkynyl)SO 2 -phenyl, N(C-3-dcycloalkyl)SO 2 -C 1 -C 4 - alkyl, N(C 3 -C 7 cycloalkyl)SO 2 -phenyl, N(phenyl)SO 2 -Crdalkyl.
  • Ri is C 3 -C 7 cycloalkyl or C 3 -C 7 cycloalkyl substituted by Crdalkyl, d-C alkoxy, d-C alkyl- thio, C ⁇ -C alkylsulfinyl, d-C 4 alkylsulfonyl or by phenyl which in turn may be substituted by halogen, nitro, cyano, d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylthio, d-C haloalkylthio, C C 4 alkyl or by C ⁇ -C 4 haloalkyl; or Ri is -(CH 2 ) q -C- 3 -C 7 cycloa!kyl, phenyl or phenyl substituted by d-C alkyl, d-C 6 haloalkyl, Crdalkoxy, C ⁇ -C haloalkoxy, C 2
  • R 2 , R 38 , R t and R 6 e are each independently of the others hydrogen, d-C 4 alkyl, phenyl or phenyl substituted by d-dalkyl, C ⁇ -C 6 haloalkyl, d-dalkoxy, d-C 4 haloalkoxy, C 2 -C 6 - alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C 4 alkyl, COOphenyl, C ⁇ -C 4 alkoxy, phenoxy, (d-C alkoxy)-C C 4 alkyl (C C 4 alkyl- thio)-d-C 4 alkyl, (C ⁇ -C 4 alkylsulfinyl)-d-C 4 alkyl, (C ⁇ -C 4 alkylsulfon
  • R 3 , R 39 and R 67 are each independently of the others C C alkyl, phenyl or phenyl substituted by d-dalkyl, CrC 6 haloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 - alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halogen, nitro, cyano, -COOH, COOC C 4 alkyl, COOphenyl, C C 4 alkoxy, phenoxy, (C C 4 alkoxy)-C ⁇ -C 4 alkyl, (C ⁇ -C 4 alkylthio)-d-C 4 alkyl, (C ⁇ -C 4 alkylsulfinyl)-d-C 4 alkyl, (d-C 4 alkylsulfonyl)-C ⁇ -C 4 alkyl, NHS
  • OSO 2 -C ⁇ -C haloalkyl OSO 2 -phenyl, CrC 4 alkylthio, C ⁇ -C haloalkylthio, phenylthio, C C alkylsulfonyl, C C 4 halo- alkylsulfonyl, phenylsulfonyl, d-C 4 alkylsulfinyl, C ⁇ -C 4 haloalkylsulfinyl, phenylsulfinyl, -(CH 2 ) t - phenyl or by -NR 56 CO 2 R 55 ; R 4 is d-dalkyl;
  • R 5 is hydrogen, C C ⁇ lkyl, C 2 -C 6 alkenyl, Cs-Cealkynyl, C 3 -C 7 cycloalkyl, phenyl or phenyl substituted by d-C alkyl, CrCehaloalkyl, d-C 4 alkoxy, d-C 4 haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 - alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, halogen, nitro, cyano, -COOH, COOd-dalkyl, COOphenyl, d-C alkoxy, phenoxy, (C C alkoxy)-C ⁇ -C 4 alkyl, (C ⁇ -C 4 alkylthio)-CrC 4 alkyl, (C ⁇ -C 4 alkylsulfinyl)-C ⁇ -C 4 alkyl,
  • R 7 is phenyl, substituted phenyl, d-dalkyl, d-dalkoxy or -NR 8 R 9 ;
  • R is C ⁇ -C 6 alkyl, CrC 6 alkoxy, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkynyl, C 2 -C 6 alkoxyalkenyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by d-C 4 alkyl, d-C 4 haloalkyl or by d-C 4 alkoxy; 3- to 6-membered, saturated heterocyclyl; or phenyl which may be substituted by halogen, d-C alkyl, C C 4 haloalkyl, d-C 4 alkoxy, C ⁇ -C haloalkoxy, nitro, cyano, C C 4 alkylthio, d
  • Ri3, Reg. R70 and R 7 ⁇ are each independently of the others hydrogen, d-C 6 alkyl, C 2 -C 6 - alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, phenyl or phenyl substituted by d-dalkyl, d-C 6 halo- alkyl, C ⁇ -C alkoxy, d-C haloalkoxy, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 - alkynyloxy, halogen, nitro, cyano, -COOH, COOd-C 4 alkyl, COOphenyl, C C alkoxy, phenoxy, (d-dalkoxyj-d-dalkyl, (C ⁇ -C 4 alkylthio)-d-C 4 alkyl, (d-C 4 alky
  • R3i > R 4 3 > R48, R52, R ⁇ , Reo, Rw, Res and R 80 are each independently of the others hydrogen, C ⁇ -C 4 alkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C 7 cycloalkyl; n is 0, 1 or 2; m, p, q, s, t, u, v and x are each independently of the others 1 , 2, 3 or 4; R25. 26, R27. R281 R29. R30, R32. 331 R ⁇ ⁇ R35. R40. R 4 i ⁇ 42i R 5. R 4 6. R471 R49, R501 R511 R53.
  • Res. Res, R77, R78 and R 79 are hydrogen, d-C 4 alkyl, C 2 -C 6 - alkenyl, C 3 -C 6 alkynyl, C 3 -C 7 cycloalkyl, phenyl or phenyl substituted by halogen, nitro, cyano, d-dalkoxy, C C haloalkoxy, C C 4 alkylthio, C C 4 haloalkylthio, d-C 4 alkyl or by d-C halo- alkyl; and agronomically acceptable salts of those compounds.
  • alkyl groups that appear in the definitions of the substituents may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso- butyl, tert-butyl, pentyl, hexyl, heptyl and octyl and their branched isomers.
  • Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals.
  • the alkenyl and alkynyl groups may be mono- or poly-unsaturated.
  • Halogen is generally fluorine, chlorine, bromine or iodine. The same applies also to halogen in connection with other meanings, such as haloalkyl or halophenyl.
  • Haloalkyl groups preferably have a chain length of from 1 to 8 carbon atoms.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichlorornethyl, tri- chloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1 -difluoro- 2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloro- methyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • haloalkenyl there come into consideration alkenyl groups mono- or poly-substituted by halogen, halogen being fluorine, chlorine, bromine and iodine and especially fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3- bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichl ⁇ ropropenyl and 4,4,4-trifluoro-but-2-en- 1 -yl.
  • halogen being fluorine, chlorine, bromine and iodine and especially fluorine and chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3- bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichl ⁇ ropropenyl and 4,4,4-trifluoro-
  • haloalkynyl there come into consideration, for example, alkynyl groups mono- or poly- substituted by halogen, halogen being bromine, iodine and, especially, fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoro- propynyl and 4,4,4-trif luoro-but-2-yn-1 -yl.
  • alkynyl groups mono- or poly-substituted by halogen preference is given to those having a chain length of from 3 to 5 carbon atoms.
  • Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert- butoxy and the isomers of pentyloxy and hexyloxy; preferably methoxy and ethoxy.
  • Alkyl- carbonyl is preferably acetyl or propionyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy- carbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxy- carbonyl.
  • Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butyl- thio or tert-butylthio, preferably methylthio and ethylthio.
  • Alkylsulfinyl is, for example, methyl- sulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl, tert-butylsulfinyl; preferably methylsulfinyl and ethylsulfinyl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Alkoxyalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms.
  • alkoxyalkoxy examples are: methoxymethoxy, methoxyethoxy, methoxy- propoxy, ethoxymethoxy, ethoxyethoxy, propoxymethoxy or butoxybutoxy.
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the isomers of butylamine.
  • Dialkylamino is, for example, dimethylamino, methylethylamino, diethylamino, n- propylmethylamino, dibutylamino and diisopropylamino.
  • Alkoxyalkyl groups preferably have from 1 to 8 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or iso- propoxyethyl.
  • Alkylthioalkyl groups preferably have from 1 to 8 carbon atoms.
  • Alkylthioalkyl is, for example, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propyl- thiomethyl, n-propylthioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butyl- thioethyl or butylthiobutyl.
  • the cycloalkyl groups preferably have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Phenyl also as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl or phenoxyalkyl
  • the substituents may be in the ortho-, meta- and/or para-position. Preferred positions for the substituents are the ortho- and para-positions with respect to the ring linkage site.
  • Heterocyclyl is to be understood as meaning ring systems which contain, in addition to carbon atoms, at least one hetero atom such as nitrogen, oxygen and/or sulfur. They may be saturated or unsaturated. Heterocyclyl ring systems within the scope of the present invention may also be substituted. Examples of suitable substituents are d-C 4 alkyl, d-C haloalkyl, d-d- alkoxy, cyano, nitro, d-C 4 alkylsulfonyl, C ⁇ -C alkylsulfinyl, d-C alkylthio and C 3 -C 6 cyclo- alkyl.
  • substituent Ar is heterocyclyl
  • two adjacent substituents on the heterocyclyl may form a 5- to 7-membered ring which may be substituted by C ⁇ -C alkyl, d-C 4 haloalkyl, d-dalkoxy, cyano, nitro, d-dalkylsulfonyl, C ⁇ -C 4 alkylsulfinyl, C ⁇ -C 4 alkylthio or by C 3 -C 6 - cycloalkyl.
  • Heterocyclyl may be, for example, furyl, thiophenyl, pyrrolidyl, piperidinyl, mo holinyl, pyridyl, imidazolyl, tetrahydrofuryl, tetrahydropyranyl, dihydrofuryl, dihydropyranyl, isoxazolyl, oxazolyl, isoxazolyl, isothiazolyl, 1 ,2,3-thiadiazolyl, 1 ,2,4-thiadiazolyl, thiazolyl, pyrazolyl, 1 ,2,4-triazolyl, 1 ,2,3-triazolyl, tetrazolyl, pyrimidyl, pyrazinyl, symmetrical or
  • asymmetrical triazinyl piperazinyl, oxazolinyl (for example: ), oxazolidinyl, imidazolinyl, imidazolidinyl, dioxanyl, oxetanyl, especially 2-oxetanyl, or phthalimidyl.
  • the invention also includes the salts which the compounds of formula I are capable of forming especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali metal and alkaline earth metal bases special mention is to be made, as salt-forming agents, of the hydroxides of lithium, sodium, potassium, magnesium and calcium, especially those of sodium and potassium.
  • amines suitable for the formation of ammonium salts both ammonia and primary, secondary and tertiary d-C 18 alkylamines, C ⁇ -C 4 hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl- nonylamine, methyl-pentadecylamine, methyl-oc
  • quaternary ammonium bases suitable for the formation of salts are [N(R a R R c R d )] + OH " , wherein R a , R b , R c and R d are each independently of the others C ⁇ -C 4 alkyl.
  • Further suitable tetraalkyl- ammonium bases containing different anions can be obtained, for example, by anion exchange reactions.
  • Preferred compounds of formula I are those wherein Ar is a group
  • R 81 , R 82 , R ⁇ 3, R ⁇ , Res. R ⁇ e, ⁇ 7 and R 88 are each independently of the others hydrogen, halogen, C ⁇ -C 4 alkyl, d-dhaloalkyl, C ⁇ -C alkoxy, d-C 4 haloalkoxy, (d-C 4 alkoxy)- d-dalkyl, (C C 4 alkylthio)-C ⁇ -C 4 alkyl, (d-dalkylsulfony -d-dalkyl, (d-C 4 alkylsulfinyl)- d-C 4 alkyl, d-C alkylthio, C C 4 haloalkylthio, phenylthio, d-C 4 alkylsulfonyl, d-C 4 haloalkyl- sulfonyl, phenylsulfonyl, C C 4 alkylsulfinyl,
  • X L X 2 , X 3) Xt, Y ⁇ , Y 2 , Y 3 and Y are each independently of the others O, S, SO, SO 2 , NR 89 ,
  • R 89 is hydrogen, C ⁇ -C 4 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or C 3 -C 7 cycloalkyl;
  • R 19 , R 20 and R90 are each independently of the others hydrogen or d-C 4 alkyl.
  • R is hydrogen, d-dalkyl, d-C 4 alkyl substituted by halogen, methoxy, ethoxy, cyano or by COOR 2 , or C 3 -C 6 alkenyl or halo-substituted C 3 -C 6 alkenyl, or C 3 -C 6 alkynyl.
  • T T1 , T2
  • T2 CN, CON(CH 3 )-OCH 3
  • Tx hydrogen, COOH or COO-d-C alkyl
  • M metal ion such as Mg(ll), Zn(ll), Cd(ll), Li(l), K(l)
  • Both the keto compound that is used and the nitrile may carry on the ⁇ -carbon atom an additional carboxyl or alkoxycarbonyl group Tx suitable for condensation.
  • Tx is COO-d-C alkyl
  • hydrolysis and decarboxylation can be carried out once the acylation is complete.
  • an acid chloride ArCOCI it may suitably be used with, for example, BuLi as the base at from -60 to -80°C and tetrahydrofuran as the solvent (Synthesis 1983. 308; Synthesis 1984. 1 ; J. Org. Chem. 54, 4229; US 5 545 762; US 5 656 373).
  • the keto compound Pill is then reacted with carbon disulfide in the presence of a base, such as NaH, an alkali alkanolate (e.g. NaOEt) or an alkali carbonate, e.g. potassium carbonate, or a fluoride salt (e.g. KF) that is free or bonded, for example, to aluminium oxide, in an inert solvent at from -20 to +80°C and alkylated using an alkylating agent R XP1 , wherein R. is as defined above and XP1 is Hal (Cl, Br, I) or OS(O)OR ⁇ , to form the ketene dithioacetal Pll (Chem. Ber. 95, 2861 , Z. Chem. 16, 397, 1976).
  • a base such as NaH, an alkali alkanolate (e.g. NaOEt) or an alkali carbonate, e.g. potassium carbonate, or a fluoride salt (e.g. KF) that
  • the intermediates of formula PI are novel and have been developed especially for the preparation of the compounds of formula I, and the present invention therefore relates also thereto.
  • cyano- or amide-substituted isoxazoles are obtained in the cyclisation (step 3), they are subsequently reacted at from -120° to +40°C in an inert solvent, such as hexane, an ether, THF, (if required after transmetallation to, for example, potassium, zinc or cadmium salts) with Grignard (RMgHal)- or alkyl lithium (RLi) to form the compound of formula ly (J. Het. Chem. 12, 413; Tetrahedr. 3 ., 499 (1975)).
  • T T1 , T2
  • T2 CN, CON(Me)-OCH 3
  • M metal ion such as Mg(ll), Zn(ll), Cd(ll), Li(l), K(l)
  • an aryl ketone Pill prepared according to Scheme 1
  • an enamine PVI Reaction step 7
  • PVIb nitrite oxides
  • Intermediates PV wherein E is halogen can then be converted, by reaction with mercaptans HSRi, preferably in the presence of an acid acceptor (e.g. bases such as tertiary amines or oxiranes such as propylene oxide) in inert solvents at temperatures of from -20 to 150°C, into the products Ix or PI already obtainable according to Scheme 1.
  • an acid acceptor e.g. bases such as tertiary amines or oxiranes such as propylene oxide
  • Some enamines PVI are known (US-A-5 656 573, EP-A-0 625 505), or they are prepared according to methods known perse, for example by reaction of a keto compound Pill with a secondary amine HN(P 1 )P 2 wherein HN(P 1 )P 2 is an open-chained or cyclic compound such as HNEt 2 , pyrrolidine or morpholine, in the presence of an acid catalyst (acetic acid, p- toluenesulfonic acid, acid earths, such as montmorillonite, or acid resins, such as Amberlyst IRA 400) and of an inert solvent, with removal of the water of reaction that forms (molecular sieve, azeotropic distillation) at temperatures of from 40 to 200°C (Tetrahedron Letters 1988. 3997).
  • an acid catalyst acetic acid, p- toluenesulfonic acid, acid earths, such as montmorillonite, or acid resins
  • Pg is a protecting group, such as Si(alkyl) 3 , C(Me) 2 OH, Sn(alkyl) 3)
  • a palladium catalyst such as Pd(Ph 3 P) 4 or Pd(Ph 3 P) 2 CI 2 or Pd(OAc) 2 and Cul
  • an amine e.g. HNEt 2
  • an inert solvent Org. React.
  • a base e.g. NaH, tertiary amine
  • a suitable tin compound e.g. (R 4 ) 3 -SnCI
  • 4-stannyl compounds XII are obtained, which can likewise be reacted with acid chlorides RCO-CI analogously to Heterocycles 43, 1301 (1996) in the presence of palladium catalysts (e.g. Pd(Ph 3 P) 2 CI 2 ) to form the compound of formula I.
  • palladium catalysts e.g. Pd(Ph 3 P) 2 CI 2
  • the compounds of formula I can be prepared also by the direct addition of nitrite oxides PIVb to unsaturated ketones of formula PIX (alkynes) or PXIII (alkenes) in accordance with the following scheme:
  • Suitable oxidising agents for the selective oxidation of the compound of formula PXVIII to the compound of formula KUb, wherein Ar, R and Ri are as defined for formula I, n is 1 or 2 and 'Hal is halogen, preferably chlorine or bromine, are metachloroper- benzoic acid, sodium perborate and tetrabutylammonium perruthenate.
  • the compound of formula KUb is novel and has been developed especially for the preparation of the compounds of formula I, and the present invention relates also thereto.
  • Alkyl- or aryl-thiomethylnitromethane derivatives of formula PXIII obtainable according to known methods (e.g. J. Org. Chem. 53, 5369 (1988)) are converted into the corresponding nitrile oxides PIVb in the presence of a dehydrating agent, for example an isocyanate of formula PXIV, and of a base, for example a tertiary amine (e.g.
  • the cyclisation is preferably carried out without isolation of the intermediates in a one-pot reaction in one of the mentioned solvents.
  • suitable catalysts are Lewis acids, such as Ti(IV) salts, such as Ti(OisoPr) 4 (J. Am. Chem. Soc. 118, 59; ibid. 111 , 5340; J. Org. Chem. 59, 5687), or complexes such as Ti(OTs) 2 (TADDOL) (Helv.
  • Eu (fod) 3 tris(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanate-dionato)europium(lll)) (Heterocycles 46, 95), and lanthanide complexes such as Yb(OTf) 3 (Chem. Lett. 1997, 1039).
  • Isoxazolines of formula PXVI can be converted into the end products of formula Iz according to methods known perse by means of aromatising oxidising agents such as, for example, MnO 2 (Synthesis 1976, 133), for example in benzene, cyclohexane or toluene, at from 20 to 140°C.
  • aromatising oxidising agents such as, for example, MnO 2 (Synthesis 1976, 133), for example in benzene, cyclohexane or toluene, at from 20 to 140°C.
  • the isoxazolines are first converted into the corresponding halides (preferably chlorine or bromine derivatives) PXVIII by means of a halogenating agent, such as Br 2 , Cl 2 , N-bromosuccinimide, if required with the addition of a radical initiator, such as dibenzoyi peroxide, in an inert solvent, for example carbon tetrachioride or a sulfochloride, such as thionyl chloride or trifluoromethane sulfochloride, and the halides are then reacted with a base (preferably a tertiary amine, such as triethylamine or DBU (1 ,8- diazabicyclo-(5.4.0)-undec-7-ene)) in an inert solvent, such as dichloromethane, at from -20°C to +80°C to form the products of formula I.
  • a halogenating agent such as Br 2 , Cl 2 , N-bromos
  • WO 97/43270 using 1 or 2 equivalents of an oxidising agent such as m-chloroperbenzoic acid in an inert solvent, for example dichloromethane, at temperatures of from -20°C to
  • Isoxazolines of formulae PXVI and PXVIII wherein Ar, R and R. are as defined for formula I and 'Hal is halogen, preferably chlorine or bromine, are novel and, as intermediates, the present invention relates also thereto.
  • the compounds of formulae PXVI and PXVIII have herbicidal activity.
  • Enones of formula PXV are either known or can be prepared according to known methods, for example by Wittig or Wittig-Homer condensation of an aldehyde of formula PXXI with a phosphorane PXX obtained from a halide PXIX, in an inert solvent, such as tetrahydrofuran, dioxane or acetonitrile, at temperatures of from 20°C to 160°C (analogously to Tetrahedron Lett. 1974, 2491 , scheme below).
  • enones of formula PXV are obtainable by condensation of aldehydes of formula PXXI with a methyl ketone of formula XXII
  • a bifunctional catalyst such as ammonium acetate, a pyridine/piperidine mixture (analogously to Synthesis 1980, 806), an alkali fluoride (KF, Synthesis 1983, 173), and subsequent removal of the activating group (customary hydrolysis and decarboxylation (-COOalkyl) in the case of a 1 ,3-keto ester).
  • a further process for the preparation of unsaturated ketones of formula PXV comprises the Heck reaction of an aryl halide of formula PXXIIIa
  • a palladium catalyst for example Pd(OAc) 2
  • a base such as triethylamine
  • an inert solvent such as acetonitrile or N,N-dimethylformamide
  • arylaldehydes (PXXI) required for the above-mentioned condensation reactions are either known or can be prepared according to known methods, for example by catalytic reduction of appropriate carboxylic acid halides according to Rosenmund or an analogous variant in the presence of a catalyst, for example Pd/BaSO 4 , and of a pyridine base, such as lutidine.
  • a catalyst for example Pd/BaSO 4
  • a pyridine base such as lutidine.
  • oxidising agent such as cerium(IV)-ammonium nitrate (J. prakt. Chem. 336, 470 (1994)) or phenyl dichlorophosphate/DMSO/NEt 3 (J. Org. Chem. 59, 7704 (1994)) or oxalyl chloride/DMSO (Synth. 1990, 857), to the aldehyde PXXI
  • isoxazoles of formula I are also obtainable from the dihaloformaldoximes PIVa, as shown below, by means of addition to olefins PXV via isoxazolines of formula PXVI.
  • the 3-halo-isoxazoline of formula PXVII may also be isolated.
  • reaction step (1 ) there are added to the olef in PXV in an inert solvent, such as 1 ,2- dimethoxyethane, at a temperature of from 0°C to +60°C, a base, for example an alkali hydrogen carbonate, as well as a small amount of water and the oxime PIVa and then the thiolate RiSMi is introduced in small portions over a prolonged period of about from 1 to 6 hours.
  • an inert solvent such as 1 ,2- dimethoxyethane
  • Ms is an alkali metal, preferably lithium.
  • suitable oxidising agents for the selective oxidation of the compound of formula PXVI to the compound of formula KUa, wherein Ar, R and Ri are as defined for formula I and n is 1 or 2, are metachloroperbenzoic acid, sodium perborate and tetrabutylammonium perruthenate.
  • the compound of formula KUa is novel and has been developed especially for the preparation of the compounds of formula I, and the present invention relates also thereto.
  • Dihaloformaldehyde oximes and dithioalkylformaldehyde oximes of formula PIVa are known or can be prepared according to known methods, for example Chem. Ber. 43, 3362; Synth. Comm. 12, 601 or according to CH-A-563 967, Chem. and Industry 1979. 826.
  • Dithio-substituted formaldehyde oximes can also be obtained from the dihalo compounds and appropriate thiols in the presence of a base.
  • Substituted aryl derivatives (Ar-P3, A ⁇ -COOP ) are for the most part also known or can be prepared according to known methods (as described, for example, in US-A-5 658 858, US-A-5 656 573, EP-A-0 524 018, EP-A-0 527 037, EP-A-0 609 797, EP-A-0 588 357, WO 97/19076, WO 97/09324, WO 97/09327, WO 97/19071 , WO 96/26192, EP-A-0 768 033, WO 96/26206, WO 97/12885, WO 96/26200 and US-A-0 5 607 898).
  • the reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N- methylpyrrolidinone.
  • the reaction temperatures are preferably from -20°C to +120°C.
  • the reactions are generally slightly exothermic and can usually be carried out at room temperature.
  • the reaction mixture may if required be heated for a short time up to its boiling point.
  • the reaction times may also be shortened by adding a few drops of a base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diaza- bicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5-diazabicyclo[5.4.0]undec-7- ene.
  • bases inorganic bases for example hydrides, such as sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.
  • the compounds of formula I may be isolated in customary manner by concentration and/or evaporation of the solvent, and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • the compounds of formula I or of compositions comprising them there come into consideration any methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, as well as various methods and techniques such as, for example, the controlled release of active ingredient.
  • a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If r equired, a coating may additionally be applied (coated granules), which allows the active in igredient to be released in metered amounts over a specific period of time.
  • the compounds of formula I may be used as herbicides in unmodified form, i.e. as they are formed in the synthesis. Preferably, however, they are processed in customary manner together with the adjuvants conventionally employed in formulation technology e.g. into emulsif iable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wet- table powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, in WO 97/34485, pages 9 to 13. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and generally one or more solid or liquid formulation adjuvants
  • formulation adjuvants e.g. solvents or solid carriers.
  • surface-active compounds surfactants
  • solvents and solid carriers are given, for example, in WO 97/34485, page 6.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • anionic, non-ionic and cationic surfactants examples include WO 97/34485, pages 7 and 8.
  • Also suitable for the preparation of the herbicidal compositions according to the invention are the surfactants customarily employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
  • the herbicidal formulations usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a herbicide, 1 to 99.9 % by weight, preferably 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
  • a surfactant e.g. a surfactant.
  • the compositions may also comprise other auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the type of action, on the stage of development of the cultivated plant and of the weed, and also on the application (place, time, method) and, in dependence on those parameters, may vary within wide limits.
  • the compounds of formula I are distinguished by herbicidal and growth inhibiting properties, which render them suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, as well as for non-selective weed control. Crops are also to be understood as meaning crops that have been rendered tolerant to herbicides or classes of herbicide by conventional cultivation or genetic engineering methods.
  • the weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida,
  • a solution of 1.27 g of 2-chloro-4-trifluoromethyl-benzoic acid ethyl ester in 3.5 ml of DMF is added at room temperature to a suspension of 0.39 g of sodium ethanethiolate in 3 ml of DMF, and the mixture is heated for 4 hours at a temperature of 50°C.
  • the reaction mixture is then cooled, poured into ice-water and extracted with toluene; the extracts are washed with water and dried.
  • phenyl dichlorophosphate 8.6 g of phenyl dichlorophosphate are added dropwise at a temperature of -60°C to a suspension of 6 g of 4-hydroxymethyl-2-methylsulfonyl benzotrifluoride, 12.1 g of triethylamine and 7.5 g of dimethyl sulfoxide in 120 ml of ethyl acetate, and the mixture is cooled, with stirring, to a temperature of 0°C. After 1.5 hours, 13.5 ml of concentrated hydrochloric acid are added to the brownish suspension, with cooling.
  • Example P1 1 Preparation of 2-methylsulfonyl-4-trifluoromethyl-benzaldehvde via catalytic hvdro ⁇ enation:
  • a solution of 12.3 ml of nitromethane in 200 ml of chloroform is added dropwise at a temperature of -5°C, in the course of 25 minutes, to a solution of 5.7 g of sodium in 200 ml of absolute methanol, whereupon a white suspension forms. After 30 minutes' stirring at that temperature, a solution of 12.3 ml of nitromethane in 200 ml of chloroform is added to the reaction mixture at a temperature of -5°C, and stirring is carried out for a further 30 minutes.
  • Example P14 Preparation of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyll-3-methyl- sulfanyl-4.5-dihvdro-isoxazol-4-yl-cvclopropyl-methanone: a) via methylthiomethylnitromethane
  • 0.5 ml of triethylamine is added in the course of 15 minutes, with stirring and under a nitrogen atmosphere, at a temperature of 20°C to a solution of 1.59 g of 1 -cyclopropyl-3-(2- methylsulfonyl-4-trifluoromethyl)-phenyl-2-propen-1 -one, 0.643 g of methylthiomethylnitromethane and 1.3 ml of phenyl isocyanate in 40 ml of benzene. Stirring is then carried out for 3 hours at a temperature of 20°C, for one hour at a temperature of 40°C and for 15 hours at a temperature of 20°C.
  • the brownish red suspension is then filtered over a small amount of Hyflo (commercially available) and washed with diethyl ether, and the filtrate is concentrated by evaporation.
  • the residue is filtered first over silica gel (hexane/- ethyl acetate 7:3) and then purified by means of HPLC chromatography (Lichrospher Si60 12 ⁇ * m; hexane/ethyl acetate 9:1 with increasing gradients in respect of the more polar component).
  • a solution of 6 ml of 0.1 M DBU (1 ,8-diazabicyclo(5.4.0)undec-7-ene) in dioxane is added dropwise, with stirring, to a solution of 1.0 g of 1-(4-bromo-5-(2-methanesulfonyl-4-trifluoro- methyl-phenyl)-3-methylsulfanyl-4,5-dihydroisoxazol-4-yl-cyclopropyl-methanone in 60 ml of dioxane, and stirring is carried out for a short time at a temperature of 20°C. A further 3 ml of 0.1 M DBU solution are then added, and stirring is carried out for one hour.
  • the reaction mixture is cooled, neutralised with a few drops of dilute aqueous acetic acid and extracted between dichloromethane and a small amount of water.
  • the extracts are washed with a small amount of water, dried over sodium sulfate and filtered over a small amount of silica gel.
  • the filtrate is concentrated by evaporation and dried in vacuo. 20 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl- isoxazol-4-yl-cyclopropyl-methanone having a melting point of from 161 to 162°C are obtained.
  • a solution of 166 mg of m-chloroperbenzoic acid in 2 ml of dichloromethane is added dropwise, while cooling and with stirring at a temperature of from -15 to -18°C, to a solution of 256 mg of 5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3-methylsulfanyl-isoxazol-4-yl- cyclopropyl-methanone in 10 ml of dichloromethane, and stirring is carried out for 4 hours at the same temperature.
  • a further 30 mg of m-chloroperbenzoic acid are then added; after 20 minutes, the mixture is diluted with dichloromethane and washed with sodium hydrogen carbonate solution and water.
  • Example P19 Preparation of 1-(4-bromo-5-(2-methanesulfonyl-4-trifluoromethyl-phenyl)-3- methylsulfanyl-4.5-dihvdroisoxazol-4-yl-cvclopropyl-methanone:

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Abstract

L'invention concerne des composés de la formule (I) dans laquelle Z est S, SO ou SO2; Q est C=O ou CHOH; Ar est phényle ou phényle substitué par un à quatre substituants identiques ou différents. Lesdits composés et leurs sels agronomiquement acceptables sont efficaces comme herbicides.
PCT/EP1998/007177 1997-11-12 1998-11-10 Derives d'isoxazole et leur utilisation comme herbicides Ceased WO1999024409A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369276B1 (en) 1998-11-19 2002-04-09 Eagleview Technologies, Inc. Catalyst structure for ketone production and method of making and using the same
US6392099B1 (en) 1998-11-19 2002-05-21 Eagleview Technologies, Inc. Method and apparatus for the preparation of ketones
US6545185B1 (en) 2001-03-29 2003-04-08 Eagleview Technologies, Inc. Preparation of ketones from aldehydes
US7465805B2 (en) 2004-10-05 2008-12-16 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2018004223A1 (fr) * 2016-06-27 2018-01-04 (주)목우연구소 Composé à base de pyridine comprenant un cycle isoxazoline, et son utilisation comme herbicide
CN113666883A (zh) * 2021-07-23 2021-11-19 华南理工大学 一种合成4-乙烯基异噁唑衍生物的方法
JPWO2023210792A1 (fr) * 2022-04-28 2023-11-02

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EP0418175A2 (fr) * 1989-09-11 1991-03-20 Rhone Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0503410A1 (fr) * 1991-03-14 1992-09-16 BASF Aktiengesellschaft Amides d'acides isoxazole et isothiazole-5-carboxyliques
EP0524018A1 (fr) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazoles herbicides
JPH05105672A (ja) * 1991-10-17 1993-04-27 Sankyo Co Ltd イソオキサゾリン誘導体、その製法及び農園芸用殺菌剤
WO1997043270A1 (fr) * 1996-05-14 1997-11-20 Novartis Ag Derives d'isoxazole et leur utilisation comme desherbants

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Publication number Priority date Publication date Assignee Title
EP0418175A2 (fr) * 1989-09-11 1991-03-20 Rhone Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0503410A1 (fr) * 1991-03-14 1992-09-16 BASF Aktiengesellschaft Amides d'acides isoxazole et isothiazole-5-carboxyliques
EP0524018A1 (fr) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazoles herbicides
JPH05105672A (ja) * 1991-10-17 1993-04-27 Sankyo Co Ltd イソオキサゾリン誘導体、その製法及び農園芸用殺菌剤
WO1997043270A1 (fr) * 1996-05-14 1997-11-20 Novartis Ag Derives d'isoxazole et leur utilisation comme desherbants

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Title
CHEMICAL ABSTRACTS, vol. 119, no. 19, 8 November 1993, Columbus, Ohio, US; abstract no. 203404h, page 896; XP002094410 *
CHEMICAL ABSTRACTS, vol. 93, no. 21, 24 November 1980, Columbus, Ohio, US; abstract no. 204021n, MANFRED PALLAS ET AL: "Preparation of hydroxyiminodithiocarbonic acid esters" page 631; XP002094411 *
Z.CHEM., vol. 20, no. 6, 1980, pages 207 - 209 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369276B1 (en) 1998-11-19 2002-04-09 Eagleview Technologies, Inc. Catalyst structure for ketone production and method of making and using the same
US6392099B1 (en) 1998-11-19 2002-05-21 Eagleview Technologies, Inc. Method and apparatus for the preparation of ketones
US6495696B1 (en) 1998-11-19 2002-12-17 Eagleview Technologies, Inc. Method and apparatus for the preparation of ketones
US6545185B1 (en) 2001-03-29 2003-04-08 Eagleview Technologies, Inc. Preparation of ketones from aldehydes
US7465805B2 (en) 2004-10-05 2008-12-16 Syngenta Limited Isoxazoline derivatives and their use as herbicides
WO2018004223A1 (fr) * 2016-06-27 2018-01-04 (주)목우연구소 Composé à base de pyridine comprenant un cycle isoxazoline, et son utilisation comme herbicide
CN113666883A (zh) * 2021-07-23 2021-11-19 华南理工大学 一种合成4-乙烯基异噁唑衍生物的方法
CN113666883B (zh) * 2021-07-23 2023-06-16 华南理工大学 一种合成4-乙烯基异噁唑衍生物的方法
JPWO2023210792A1 (fr) * 2022-04-28 2023-11-02
WO2023210792A1 (fr) * 2022-04-28 2023-11-02 日本農薬株式会社 Composé hétérocyclique contenant de l'azote ayant un groupe oxime, herbicide agricole/horticole contenant ledit composé et leur utilisation
TWI870837B (zh) * 2022-04-28 2025-01-21 日商日本農藥股份有限公司 具肟基之含氮雜環化合物及含有該化合物之農園藝用除草劑、以及彼等之使用方法
JP7733225B2 (ja) 2022-04-28 2025-09-02 日本農薬株式会社 オキシム基を有する含窒素複素環化合物及び該化合物を含有する農園芸用除草剤並びにそれらの使用方法

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