WO1999009023A1 - Utilisation des derives du benzothiophene comme herbicides - Google Patents

Utilisation des derives du benzothiophene comme herbicides Download PDF

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Publication number
WO1999009023A1
WO1999009023A1 PCT/EP1998/005247 EP9805247W WO9909023A1 WO 1999009023 A1 WO1999009023 A1 WO 1999009023A1 EP 9805247 W EP9805247 W EP 9805247W WO 9909023 A1 WO9909023 A1 WO 9909023A1
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Prior art keywords
alkyl
haloalkyl
substituted
formula
alkenyl
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PCT/EP1998/005247
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English (en)
Inventor
Hermann Rempfler
Andrew Edmunds
Alain De Mesmaeker
Karl Seckinger
Original Assignee
Novartis Ag
Novartis-Erfindungen
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Publication date
Application filed by Novartis Ag, Novartis-Erfindungen filed Critical Novartis Ag
Priority to EP98946374A priority Critical patent/EP1005467A1/fr
Priority to BR9811314-3A priority patent/BR9811314A/pt
Priority to CA002291101A priority patent/CA2291101A1/fr
Priority to AU93441/98A priority patent/AU732154B2/en
Publication of WO1999009023A1 publication Critical patent/WO1999009023A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
    • C07D333/68—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
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to novel herbicidally active substituted bicyclic benzoyi derivatives, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth.
  • Isoxazolyl- and pyrazolyl-benzoyi and bicyclic benzoyi derivatives having herbicidal activity are known and are described, for example, in WO 96/26192, WO 96/26206 and WO 97/08164.
  • the present invention therefore relates to compounds of formula I
  • R 2 o and R 2 ⁇ are each independently of the other C C 4 alkyl; or R 20 and R 21 together are -(CH 2 ) n1 -;
  • R 2 is hydrogen or C ⁇ -C 4 alkyl
  • R 3 and R are each independently of the other hydrogen, C C 4 alkyl or halogen; n is 0, 1 or 2; R 5 is C C 4 alkyl, CrC 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C C 4 alkoxy, C 1 -C haloalkoxy, C ⁇ -C 4 alkyl-S(O) n2 , (CrC alkyl)2NS(O) 2 , C C 4 alkyl-S(O) 2 O, halogen, nitro or cyano; n 2 is O, 1 or 2;
  • Q is OH, halogen or a group (Q 2 ),
  • R 6 and R 7 are each independently of the other hydrogen, OH, CrOjalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, d-C 4 alkoxycarbonyl, CrC 4 alkyl-S(O) n2 , CrC 4 alkyl-NHS(O) 2 , phenyl or phenyl substituted by C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl, CrC alkoxy, C ⁇ -C 4 haloalkoxy, CrC alkylcarbonyl, CrC 4 alkoxycarbonyl, amino, d-C alkylamino, di-C ⁇ -C 4 alkylamino, CrC 4 alkyl-S(O) n2 , C C 4 alkyl-S(O) 2 O, C ⁇ -C 4 haloalkyI-S(O) n2 , C C 4 haloalkyl-S(O) 2 O, CrC
  • W is oxygen, sulfur, -C(R 18 ) 2 - or -N(R 22 )- ; n 6 is 0 or 1 , or when W is -C(R 18 ) 2 - , n 6 may additionally be 2 or 3; each R 18 independently of the other is hydrogen, C C 4 alkyl, C C 4 haloalkyl or C C 4 alkoxy- carbonyl; or R 18 together with one of the adjacent substituents R 7 forms a single bond when n 6 is 1 , and the remaining geminal R 6 and R 7 are other than hydrogen;
  • R 2 is hydrogen, C ⁇ -C 4 alkyl or C ⁇ -C 4 alkoxycarbonyl
  • R 8 is OH, CrC 4 alkoxy, CrC alkylcarbonyloxy, C C alkoxycarbonyloxy, R 23 R 24 N-C(O)O, phenylthio, C C 4 alkylthio, C C 4 alkyl-S(O) 2 O, (C C 4 alkoxy) 2 P(O)O, C 1 -C 4 alkyl(C 1 -C 4 - alkoxy)P(O)O, H(d-C 4 alkoxy)P(O)O or benzoyloxy;
  • R 23 and R 24 are each independently of the other hydrogen or d-C 4 alkyl
  • Y is oxygen, sulfur or -(CH 2 ) n5 -; n 5 is O, 1 , 2, 3 or 4;
  • R 9 is hydrogen, C ⁇ -C 6 alkyl, d-C 4 alkylcarbonyl, d-C 4 alkoxycarbonyl, (C C alkyl)NHCO or (C 1 -C 4 alkyl) 2 NCO;
  • R 10 , R 11 and R 12 are each independently of the others hydrogen, d-C 4 alkyl, C C 4 alkoxy- carbonyl, phenyl or phenyl substituted by C ⁇ -C 4 alkyl, C C 4 haloalkyl, C ⁇ -C 4 alkoxy, C C 4 - haloalkoxy, C ⁇ -C 4 alkylcarbonyl, C C 4 alkoxycarbonyl, amino, d-C alkylamino, di-d-daikyl- amino, C ⁇ -C 4 alkyl-S(O) n2 , C C 4 alkyl-S(O)2 ⁇ , C ⁇ -C 4 haloalkyl-S(O)n , C ⁇ -C 4 haloalkyl-S(O) 2 O, CrC 4 alkyl-S(O) 2 NH, C C 4 alkyl-S(O) 2 N(C ⁇ -C 4 alkyl), halogen, nitro, COOH or
  • R 13 is hydrogen; halogen; C C 4 alkyl; C C alkyl substituted by unsubstituted or R 17 - substituted phenyl; C ⁇ -C 4 haloalkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkenyl substituted by unsubstituted or R 17 -substituted phenyl; C 2 -C 6 alkynyl; C 2 -C 6 alkynyl substituted by unsubstituted or R 17 - substituted phenyl; C 3 -C 6 haloalkenyl; C 3 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 3 -C 6 cycloalkyl substituted by halogen, R 15 or COOR ⁇ 6 ; COOR 16 ; COR 15 ; cyano; nitro; CONH 2 ; (d-C 4 - alkyl)NHCO; (CrC 4
  • R 15 is d-C 4 alkyl, C C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C -C 6 alkynyl, C 3 -C 6 halo- alkynyl, phenyl or R ⁇ 7 -substituted phenyl;
  • R 16 is hydrogen, C ⁇ -C 4 alkyl or d-C 4 haloalkyl
  • R 17 is halogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, d-C 4 alkoxy-C ⁇ -C 4 alkyl, C ⁇ -C alkoxy-C 3 -C 6 alkenyl, d-C alkoxy-C 3 -C 6 - alkynyl, cyano, nitro, COOH, C C 4 alkoxycarbonyl, CrC 4 haloalkoxycarbonyl, C C 4 alkyl- S(O) n2 , C 1 -C 4 haloalkyl-S(O) n2 , phenyl-S(O) n 2; phenyl-S(O) n2 substituted on the phenyl ring by halogen, d-C
  • R 14 is d-C 4 alkyl, C ⁇ -C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 halo- alkynyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by halogen, C C 4 alkyl, C C 4 halo- alkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, phenyl or phenyl substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, cyano, nitro, COOH, d-C al
  • halogen is to be understood as meaning iodine or, preferably, fluorine, chlorine or bromine.
  • alkyl, alkenyl and alkynyl groups in the substituent definitions may be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of the following groups: alkylcarbonyl, cyanoalkyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylaminocarbonyl, dialkyl- aminocarbonyl, (alkyl) 2 NS(O) 2 , alkyl(alkoxy)P(O)O, alkyl substituted by unsubstituted or R 17 - substituted phenyl, alkenyl substituted by unsubstituted or R 17 -substituted phenyl, alkoxy- carbonylalkenyl, alkylS(O) 2 N(alkyl), (alkyl) 2 NCO, (alkyl) 2 NCS ,alkenyl-S(O) n2 substituted by unsub
  • Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and the various isomers of pentyl and hexyl. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
  • alkenyl radicals examples include vinyl, allyl, methallyl, 1 -methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals having a chain length of from 3 to 5 carbon atoms.
  • alkynyl radicals examples include ethynyl, propargyl, 1-methyl- propargyl, 3-butynyl, but-2-yn-1 -yl, 2-methylbut-3-yn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4- yn-1-yl and 2-hexynyl, with preference being given to alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
  • Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro- ethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.
  • Suitable haloalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-1 -yl and 4,4,4-trichlorobut-2-en-1-yl.
  • alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms.
  • the alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
  • Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3- fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4- trifluoro-but-2-yn-1 -yl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri- fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
  • Alkenylsulfonyl is, for example, allylsulfonyl, methallylsulfonyl, but-2-en-1-ylsulfonyl, pentenylsulfonyl or 2-hexenylsulfonyl.
  • Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
  • Alkylamino is, for example, methylamino, ethylamino or an isomer of propyl- or butyl-amino.
  • Dialkylamino is, for example, dimethylamino, diethyiamino or an isomer of dipropyl- or dibutyl-amino.
  • Alkylcarbonyl is especially acetyl or propionyl.
  • Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or tert-butoxy.
  • Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1 -yloxy.
  • Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2,2-trichloroethoxy or pentafluoroethoxy.
  • cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or per- halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromo- cyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl, 2- fluoro-2-chlorocyclopropyl, 2-chloro-2-bromocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, pentafluorocyclopropyl, fluorocyclobutyl, chlorocyclobutyl, 2,2-difluorocyclobutyl, 2,2,3,3-tetrafluorocyclobutyl, 2,2,3-trifluoro-3-chlorocyclobutyl, 2,2- dich
  • Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
  • Phenyl per se, or as part of a substituent may be unsubstituted or substituted, in which case the substituents may be in the ortho-, meta- or para-position.
  • substituents are, for example, d-C 4 - alkyl, C ⁇ -C alkoxy, halogen or C ⁇ -C haloalkyl.
  • cyanoalkyl alkylcarbonyl, alkoxycarbonylalkenyl, alkylcarbonyloxy, alkoxycarbonyl, alkoxycarbonyloxy and haloalkoxycarbonyl
  • the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be.
  • the compounds of formula I wherein Q is a group Q 5 may also be in the form of mixtures of the following isomeric forms l 6 , l and le:
  • the invention includes all those isomeric forms to l 4> Ic, l 6 , l 7 and le and their mixtures to l 4 and Ic, and l 6 , l 7 and le.
  • the invention likewise includes the salts that the compounds of formula I having azide
  • sulfonamide groups are able to form with bases.
  • bases e.g. alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium.
  • Suitable salt formers are described, for example, in WO 97/41112.
  • alkali metal and alkaline earth metal hydrides attention is drawn, for example, to sodium hydride and calcium hydride, and among the carbonates attention is drawn to the carbonates of sodium, potassium, caesium, calcium, barium, magnesium and lithium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary d-C ⁇ 8 alkylamines, C ⁇ -C hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptyiamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyioctadecylamine
  • the salts of compounds of formula I having basic groups, especially having basic amino groups, for example alkylamino and dialkylamino groups, in the definition of R 6 , R 7 or R 17 are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid, nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid
  • sulfuric acid phosphoric acid
  • the compounds of formula I may also be in the form of rotational isomers (atropisomers).
  • Ri is d-C 4 alkyl, d-C 4 haloalkyl, C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkyl, d-C 4 alkoxycarbonyl, cyano, cyano-C C 4 alkyl, CHO, C ⁇ -C 4 alkyl-
  • ON CH, C 2 -C 6 alkenyl, d-C 4 alkoxycarbonyl-C 2 -C 6 alkenyl or a group — CH(OR 20 )OR 21 ;
  • W is oxygen, sulfur, -C(R 18 ) 2 - or -N(R 22 )-; each R 18 independently of the other is hydrogen, C ⁇ -C alkyl or C ⁇ -C 4 alkoxycarbonyl; and R 22 is hydrogen, d-C 4 alkyl or C C 4 alkoxycarbonyl.
  • R 8 is OH, C C alkoxy, C ⁇ -C 4 alkylcarbonyloxy, phenylthio or C ⁇ -C 4 alkylthio;
  • R 10 , Rn and R 12 are each independently of the others hydrogen, d-C 4 alkyl or C C alkoxycarbonyl;
  • R 13 is halogen, d-C 4 alkyl, C 3 -C 6 - cycloalkyl, COOR ⁇ 6 , COR 15 or cyano;
  • R is C C 4 alkyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl substituted by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 halo- alkyl
  • R 6 and R 7 are each independently of the other d-C 4 alkyl or
  • R ⁇ to R 5 and n are as defined and X is a leaving group, e.g. halogen, in an inert organic solvent in the presence of a base with a compound of formula IV
  • Zi is NR 10
  • Z 2 is oxygen
  • R 6 , R , R9, R 1 0, W, n 6 and n 5 are as defined for formula I, to form a compound of formula Ic
  • Ri to R 5 and n are as defined for formula I; Q is a group (Q 5 ); and
  • Rn and R 2 are as defined for formula I is carried out analogously to known procedures and comprises either:
  • Ri to R 5 and n are as defined and X is a leaving group, e.g. halogen, with a compound of formula IVa
  • Rn and R ⁇ 2 are as defined, in an inert organic solvent in the presence of a base and a coupling agent to form a compound of formula le
  • Ri to R 5 and n are as defined for formula I;
  • Q is a group (Q 6 );
  • R ⁇ 3 i IS hydrogen, d-C 4 alkyl, C ⁇ -C alkyl substituted by unsubstituted or R 17 -substituted phenyl, d-C haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R ⁇ 7 -substituted phenyl, C 2 -C 6 alkynyl, C 2 -C 6 alkynyl substituted by unsubstituted or R 17 -substituted phenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl substituted by halogen, R 15 or COOR ⁇ 6 ;
  • Ri to R 5 , R i4 and n are as defined, in the presence of a base, carbon disulfide and an alkylating reagent of formula VI wherein R 25 is d-C 4 alkyl, d-C 4 alkyl substituted by unsubstituted or R ⁇ 7 -substituted phenyl, d-C 4 alkoxy-C 2 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R 17 - substituted phenyl, C -C 6 alkynyl or C 2 -C 6 alkynyl substituted by unsubstituted or R 17 - substituted phenyl; R ⁇ 7 is as defined for formula I, and Xi is a leaving group, e.g. halogen or sulfonate, into a compound of formula VII
  • Ri to R 5 , R M , R 25 and n are as defined, then cyclising that compound with hydroxyl- amine hydrochloride, optionally in a solvent, in the presence of a base to form a compound of formula If wherein R to R 5 , R 14 and n are as defined, R 13 is R 25 S and R 25 is CrC 4 alkyl, C ⁇ -C 4 alkyl substituted by unsubstituted or R ⁇ -substituted phenyl, d-C 4 alkoxy-C 2 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyl substituted by unsubstituted or R 17 -substituted phenyl, C 2 -C 6 alkynyl or C 2 -C 6 - alkynyl substituted by unsubstituted or R ⁇ 7 -substituted phenyl, and then oxidising that compound, for example with meta-chlor
  • Ri, R 3 to R 5 and n are as defined for formula I and R 2 is CH 3 is carried out analogously to known procedures and comprises either:
  • R 5 is as defined for formula I and R 28 is d-C 4 alkyl, with a compound of formula XXV
  • Hal is chlorine, bromine or iodine, to yield a compound of formula XXIII
  • R 1 R 3 to R 5 and n are as defined for formula I and R 2 is CH 3 is carried out analogously to known procedures and comprises reacting a compound of formula XXa
  • R 5 is as defined and R 28 is d-C 4 alkyl, with a compound of formula XXVa
  • Ri to R 5 and n are as defined for formula I and Q is halogen is carried out analogously to known procedures and comprises treating a compound of formula Id
  • Ri to R 5 and n are as defined, with a halogenating agent.
  • the starting materials used are carboxylic acid derivatives of formula III wherein X is a leaving group, e.g. halogen, for example iodine, bromine or especially chlorine, N-oxyphthalimide or N,O-dimethylhydroxylamino or part of
  • an activated ester e.g. (formed from dicyclohexylcarbodiimide
  • N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide and the corresponding carboxylic acid).
  • Those starting materials are reacted in an inert organic solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene, and in the presence of a base, for example an alkylamine, e.g. triethylamine, an aromatic amine, e.g. pyridine or 4-dimethylaminopyridine (DMAP), with a dione derivative of formula IV to form isomeric enol ethers of formula Ic.
  • the esterification takes place at temperatures of from 0°C to 110°C.
  • a base for example an alkylamine, e.g. triethylamine, or a carbonate, e.g. potassium carbonate, and a catalytic amount of a cyanide source, for example acetone cyanohydrin or potassium cyanide.
  • an inert solvent for example a halogenated hydrocarbon, e.g. dichloromethane, a nitrile, e.g. acetonitrile, or an aromatic hydrocarbon, e.g. toluene
  • a base for example an alkyl
  • the compounds of formula I wherein Q is a group Q 5 can be obtained in a manner analogous to that described, for example, in Reaction Scheme 1 or Tetrahedron 36, 2409 (1976), either
  • the reaction is advantageously carried out in a solvent, for example an amide, e.g. N,N-dimethylformamide (DMF), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), or a nitrile, e.g. acetonitrile.
  • a solvent for example an alcohol, e.g.
  • the carboxylic acids of formula Id can be prepared analogously to known procedures, e.g. in accordance with the methods given in Reaction Schemes 4 and 5 below.
  • DMSO dimethyl sulfoxide
  • ketone e.g. acetone
  • nitrile e.g. acetonitrile
  • a base for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride.
  • the reaction temperatures are generally in the range of from 0°C to 110°C.
  • the subsequent Claisen rearrangement of the allyl ether of formula XXI in Reaction Scheme 4 can be carried out, for example, thermally at temperatures of from 100°C to 300°C, optionally in an inert solvent, for example an aromatic hydrocarbon, e.g. xylene.
  • an inert solvent for example an aromatic hydrocarbon, e.g. xylene.
  • the thermal Claisen rearrangement can be carried out, for example, also without a solvent in a microwave oven.
  • Such Claisen rearrangements are described, for example, in C. Ferri, "Retician der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff..
  • the resulting phenol derivative of formula XXII is then acylated, for example with a thiocarbamoyl halide of formula XXVI, e.g. N,N-dimethyl- thioformyl chloride, in an aprotic solvent, for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sulfoxide (DMSO), a ketone, e.g.
  • a thiocarbamoyl halide of formula XXVI e.g. N,N-dimethyl- thioformyl chloride
  • an aprotic solvent for example an amide, e.g. N,N-dimethylformamide (DMF) or 1-methyl-2-pyrrolidone (NMP), a sulfoxide, e.g. dimethyl sul
  • acylation is advantageously carried out at temperatures of from 0°C to 110°C.
  • a metal hydroxide e.g. sodium hydroxide
  • a mineral acid e.g. hydrochloric acid or sulfuric acid
  • Suitable solvents are, for example, water, ethers, e.g. tetrahydrofuran, halogenated hydrocarbons, e.g. dichloromethane, and aromatic hydrocarbons, e.g. toluene.
  • the resulting benzothiophene derivative of formula Id wherein R 2 is methyl and n is 0 can then be oxidised in accordance with various standard methods.
  • the oxidation is carried out, for example, with hydrogen peroxide in an acidic solvent, for example an organic acid, e.g.
  • acetic acid or with an organic peracid, for example meta- chloroperbenzoic acid (m-CPBA), in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene.
  • m-CPBA meta- chloroperbenzoic acid
  • an inert solvent for example a halogenated hydrocarbon, e.g. dichloromethane, or an aromatic hydrocarbon, e.g. toluene.
  • the reaction temperatures for the oxidation are generally in the range of from 0°C to 110°C.
  • the electrophilic bromination according to Route b) in Reaction Scheme 4 is carried out, for example, analogously to Chem. Communic. 1972, 214.
  • the bromination of the salicylic acid derivative of formula XX can be effected, for example, in an inert solvent, for example a halogenated hydrocarbon, e.g. dichloromethane, and in the presence of a Lewis acid, for example titanium halide, e.g. titanium tetrachloride, at temperatures of from 0°C to 100°C.
  • the coupling product of formula XXII obtained by Route b) can then, for example in a manner analogous to that described under Route a), be acylated, rearranged, hydrolysed and cyclised, and optionally oxidised to form a compound of formula Id.
  • DMSO dimethyl sulfoxide
  • ketone e.g. acetone
  • nitrile e.g. acetonitrile
  • a base for example a carbonate, e.g. potassium or caesium carbonate, or a metal hydride, e.g. sodium hydride, at temperatures of from 0°C to 200°C.
  • the activated carboxylic acid derivatives of formulae III and I in Reaction Schemes 1 and 2 (Route a)) wherein X is a leaving group, for example halogen, e.g. bromine, iodine or especially chlorine, can be prepared according to known standard procedures as described, for example, by C. Ferri in "Restrokeen der organischen Synthese", Georg Thieme Verlag, Stuttgart, 1978, page 461 ff., such as, for example, in accordance with Reaction Scheme 6 below.
  • a halogenating agent for example a thionyl halide, e.g. thionyl chloride or bromide; a phosphorus halide or phosphorus oxyhalide, e.g. phosphorus pentachloride or phosphorus oxychloride, or phosphorus pentabromide or phosphoryl bromide; or an oxalyl halide, e.g.
  • oxalyl chloride or by the use of a reagent for forming activated esters, for example N,N'- dicyclohexylcarbodiimide (DCC) or N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) of formula X.
  • a reagent for forming activated esters for example N,N'- dicyclohexylcarbodiimide (DCC) or N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide (EDC) of formula X.
  • the compound of formula X is a halogenating agent
  • the group X is, for example, a leaving group, for example halogen, e.g. fluorine, bromine or iodine or especially chlorine
  • Wi is, for example, PCI 2 , SOCI, SOBr or CICOCO.
  • the operation is optionally carried out in an inert organic solvent, for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, for example n-hexane, benzene, toluene, a xylene, dichloromethane, 1 ,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of from -20°C to the reflux temperature of the reaction mixture, preferably at from 40 to 150°C, and in the presence of a catalytic amount of N,N-dimethylformamide.
  • an inert organic solvent for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, for example n-hexane, benzene, toluene, a xylene, dichloromethane, 1 ,2-dichloroethane or chlorobenzene, at reaction temperatures in the range of from -20°C to the reflux temperature of the
  • Ri to R 5 and n are as defined for formula I and R 28 is d-C 4 alkyl, for example via Claisen condensation, or from the compounds of formula III by reaction with a ketocarboxylic acid salt of formula XXVIII
  • R ⁇ 4 is as defined for formula I and M + is an alkali metal ion (see, for example, WO 96/26192, EP-A-0 496 631 ).
  • the salicylic acid derivatives of formula XX (Reaction Scheme 4) are either known (some of them being commercially available, for example when R 5 is amino (4-aminosalicylic acid)) or can readily be prepared by standard procedures, for example starting from 4-aminosalicylic acid via diazotisation, Sandmeyer reaction and aromatic, nucleophilic substitution (see e.g. J. March, "Advanced Organic Chemistry", 4th Edition, John Wiley & Sons, New York, 1992, pages 641 -676) or Heck reaction of the resulting halide.
  • the benzoic acid derivatives of formula XXa (Reaction Scheme 5) are either known or can readily be obtained by bromination of the corresponding benzoic acid derivatives (see Reaction Scheme 4, Route b)).
  • reagents of formulae VI, VIII, X, XXV, XXVa, XXVb and XXVI used in Reaction Schemes 3 to 6 are either known or can be prepared analogously to disclosed procedures.
  • a large number of known standard procedures are available, for example alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction, the choice of a suitable preparation process being governed by the properties (reactivities) of the substituents in the respective intermediates (see e.g. EP-A-0 796 856).
  • the end products of formula I can in conventional manner be isolated by concentration 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, by distillation or by means of column chromatography and a suitable eluant.
  • solvents in which they are not readily soluble such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons
  • the sequence in which it is advantageous to carry out certain reactions in order to avoid possible secondary reactions will also be familiar to the person skilled in the art. Unless the synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers.
  • the isomers can be separated according to methods known per se.
  • the compounds of formula I may be used in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • 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, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
  • surfactants conventionally employed in formulation technology, which are described in, inter alia, "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, 1980-81 , are also suitable for the preparation of the compositions according to the invention.
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I can be used successfully either in the form of a mixture of the isomeric forms li to l and Ic (Q is a group Qi to Q 4 and R 8 is OH) or l 6 , 17 and le (Q is a group Q 5 ) or in the form of pure isomeric forms to l or Ic, or l 6 , I7 or le, generally on plants or the locus thereof, at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • the concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques.
  • the weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, 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, Phaseolus
  • Echinochloa, Scirpus Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottbo
  • reaction mixture is poured into an ice-water mixture and extracted by shaking with ethyl acetate.
  • the ethyl acetate phase is washed with water, then with brine, dried over sodium sulfate and concentrated by evaporation.
  • the residue is chromatographed on silica gel (eluant: ethyl acetate/hexane 1/3), yielding 114.5 g (85 % of theory) of the desired product in the form of an oil.
  • Example P6 4-Chloro-2-methyl-1 ,1 -dioxo-2.3-dihvdro-benzofblthiophene-7-carboxylic acid
  • Example P7 4-Chloro-2-methyl-1.1 -dioxo-2.3-dihvdro-benzorblthiophene-7-carboxylic acid chloride
  • _ ⁇ ⁇ _ C o ⁇ ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox ox
  • CD S o 3 O Q X - ⁇ Z 2

Abstract

La présente invention concerne les composés de la formule (I) dans laquelle R1 représente C¿1?-C4alkyle, C1-C4haloalkyle, C1-C4alcoxy-C1-C4alkyle, C1-C4alcoxycarbonyle, cyano, cyano-C1-C4alkyle, hydroxy-C1-C4-alkyle, amino-C1-C4-alkyle, CHO, C1-C4-alkyle-ON=CH, C2-C6alcényle, C1-C4alcoxycarbonyle-C2-C6alcényle ou un groupe -CH(OR20)OR21; R20 et R21 représentent chacun indépendamment l'autre C1-C4alkyle; ou R20 et R21 représentent ensemble -(CH2)n1-; n1 représente 2, 3 ou 4; R2 représente un hydrogène ou C1-C4alkyle; R3 et R4 représentent chacun indépendamment l'autre hydrogène, C1-C4alkyle ou halogène; n représente 0, 1 ou 2; R5 représente C1-C4alkyle, C1-C4haloalkyle, C2-C6alcényle, C2-C6alkynyle, C1-C4alcoxy, C1-C4haloalcoxy, C1-C4alkyle-S(O)n2, (C1-C4alkyle)2NS(O)2, C1-C4alkyle-S(O)2O, un halogène, un nitro ou un cyano; n2 représente 0, 1 ou 2; Q représente OH, un halogène ou un groupe (Q1), (Q2), (Q3), (Q4), (Q5) ou (Q6); R6 à R14, W, Y et n6 sont tels que définis dans la revendication 1, les sels et les stéréoisomères acceptables agrochimiquement des composés de la formule (I) possédant de bonnes propriétés herbicides sélectives de pré-levée et de post-levée. Cette invention concerne également la préparation de ces composés et leur utilisation comme ingrédients actifs à action herbicide.
PCT/EP1998/005247 1997-08-20 1998-08-18 Utilisation des derives du benzothiophene comme herbicides WO1999009023A1 (fr)

Priority Applications (4)

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EP98946374A EP1005467A1 (fr) 1997-08-20 1998-08-18 Utilisation des derives du benzothiophene comme herbicides
BR9811314-3A BR9811314A (pt) 1997-08-20 1998-08-18 Derivados de benzotiofeno como herbicidas
CA002291101A CA2291101A1 (fr) 1997-08-20 1998-08-18 Utilisation des derives du benzothiophene comme herbicides
AU93441/98A AU732154B2 (en) 1997-08-20 1998-08-18 Benzothiophene derivates as herbicides

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Cited By (7)

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WO2000020408A1 (fr) * 1998-10-06 2000-04-13 Idemitsu Kosan Co., Ltd. Derive de tricetone et herbicide
WO2001007422A1 (fr) * 1999-07-27 2001-02-01 Aventis Cropscience Gmbh Benzoylcyclohexanediones a substitution isoxazolyle et isoxazolinyle, leur procede de production et leur utilisation comme herbicides et regulateurs de la croissance vegetale
WO2001066522A1 (fr) * 2000-03-09 2001-09-13 Syngenta Participations Ag Herbicides phenyl acyle ou pyridine
WO2002050055A1 (fr) * 2000-12-21 2002-06-27 Idemitsu Kosan Co., Ltd. Derives de benzothiophene et compositions herbicides a base de ces derives
US20060240984A1 (en) * 1999-09-08 2006-10-26 Ken Pallett Herbicidal compositions
WO2015000715A1 (fr) 2013-07-02 2015-01-08 Syngenta Participations Ag Hétérocycles bi- ou tricycliques à action pesticide avec substituants soufrés
WO2023094304A1 (fr) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Dérivés amides hétérobiaryles microbiocides

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CN112430228B (zh) * 2020-11-25 2021-09-07 四川大学 一种手性2,3-二氢苯并[b]噻吩1,1-二氧化物、衍生物及制备方法

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000020408A1 (fr) * 1998-10-06 2000-04-13 Idemitsu Kosan Co., Ltd. Derive de tricetone et herbicide
US6756343B1 (en) 1998-10-06 2004-06-29 Idemitsu Kosan Co., Ltd. Triketone derivatives and herbicide
WO2001007422A1 (fr) * 1999-07-27 2001-02-01 Aventis Cropscience Gmbh Benzoylcyclohexanediones a substitution isoxazolyle et isoxazolinyle, leur procede de production et leur utilisation comme herbicides et regulateurs de la croissance vegetale
US6211216B1 (en) 1999-07-27 2001-04-03 Aventis Corpscience Gmbh Isoxazolyl- and isoxazolinyl-substituted benzoylcyclohexanediones, process for their preparation and their use as herbicides and plant growth regulators
US20060240984A1 (en) * 1999-09-08 2006-10-26 Ken Pallett Herbicidal compositions
US8642509B2 (en) * 1999-09-08 2014-02-04 Aventis Cropscience Uk Limited Herbicidal compositions
WO2001066522A1 (fr) * 2000-03-09 2001-09-13 Syngenta Participations Ag Herbicides phenyl acyle ou pyridine
WO2002050055A1 (fr) * 2000-12-21 2002-06-27 Idemitsu Kosan Co., Ltd. Derives de benzothiophene et compositions herbicides a base de ces derives
WO2015000715A1 (fr) 2013-07-02 2015-01-08 Syngenta Participations Ag Hétérocycles bi- ou tricycliques à action pesticide avec substituants soufrés
EP3778598A2 (fr) 2013-07-02 2021-02-17 Syngenta Participations Ag Les hétérocycles bi- ou tricycliques à activité pesticide avec des substituants contenant du soufre
WO2023094304A1 (fr) 2021-11-25 2023-06-01 Syngenta Crop Protection Ag Dérivés amides hétérobiaryles microbiocides

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AU9344198A (en) 1999-03-08
CA2291101A1 (fr) 1999-02-25

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