WO1997027187A1 - Derives de l'isoxazole et de 2-cyano-1,3-diones et leur utilisation comme desherbants - Google Patents

Derives de l'isoxazole et de 2-cyano-1,3-diones et leur utilisation comme desherbants Download PDF

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WO1997027187A1
WO1997027187A1 PCT/EP1997/000258 EP9700258W WO9727187A1 WO 1997027187 A1 WO1997027187 A1 WO 1997027187A1 EP 9700258 W EP9700258 W EP 9700258W WO 9727187 A1 WO9727187 A1 WO 9727187A1
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formula
compound
carbon atoms
optionally substituted
halogen
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PCT/EP1997/000258
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English (en)
Inventor
Atsushi Go
Koichi Araki
Norishige Toshima
Oe Yukiko
Claude Lambert
Masahito Itoh
Yoshie Kirio
Norio Sasaki
Takako Brett
Hidesi Mukaida
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Rhone-Poulenc Agriculture Ltd.
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Priority claimed from GBGB9601575.5A external-priority patent/GB9601575D0/en
Priority claimed from GBGB9626435.3A external-priority patent/GB9626435D0/en
Application filed by Rhone-Poulenc Agriculture Ltd. filed Critical Rhone-Poulenc Agriculture Ltd.
Priority to AU15934/97A priority Critical patent/AU1593497A/en
Publication of WO1997027187A1 publication Critical patent/WO1997027187A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon 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
    • A01N43/48—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
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • This invention relates to novel 4-benzoylisoxazole derivatives, 5- phenylisoxazole derivatives, 2-cyano-l,3-dione derivatives, compositions containing them, processes for their preparation, intermediates in their preparation and their use as herbicides.
  • Herbicidal 4-benzoylisoxazoles are described in European Patent Publication Numbers 0418175, 0487357, 0527036, 0527037, 0560482 and 0560483.
  • Herbicidal 2-cyano-l,3-diones are described in European Patent Publication Numbers 0213892, 0496630 and 0496631 and International Patent Publication No. WO 95/25099.
  • Herbicidal 5-phenylisoxazoles are described in European Patent Publication Number 0524018.
  • none ofthe above publications disclose or suggest the presence of an aromatic heterocyclic ring linked by a ring nitrogen atom to a hydrocarbon group as a substituent on the phenyl ring.
  • the present invention provides 4-benzoylisoxazole derivatives of formula (Ia), 5-phenylisoxazole derivatives of formula (lb) and 2-cyano- 1,3-dione derivatives of formula (Ic):
  • R represents hydrogen or -CO2R ;
  • Rl represents a straight- or branched- chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; or a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more R ⁇ groups or one or more halogen atoms;
  • R2 represents:- . 7 .
  • halogen a straight- or branched- chain alkyl group containing up to six carbon atoms which is substituted by one or more groups -OR 5 ; a cycloalkyl group containing from three to six carbon atoms; or a group selected from nitro, cyano, -CO2R 5 , -S(O) p R 7 , -O(CH 2 ) m OR 5 ,
  • X represents -C(R I 3 R 14 )- or -C(R 13a R 14a ) -C(R 15 R 16 )-;
  • R 3 represents a 5-membered heteroaromatic ring of formula (II)
  • D, E, G and J independently represent -CR* 7 - or a nitrogen atom, with at least one of D, E, G and J representing -CR 7 -; two adjacent groups D, E, G and J may together form a second phenyl or 5- to 7- membered heteroaromatic ring optionally substituted by one or more groups R* 30 , in which the 5- to 7- membered heterocyclic ring contains from one to four heteroatoms in the ring which may be the same or different selected from nitrogen, oxygen and sulphur; R 4 represents :- a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more groups selected from halogen, -OR 5 , -CO2R 5 , -S(O) p R 7 , phenyl and cyano; or phenyl optionally substituted by one or more groups selected from halogen, -OR 5 and R 12 ;
  • R 5 and R ⁇ which may be the same of different, each represents hydrogen or R 12 ;
  • R 7 represents :-
  • R 12 or a cycloalkyl group containing from three to six carbon atoms; or a group -(CH2) w -[phenyl optionally substituted by from one to five groups R 1 a which may be the same or different]; w represents zero or one;
  • R 8 represents :- hydrogen; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to ten carbon atoms optionally substituted by one or more halogen atoms; a cycloalkyl group containing from three to six carbon atoms;
  • R 9 and R 1 ⁇ independently represent hydrogen or a straight- or branched- chain alkyl group containing up to six (preferably up to three) carbon atoms optionally substituted by one or more halogen atoms;
  • R 12 represents :- a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • R 13 , R 13a , R 14a and R 15 independently represent R 5 ;
  • R 1 ⁇ represents halogen, or R 12 ;
  • R 14 represents R 5 , cyano, -OR 12 , -S(O) p R 12 or halogen
  • R 16 represents R 5 , cyano, -OR 12 or -S(O)pR 12 ;
  • R 17 represents: - a group selected from hydrogen, halogen, R 8 , nitro, cyano, -CO 2 R 5 , -S(O) p R 18 , -OR 18 , -NR 5 R 6 and cyclopropyl;
  • R 17a represents R 17 with the exclusion of hydrogen and cyclopropyl
  • R 18 represents a straight- or branched- chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms
  • Y is oxygen or sulphur (preferably Y represents oxygen); Z represents a group selected from R 1 , -NR 8 R 1 ,
  • R 19 and R 2 ⁇ independently represent R 8 ; and agriculturally acceptable salts and metal complexes thereof, which possess valuable herbicidal properties.
  • Compounds of formula (Ic) may exist in enolic tautomeric forms that may give rise to geometric isomers around the enolic double bond.
  • the substituents R, R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R!0, R 1 1, R 12 , R 13 , R 13 , R 13 °, R 14 R 14a R 15 f R 16 ( R 17 , R 17a R 18 , R 19 , R 20 , X and Z may contribute to optical isomerism and/or stereoisomerism. All such forms are embraced by the present invention.
  • reference to compounds of formula (I) means reference to a compound of formula (Ia), (lb), or (Ic). It will be also understood that when X represents -C(R 13a R 14a )-C(R 15 R 16 )- it is attached to the phenyl ring by the -C(R 13a R 14a ) linking carbon.
  • agriculturally acceptable salts salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use.
  • the salts are water-soluble.
  • Suitable salts with bases include alkali metal (eg. sodium and potassium), alkaline earth metal (eg. calcium and magnesium), ammonium and amine (eg. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts.
  • Suitable acid addition salts formed by compounds of formula (I) containing an amino group, include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids, for example acetic acid.
  • metal complexes compounds in which one or both ofthe oxygen atoms ofthe 1,3-dione of formula (Ic) act as chelating agents to a metal cation.
  • examples of such cations include zinc, manganese, cupric, cuprous, ferric, ferrous, titanium and aluminium.
  • the compounds of the invention in certain aspects of their properties, for example their control of Echinochloa orvzicola and their selectivity in paddy rice, show advantageous properties over known compounds.
  • R 7 is selected from hydrogen, halogen, R 18 , nitro, cyano, -CO 2 R 5 , S(O) p R 18 , -OR 18 and -NR 5 R 6 are preferred.
  • R 3 represents an N-linked ring of formula (II) in which: -
  • D is nitrogen and E, G and J represent -CR 17 - (i.e. a pyrazol- 1 -yl group);
  • D, G and J are -CR 17 - and E is nitrogen (i.e. an imidazol- 1-yl group);
  • D and G are nitrogen and E and J are -CR 17 - (i.e. a
  • D and E are nitrogen and G and J are -CR 17 - (i.e. a 1,2,3-triazol-l-yl group).
  • R 3 is a ring of formula (II) in which D is nitrogen, E and J are -CR 17 - and G is nitrogen or CR 17 .
  • R 1 represents a straight- or branched- chain alkyl group containing up to three carbon atoms which is optionally substituted by one or more halogen atoms; or cyclopropyl or 1-methylcyclopropyl.
  • R 1 represents a cyclopropyl group.
  • R 2 represents halogen; a straight- or branched- chain alkyl or alkenyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from nitro, cyano, -S(O) p R 7 , -OR 7 and -OH.
  • n zero, one or two.
  • R 7 represents a straight- or branched- chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms.
  • a preferred class of compounds of formula (Ia) above are those wherein: -
  • R represents hydrogen or -CO2R 4 ;
  • R 1 represents cyclopropyl or 1-methylcyclopropyl
  • R 2 represents :- a straight- or branched- chain alkyl or alkenyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; a group selected from halogen, nitro, cyano, -S(O) p R 7 , -OR 7 and -OH; n represents zero, one or two; X represents -CHR 13 -;
  • R 3 represents an N-linked 5-membered heteroaromatic ring of formula (II) in which D, E, G and J independently represent -CR 17 - or a nitrogen atom, with at least one of D, E, G and J representing a CR 1 group; R 4 represents methyl or ethyl;
  • R 13 represents hydrogen or a straight- or branched- chain alkyl or alkenyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms.
  • a particularly preferred class of compounds of formula (Ia) above are those wherein:-
  • R represents hydrogen or -CO2R 4 ;
  • R 1 represents cyclopropyl or 1-methylcyclopropyl
  • R 2 represents :- halogen; a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or a group selected from -S(O) p R 7 or -OR 7 ;
  • X represents -CH2
  • R 3 represents a pyrazole, imidazole or 1,2,4-triazole ring
  • R 4 represents a methyl or ethyl group
  • R 7 represents:- a methyl or ethyl group which is optionally substituted by one or more halogen atoms
  • n represents 0, 1 or 2;
  • R 17 represents hydrogen, methyl or ethyl.
  • a further particularly preferred class of compounds of formula (Ia) are those wherein:-
  • R represents hydrogen or -CO2R 4 ;
  • R represents cyclopropyl
  • R 2 represents :- halogen; a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or -S(O) p R 7 ;
  • X represents -CH -
  • R 3 represents a pyrazole, imidazole or 1,2,4-triazole ring in which the ring carbon atoms bear a group R 17 ;
  • R 4 represents a methyl or ethyl group
  • R 7 represents a methyl or ethyl group which is optionally substituted by one or more halogen atoms; n represents 0, 1 or 2; and R 17 represents hydrogen or a straight- or branched- chain alkyl group containing up to three carbon atoms.
  • a further particularly preferred class of compounds of formula (I) above are those wherein: -
  • R 1 represents cyclopropyl
  • R 2 represents :- halogen; a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or -S(O) p R 7 ; or two groups R 2 , together with adjacent carbon atoms ofthe phenyl ring, form a 1,3-benzodioxole ring which is optionally substituted by one or two halogen (preferably chlorine or fluorine) atoms at the 2- position ofthe 1,3-benzodioxole ring;
  • halogen preferably chlorine or fluorine
  • X represents -CH 2 -, -CH(Me)- or -CH(Et)-;
  • R 3 represents a pyrazole, imidazole or 1,2,4-triazole ring optionally substituted on the ring carbon atoms by one or two groups selected from a straight- or branched- chain alkyl group containing up to four carbon atoms, -S(O) p R 18 or cyclopropyl;
  • R 4 represents methyl or ethyl
  • R 7 represents methyl or ethyl which are optionally substituted by one or more halogen atoms
  • R 1 is methyl or ethyl; and n and p represent 0, 1 or 2.
  • Particularly important compounds of formula (I) include the following ethyl 5-cyclopropyl-4-[2-( 1,2,4-t ⁇ azol- 1 -ylmethyl)-4- t ⁇ fluoromethylbenzoyl] ⁇ soxazole-3-carboxylate, ethyl 5-cyclopropyl-4-[2-(l-pyrazolylmethyl)-4- t ⁇ fluoromethylbenzoyl] ⁇ soxazole-3-carboxylate, ethyl 5-cyclopropyl-4-[2-(l-pyrazolylmethyl)benzoyl] ⁇ soxazole-3- carboxylate, ethyl 5-cyclopropyl-4-[2-( 1 ,2,4-triazol- 1 - ylmethyl)benzoyl]isoxazole-3-carboxylate, ethyl 5-cyclopropyl-4-[2-(l-imidazolylmethyl)benzoyl]isoxazole-3- carboxylate
  • L is a leaving group and R 1 , R 2 , R 3 , n and X are as hereinbefore defined, with hydroxylamine or a salt of hydroxylamine.
  • Hydroxylamine hydrochloride is generally preferred.
  • L is alkoxy, for example ethoxy, or N,N-dialkylamino, for example dimethylamino.
  • the reaction is generally carried out in an organic solvent such as ethanol or acetonitrile or a mixture of a water-miscible organic solvent and water, preferably in a ratio of organic solvent: water of from 1:99 to 99:1, optionally in the presence of a base or acid acceptor such as triethylamine or sodium acetate at a temperature from room temperature to the boiling point ofthe solvent.
  • organic solvent such as ethanol or acetonitrile or a mixture of a water-miscible organic solvent and water, preferably in a ratio of organic solvent: water of from 1:99 to 99:1, optionally in the presence of a base or acid acceptor such as triethylamine or sodium acetate at a temperature from room temperature to the boiling point ofthe solvent.
  • a base or acid acceptor such as triethylamine or sodium acetate
  • R 1 is as hereinbefore defined and Y' represents a carboxy group or a reactive derivative thereof (such as a carboxyiic acid chloride or carboxyiic ester), or a cyano group, with an appropriate organometallic reagent such as a Grignard reagent or an organolithium reagent.
  • the reaction is generally carried out in an inert solvent such as ether or tetrahydrofuran at a temperature from 0°C to the reflux temperature ofthe mixture.
  • X and n are as defined above, may be prepared by the reaction of a compound of formula (IV):
  • R 1 , R 2 , R 3 , X and n are as hereinbefore defined and P 1 is a leaving group such as N,N-dialkylamino, with a compound of formula wherein R 4 is as hereinbefore defined and Z 1 is a halogen atom. Generally Z 1 is chlorine or bromine.
  • the reaction is generally performed in an inert solvent such as toluene or dichloromethane either in the presence of a base such as triethylamine or a catalyst such as a 4 Angstrom molecular sieve or fluoride ion.
  • Compounds of formula (IV) are novel and therefore constitute a further feature ofthe invention.
  • compounds of formula (Ia) in which R represents a group -CO2R 4 and R 1 , R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of formula (V):
  • compounds of formula (Ia) or (lb) wherein R represents -CO2R 4 and R 1 , R 2 , R 3 , X and n are as defined above, may be prepared by the reaction of a salt of a compound of formula (VI):
  • Preferred salts include sodium or magnesium salts.
  • the reaction is generally performed in an inert solvent such as dichloromethane or acetonitrile at a temperature between room temperature and the reflux temperature ofthe mixture.
  • the salt of a compound of formula (VI) is generally prepared in-situ by treating the compound of formula (VI) with a base.
  • suitable bases include alkaline earth metal alkoxides such as magnesium methoxide
  • compounds of general formula (lb) in which R represents a -CO2R 4 group and R , R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of general formula (X):
  • R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of general formula (XI):
  • compounds of formula (Ia) and (lb) wherein R, R 1 , R 2 , R 3 , R 4 , X and n are as defined above, may be prepared by the reaction of a compound of formula (XII) and (XIII) respectively:
  • a radical initiator e.g. benzoyl peroxide with irradiation by light from a Tungsten lamp at a temperature from ambient to the reflux temperature.
  • compounds of formula (Ia) and (lb) in which R, R 1 , R 2 , R 3 and n are as defined above, X represents -C(R 13a R 14a )-C(R 15 R 16 )- and R 13a , R 14a , R 15 and R 1 ⁇ are as defined above may be prepared by the reaction of the corresponding compound of formula (XII) or (XIII) wherein X represents -C(R 13a )(R 14a )- and Z 1 is as defined above, preferably bromine or chlorine, with a compound of formula HC(R 1 R 1 ( >)R 3 .
  • the reaction is generally performed in the presence of a base e.g. sodium hydride and in an inert solvent e.g. N,N-dimethylformamide at a temperature from 0°C to 100°C.
  • compounds of formula (Ia) or (lb) in which R, R 1 , R 2 , R 3 and n are as defined above, and X represents -C(R 13 )(CN)- may be prepared by the reaction ofthe corresponding compound of formula (Ia) or (lb) in which X is -
  • an alkali metal cyanide preferably sodium cyanide or potassium cyanide
  • an inert solvent e.g. dimethylsulfoxide at a temperature from 10°C to 100°C.
  • the halogen is bromine or chlorine.
  • compounds of formula (Ia) or (lb) in which R, R 1 , R 2 , R 3 , R 12 , R 13 and n are as defined above, and X represents -C(R 13 )(ORl )- may be prepared by the reaction ofthe corresponding compound of formula (Ia) or (lb) in which X is -C(R 1 )(halogen)-, with a compound of formula R 12 OM where M represents hydrogen or an alkali metal (e.g. sodium, potassium or lithium).
  • the halogen is bromine or chlorine.
  • the reaction is generally performed in an inert solvent e.g.
  • compounds of formula (Ia) or (lb) in which R, R 1 , R 2 , R 3 , R 12 , R 13 and n are as defined above, and X represents -C(R 13 )(SR 12 )- may be prepared by the reaction of the corresponding compound of formula (Ia) or (lb) wherein X is -C(R 13 )(halogen)-, by the same procedure as used for the compounds above wherein X represents -C(R 13 )(OR 12 )-, by replacing the compound R 12 OM by a compound R 12 SM.
  • compounds of formula (Ic) may be prepared from the co ⁇ esponding compound of formula (Ia) or (lb) in which R is as defined above, or in which R is replaced by an amide or nitrile.
  • R represents a hydrogen atom
  • the reaction is preferably carried out by treatment with a base.
  • suitable bases include alkali or alkaline earth metal hydroxides, alkoxides such as sodium ethoxide or organic bases such as triethylamine.
  • R represents -CO2R 4 , or where R is replaced by amide or nitrile
  • the conversion is generally carried out by a hydrolytic reaction.
  • the hydrolytic reaction may be performed in the presence of an acid or base.
  • Acidic hydrolysis may be achieved for example using aqueous hydrochloric acid.
  • Basic hydrolysis may be achieved for example using sodium hydroxide in a mixture of alcohol and water. The reactions are preferably carried out at a temperature between room temperature and the reflux temperature of the mixture.
  • compounds of formula (Ic) in which R 1 , R 2 , R 3 , X and n are as defined above may also be prepared by the reaction of a benzoyl chloride of formula (XIV):
  • compounds of formula (Ic) in which R 1 , R 2 , R 3 , X and n are as defined above may also be prepared by the reaction of an acid chloride of formula R ⁇ OCl wherein R 1 is as hereinbefore defined, with a beta-ketonitrile of formula (XVI):
  • compounds of formula (Ic) in which R 1 , R 2 , R 3 , X and n are as defined above may also be prepared by the reaction of a benzoyl chloride of formula (XTV) above wherein R 2 , R 3 , X and n are as hereinbefore defined, with a beta- ketonitrile of formula (XV) wherein R 1 is as hereinbefore defined, via an intermediate of fo
  • R 1 , R 2 , R 3 , X and n are as hereinbefore defined.
  • the formation ofthe intermediate of formula (XVII) may be carried out in the presence of a mild base such as an organic base e.g. triethylamine, in an inert solvent such as acetonitrile or dichloromethane at a temperature between room temperature and the reflux temperature ofthe mixture.
  • a mild base such as an organic base e.g. triethylamine
  • an inert solvent such as acetonitrile or dichloromethane
  • the rearrangement ofthe intermediate of formula (XVII) to a compound of formula (Ic) is generally carried out in situ in an inert solvent such as acetonitrile or dichloromethane in the presence of a catalyst such as a source of cyanide.
  • a catalyst such as a source of cyanide.
  • sources of cyanide are acetone cyanohydrin or an alkali metal cyanide such as potassium cyanide, optionally in the presence of a crown ether such as 18-crown-6.
  • compounds of formula (Ic) in which R 1 , R 2 , R 3 , X and n are as defined above, may be prepared by the reaction of an acid chloride of formula R COCl wherein R is as hereinbefore defined, with a beta-ketonitrile of formula
  • Compounds of formula (lla) may be prepared by the reaction of compounds of formula (VI) with either a trialkyl orthoformate such as triethyl orthoformate or a dimethylformamide dialkyl acetal such as dimethylformamide dimethyl acetal.
  • a trialkyl orthoformate such as triethyl orthoformate
  • a dimethylformamide dialkyl acetal such as dimethylformamide dimethyl acetal.
  • reaction with a trialkyl orthoformate can be carried out in the presence of acetic anhydride at the reflux temperature ofthe mixture and the reaction with dialkylformamide dialkyl acetal is carried out optionally in the presence of an inert solvent at a temperature from room temperature to the reflux temperature ofthe mixture.
  • R 1 C(P 1 ) CH 2 (XIX)
  • RiC ⁇ CH (XX) followed by reaction ofthe metal salt thus obtained with a benzoyl chloride of formula (XIV).
  • the metallation is generally performed using n-butyl lithium in an inert solvent such as ether or tetrahydrofuran at a temperature from -78°C to 0°C.
  • the subsequent reaction with the benzoyl chloride is carried out in the same solvent at a temperature between -78°C and room temperature.
  • R 1 -C(O)-CH 3 (XXIV) wherein R 1 is as hereinbefore defined.
  • the reaction is generally performed in a solvent such as ether, tetrahydrofuran or N,N- dimethylformamide, in the presence of a base, preferably an alkali metal • base such as sodium hydride, at a temperature from 0°C to the reflux temperature.
  • a base preferably an alkali metal • base such as sodium hydride
  • R 1 , R 2 , R 13 , R 14 , Z 1 and n are defined above, may be prepared by the reaction ofthe corresponding compound of formula (XII) or (XIII) wherein Z 1 is replaced by a hydrogen atom, with a halogenating agent e.g. N-bromosuccinimide or N-chlorosuccinimide, in an inert solvent preferably carbon tetrachloride and in the presence of a radical initiator e.g. benzoyl peroxide, with irradiation by light from a tungsten lamp at a temperature from ambient to the reflux temperature.
  • a halogenating agent e.g. N-bromosuccinimide or N-chlorosuccinimide
  • an inert solvent preferably carbon tetrachloride
  • a radical initiator e.g. benzoyl peroxide
  • Acid chlorides of formula (XIV) may be prepared by the reaction of a benzoic acid of formula (XXV):
  • XXV thionyl chloride
  • benzoyl chlorides may also be prepared by reaction ofthe benzoic acid with oxalyl chloride in a solvent such as 1,2-dichloroethane at from ambient to reflux temperature.
  • Esters of formula (XXOT) may be prepared from acids of formula (XXV) according to known methods.
  • Compounds of general fo ⁇ nula may be prepared by metallation of compounds of general formula (VII) wherein A represents bromine or iodine with for example n-butyllithium in an inert solvent such as ether or tetrahydrofuran at a temperature from -78 °C to 0°C, followed by reaction with an aldehyde of general formula R 1 CHO.
  • Compounds of general formula (IX) wherein D 1 is -CO 2 -alkyl or -CN may be prepared by the reaction of compounds of general formula
  • G 1 represents CO2-alkyl or -CN and L is as hereinbefore defined, with a salt of hydroxylamine such as hydroxylamine hydrochloride, in a solvent such as ethanol or acetonitrile, optionally in the presence of a base or acid acceptor such as triethylamine or sodium acetate.
  • a salt of hydroxylamine such as hydroxylamine hydrochloride
  • a solvent such as ethanol or acetonitrile
  • XXVI Compounds of general formula (XXVI) may be prepared by the reaction of a ketonitrile of formula (XVT) or a ketoester of formula
  • Beta-ketonitriles of formula (XV) may be prepared from acid chlorides of formula R ⁇ OCl by a number of methods well known in the chemical literature. For example, see Krauss, et al, Synthesis, 1983, 308, or Muth, et al, J. Org. Chem, 1960, 25, 736.
  • beta- ketonitriles of fo ⁇ nula (XV) may be prepared by the reaction of an ester of formula R 1 -CO2Et, wherein R 1 is as hereinbefore defined, with acetonitrile. This reaction is described in the literature, for example see the article by Abramovitch and Hauser, J.Am. Chem. Soc, 1942, 64,
  • Beta-ketonitriles of formula (XVI) may be prepared from benzoyl chlorides of formula (XIV) or from co ⁇ esponding ethyl benzoates in a manner analogous to the preparation of beta-ketonitriles of formula (XV) set forth above.
  • Benzoic acids of formula (XXV) or esters of formula (XXIII) in which R 2 , R 3 , R 1 , X and n are as defined above may be prepared by the reaction ofthe co ⁇ esponding compound of formula (XXV) or (XXIII) in which R 3 is replaced by a Z 1 (Z 1 preferably being bromine or chlorine), with a compound of formula R 3 -H using the same procedure as described above for the preparation of compounds of formula (Ia) and (lb) from compounds of formula (XII) and (XIII).
  • compounds in which p and q is one or two may be prepared by the oxidation of the sulphur atom ofthe corresponding compounds in which p is 0 or 1.
  • the oxidation ofthe sulphur atom is generally carried out using for example 3-chloroperoxybenzoic acid in an inert solvent such as dichloromethane at a temperature from -40°C to room temperature.
  • 262 1 20-1 40(4H,m), 2 73(lH,m), 5 58(lH,s), 7 33(lH,d), 7 44(lH,d), 7 92(lH,s), 8.22(lH,s), 8.25(lH,s)
  • 329 1 24(2H,m), 1.27(9H,s), 1.35(2H,m), 2 63(3H,s), 2 64(lH,m), 5 43(2H,s), 7 27(lH,d), 7 37(lH,d), 7 53(lH,dd), 8 23(lH,s)
  • 331 1.10-1 40(7H,m), 2.19-2.35(lH,m), 2.57(3H,s), 4 19(2H,q), 5 61(2H,s), 7 55(lH,d), 7 64(lH,d), 7 70(lH,s), 8 24(lH,s)
  • N,N-Dimethylformamide was added to the residue and this solution added dropwise at room temperature to a solution of 1,2,4-triazole (0.23g) and sodium hydride (60% in mineral oil, 0.13 g) in N,N-dimethylformamide.
  • the reaction mixture was stirred at ambient temperature, water was added, and the mixture was extracted with ethyl acetate. The extract was washed with brine, dried over anhydrous MgSO and evaporated.
  • Dimethylformamide dimethyl acetal (2.4ml) was added to a solution of 3 -cyclopropyl- 1 -[4-methylthio-2-( 1 -pyrazolylmethyI)phenyl]- propan-l,3-dione in toluene at room temperature. The mixture was refluxed for 2 hours, evaporated and redissolved in ethanol.
  • Example 1 the following compounds were prepared from the appropriately substituted starting materials: ethyl 5-cyclopropyl-4-[3,4-dichloro-2-(3-methylthio-l,2,4-triazol- l-ylmethyl)benzoyl]isoxazole-3 -carboxylate (Compound 362), ethyl 4-[4-bromo-2-(5-methylthio- 1 ,2,4-triazol- 1 - ylmethyl)benzoyl]-5-cyclopropylisoxazole-3-carboxylate (Compound 363), ethyl 4-[4-bromo-2-(3-tert-butyI-5-methylthio- 1 ,2,4-triazol- 1 - y lmethyl)benzoyl] - 5 -cyclopropylisoxazole-3 -carboxylate (Compound 364), ethyl 4-[4-bromo-2-(5-cyclopropy
  • Example 7 A solution of dimethylformamide dimethyl acetal ( 1.22ml) and 1 -
  • Oxalyl chloride (2 ml) was added to 2-methyl-4- trifluoromethylbenzoic acid (2g) sti ⁇ ed in dichloromethane. The mixture was heated at reflux for 4 hours and evaporated. Toluene was added and the solution re-evaporated to give the co ⁇ esponding benzoyl chloride. A suspension of magnesium (0.24 g) in methanol was stirred and heated at reflux for 0.5 hours. t-Butyl 3-cyclopropyl-3-oxopropionate (1.8 g) was added and the mixture was heated at reflux for 0.5 hours. The mixture was cooled and evaporated. Toluene was added and the mixture re- evaporated.
  • N-Bromosuccinimide (3.85g) and a catalytic amount of azobisisobutyronitrile was added to a stirred solution of methyl 2-ethyl- 4-bromobenzoate (5g) in tetrachloromethane.
  • the solution was heated under reflux whilst exposed to a 300W light bulb placed 5-6 cm from the flask for 2 hours.
  • the mixture was cooled to 0°C, filtered and the filtrate evaporated to dryness.
  • a solution of 1 ,2,4-triazole (1 55g) in dimethylformamide was added dropwise to a suspension of sodium hydride (60% in mineral oil) in dimethylformamide.
  • 1-Iodopropane (1ml) was added to a sti ⁇ ed mixture of magnesium turnings (8.24g) in dry ether under nitrogen, and then heated to reflux. A solution of 1-iodopropane (31ml) in dry ether was added dropwise at such a rate as to maintain reflux. After an additional 1 hour at reflux the cooled mixture was added via a canula to a sti ⁇ ed solution of 2-(4- bromo-2-fluorophenyl)-4,4-dimethyloxazoline (25g) in dry ether at below 25°C The resultant mixture was stirred at reflux for 18 hours, cooled and poured into ice and 2M hydrochloric acid.
  • Methyl benzoates were prepared by reaction ofthe co ⁇ esponding benzoic acid derivatives with methanol by heating under reflux conditions in the presence of a strong acid (concentrated sulphuric acid).
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • the isoxazole or 2-cyano- l,3-dione derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions), for example as hereinafter described.
  • the compounds of formula (I) show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (i.e. grass) weeds by pre- and/or post-emergence application.
  • pre-emergence application application to the soil in which the weed seeds or seedlings are present before emergence ofthe weeds above the surface ofthe soil.
  • post- emergence application application to the aerial or exposed portions of the weeds which have emerged above the surface ofthe soil.
  • the compounds of formula (I) may be used to control the growth of: broad-leafed weeds, for example, Abutilon theophrasti.
  • the amounts of compounds of formula (I) applied vary with the nature ofthe weeds, the compositions used, the time of application, the climatic and edaphic conditions and (when used to control the growth of weeds in crop-growing areas) the nature ofthe crops.
  • the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop. In general, taking these factors into account, application rates between 0.01kg and 5kg of active material per hectare give good results.
  • the compounds of formula (I) may be used to control selectively the growth of weeds, for example to control the growth of those species hereinbefore mentioned, by pre- or post-emergence application in a directional or non-directional fashion, e.g by directional or non-directional spraying, to a locus of weed infestation which is an area used, or to be used, for growing crops, for example cereals, e.g wheat, barley, oats, maize and rice, soya beans, field and dwarf beans, peas, lucerne, cotton, peanuts, flax, onions, ca ⁇ ots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown grassland before or after sowing of the crop or before or after emergence ofthe crop.
  • application rates between 0.01kg and 4.0kg, and preferably between 0.01kg and 4.0kg, and preferably between 0.01kg and 4.0kg, and preferably between 0.01kg and 4.0kg, and preferably between 0.01kg and 4.0kg, and
  • the compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, by pre- or post- emergence application in established orchards and other tree-growing areas, for example forests, woods and parks, and plantations, e.g. sugar cane, oil palm and rubber plantations.
  • plantations e.g. sugar cane, oil palm and rubber plantations.
  • they may be applied in a directional or non- directional fashion (e.g. by directional or non-directional spraying) to the weeds or to the soil in which they are expected to appear, before or after planting ofthe trees or plantations at application rates between 0.25kg and 5.0kg, and preferably between
  • the compounds of formula (I) may also be used to control the growth of weeds, especially those indicated above, at loci which are not crop-growing areas but in which the control of weeds is nevertheless desirable.
  • non-crop-growing areas include airfields, industrial sites, railways, roadside verges, the verges of rivers, irrigation and other waterways, scrublands and fallow or uncultivated land, in particular where it is desired to control the growth of weeds in order to reduce fire risks.
  • the active compounds When used for such purposes in which a total herbicidal effect is frequently desired, the active compounds are normally applied at dosage rates higher than those used in crop-growing areas as hereinbefore described. The precise dosage will depend upon the nature of the vegetation treated and the effect sought.
  • Pre- or post-emergence application, and preferably pre-emergence application, in a directional or non-directional fashion (e.g. by directional or non-directional spraying) at application rates between 1 Okg and 20.0kg, and preferably between 5.0 and 10. Okg, of active material per hectare are particularly suitable for this purpose.
  • the compounds of formula (I) When used to control the growth of weeds by pre-emergence application, the compounds of formula (I) may be incorporated into the soil in which the weeds are expected to emerge. It will be appreciated that when the compounds of formula (I) are used to control the growth of weeds by post-emergence application, i.e. by application to the aerial or exposed portions of emerged weeds, the compounds of formula (I) will also normally come into contact with the soil and may also then exercise a pre-emergence control on later-germinating weeds in the soil.
  • compositions suitable for herbicidal use comprising one or more ofthe isoxazole or 2-cyano-l,3-dione derivatives of formula (I), in association with, and preferably homogeneously dispersed in, one or more compatible agriculturally- acceptable diluents or carriers and/or surface active agents [i.e. diluents or carriers and/or surface active agents ofthe type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula (I)].
  • compositions in which the compounds of formula (I) are dissolved in other components.
  • herbicide compositions is used in a broad sense to include not only compositions which are ready for use as herbicides but also concentrates which must be diluted before use.
  • the compositions contain from 0.05 to 90% by weight of one or more compounds of formula (I).
  • the herbicidal compositions may contain both a diluent or carrier and surface-active (e.g. wetting, dispersing, or emulsifying) agent.
  • Surface-active agents which may be present in herbicidal compositions of the present invention may be ofthe ionic or non-ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaryl phenols, e.g.
  • nonyl- or octyl-phenols or carboxyiic acid esters of anhydrosorbitols which have been rendered soluble by etherification ofthe free hydroxy groups by condensation with ethylene oxide, alkali and alkaline earth metal salts of sulphuric acid esters and sulphonic acids such as dinonyl- and dioctyl-sodium sulphonosuccinates and alkali and alkaline earth metal salts of high molecular weight sulphonic acid derivatives such as sodium and calcium lignosulphonates and sodium and calcium alkylbenzene sulphonates.
  • the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g. from 0.05% to 10% by weight, of surface-active agent but, if desired, herbicidal compositions according to the present invention may comprise higher proportions of surface-active agent, for example up to 15% by weight in liquid emulsifiable suspension concentrates and up to 25% by weight in liquid water soluble concentrates.
  • suitable solid diluents or carriers are aluminium silicate, talc, calcined magnesia, kieselguhr, tricalcium phosphate, powdered cork, absorbent carbon black and clays such as kaolin and bentonite.
  • the solid compositions (which may take the form of dusts, granules or wettable powders) are preferably prepared by grinding the compounds of formula (I) with solid diluents or by impregnating the solid diluents or carriers with solutions ofthe compounds of formula (I) in volatile solvents, evaporating the solvents and, if necessary, grinding the products so as to obtain powders.
  • Granular formulations may be prepared by absorbing the compounds of formula (I) (dissolved in suitable solvents, which may, if desired, be volatile) onto the solid diluents or carriers in granular form and, if desired, evaporating the solvents, or by granulating compositions in powder form obtained as described above.
  • Solid herbicidal compositions, particularly wettable powders and granules may contain wetting or dispersing agents (for example ofthe types described above), which may also, when solid, serve as diluents or carriers.
  • Liquid compositions according to the invention may take the form of aqueous, organic or aqueous-organic solutions, suspensions and emulsions which may incorporate a surface-active agent.
  • Suitable liquid diluents for incorporation in the liquid compositions include water, glycols, tetrahydrofurfuryl alcohol, acetophenone, cyclohexanone, isophorone, toluene, xylene, mineral, animal and vegetable oils and light aromatic and naphthenic fractions of petroleum (and mixtures ofthese diluents).
  • Surface-active agents which may be present in the liquid compositions, may be ionic or non-ionic (for example of the types described above) and may, when liquid, also serve as diluents or carriers Powders, dispersible granules and liquid compositions in the form of concentrates may be diluted with water or other suitable diluents, for example mineral or vegetable oils, particularly in the case of liquid concentrates in which the diluent or carrier is an oil, to give compositions ready for use. Liquid concentrates in which the diluent or carrier is an oil may be used without further dilution using the electrostatic spray technique.
  • Herbicidal compositions according to the present invention may also contain, if desired, conventional adjuvants such as adhesives, protective colloids, thickeners, penetrating agents, spreading agents, stabilisers, sequestering agents, anti-caking agents, colouring agents and co ⁇ osion inhibitors. These adjuvants may also serve as carriers or diluents. Unless otherwise specified, the following percentages are by weight.
  • Preferred herbicidal compositions according to the present invention are aqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of formula I, from 2 to 10% of surface-active agent, from 0.1 to 5% of thickener and from 15 to 87.9% of water; wettable powders which comprise from 10 to 90% of one or more compounds of formula I, from 2 to 10% of surface-active agent and from
  • solid diluent or carrier water dispersible granules which comprise from 1 to 75%, e.g. 50 to 75%, of one or more compounds of formula (I), from 2 to 10% of surface-active agent and from 1 to 20%, e.g. 5-15%, of water soluble binder; liquid emulsifiable suspension concentrates which comprise from 10 to 70% of one or more compounds of formula I, from 5 to 15% of surface-active agent, from 0.1 to 5% of thickener and from 10 to 84.9% of organic solvent, e.g. mineral oil; granules which comprise from 1 to 90%, e.g. 2 to 10% of one or more compounds of formula (I), from 0.5 to 7%, e.g.
  • granular carrier and emulsifiable concentrates which comprise 0 05 to 90%, and preferably from 1 to 60% of one or more compounds of formula (I), from 0 01 to 10%, and preferably from 1 to 10%, of surface-active agent and from 9 99 to 99 94%, and preferably from 39 to 98 99%, of organic solvent
  • Herbicidal compositions according to the present invention may also comprise the compounds of formula I in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
  • synthetic pyrethroids e.g permethrin and cypermethrin
  • fungicides e.g. carbamates, e.g. methyl N-(l -butyl-carbamoyl- benzimid-izol-2-yl)carbamate, and triazoles e.g. 1 -(4-chloro-phenoxy)- 3,3-dimethyl- 1 -( 1 ,2,4-triazol- 1 -yl)-butan-2-one.
  • Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions ofthe present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilised in the form of conventional derivatives, for example alkali metal and amine salts and esters.
  • an article of manufacture comprising at least one ofthe isoxazole or 2-cyano- 1,3 -dione derivatives of formula (I) or, as is preferred, a herbicidal composition as hereinbefore described, and preferably a herbicidal concentrate which must be diluted before use, comprising at least one of the isoxazole or 2-cyano- 1,3 -dione derivatives of formula (I) within a container for the aforesaid derivative or derivatives of formula I, or a said herbicidal composition, and instructions physically associated with the aforesaid container setting out the manner in which the aforesaid derivative or derivatives of formula I or herbicidal composition contained therein is to be used to control the growth of weeds.
  • the containers will normally be ofthe types conventionally used for the storage of chemical substances which are solid at normal ambient temperatures and herbicidal compositions particularly in the form of concentrates, for example cans and drums of metal, which may be internally lacquered, and plastics materials, bottles or glass and plastics materials and, when the contents ofthe container is a solid, for example granular, herbicidal compositions, boxes, for example of cardboard, plastics materials and metal, or sacks.
  • the containers will normally be of sufficient capacity to contain amounts of the isoxazole or 2-cyano- 1,3 -dione derivative or herbicidal compositions sufficient to treat at least one acre of ground to control the growth of weeds therein but will not exceed a size which is convenient for conventional methods of handling.
  • the instructions will be physically associated with the container, for example by being printed directly thereon or on a label or tag affixed thereto.
  • the directions will normally indicate that the contents ofthe container, after dilution if necessary, are to be applied to control the growth of weeds at rates of application between 0.1kg and 20kg of active material per hectare in the manner and for the purposes hereinbefore described.
  • An emulsifiable concentrate is formed from: Active ingredient (Compound 1) 20% w/v
  • NMP N-Methylpyrrolidone 25% w/v Calcium dodecylbenzenesulphonate 70%
  • Nonylphenol ethylene oxide propylene oxide condensate (Synperonic NPE 1800) 6% w/v Aromatic solvent (Solvesso) to 100 volumes by stirring NMP, active ingredient (Compound 1), CaDDBS,
  • Example C2 A wettable powder is formed from:
  • Active ingredient 50% w/w Sodium dodecylbenzenesulphonate
  • Microfine silicon dioxide (Tixosil 38) 3% w/w
  • a suspension concentrate is formed from:
  • Attaclay 1.5% w/v Antifoa (Rhodorsil AF426R) 0.003% w/v
  • a water dispersible granule is formed from: Active ingredient (Compound 1) 50% w/w
  • Binder (Sodium lignosulphonate) 8% w/w
  • Microfine silicon dioxide (Tixosil 38) 3% w/w by blending the above ingredients together, grinding the mixture in an air jet mill and granulating by addition of water in a suitable granulation plant (e.g. Fluid bed drier) and drying.
  • a suitable granulation plant e.g. Fluid bed drier
  • the active ingredient may be ground either on its own or admixed with some or all ofthe other ingredients.
  • the compounds ofthe invention have been used in herbicidal applications according to the following procedures.
  • the seeds were sown in 70 mm square, 75 mm deep plastic pots in non-sterile soil .
  • the quantities of seed per pot were as follows:- Weed species Approx number of seeds/pot
  • the compounds used to treat the plants were applied to the plants as described in (a). A single pot of each crop and weed species was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
  • Paddy field soil was filled in 170 cm 2 plastic pots, a suitable amount of water and chemical fertilisers were added thereto and kneaded to convert it to a state of a paddy.
  • Paddy rice plants variety; Koshihikari
  • that had been grown in advance in a greenhouse to a stage of two leaves were transplanted to each pot (two seedlings per pot). Then in each pot there were sown predetermined amounts of seeds of Echinochloa orvzicola.
  • Monochoria vaginalis Lindernia procumbens and Scirpus iuncoides respectively, and water was added to a depth of 3 cm.
  • solutions were prepared in 1'00% acetone using compounds described in the Examples so that they contained active ingredients in an amount equivalent to 75, 300 and 1200 g/ha.
  • the solutions were applied by dropping with a pipette.

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Abstract

L'invention concerne un dérivé de 4-benzoylisoxazole présentant la formule (Ia), un dérivé de 5-phénylisoxazole présentant la formule (Ib) ou un dérivé de 2-cyano-1,3-dione ayant la formule (Ic). Dans ces formules R?1, R2, R3¿, X et n sont tels que définis dans le descriptif. L'invention traite de l'utilisation de ces dérivés comme désherbants.
PCT/EP1997/000258 1996-01-26 1997-01-21 Derives de l'isoxazole et de 2-cyano-1,3-diones et leur utilisation comme desherbants WO1997027187A1 (fr)

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AU15934/97A AU1593497A (en) 1996-01-26 1997-01-21 Isoxazole and 2-cyano-1,3-diones derivatives and their use as herbicides

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GBGB9601575.5A GB9601575D0 (en) 1996-01-26 1996-01-26 New herbicides
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GBGB9626435.3A GB9626435D0 (en) 1996-12-23 1996-12-23 New herbicides

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000068204A1 (fr) * 1999-05-08 2000-11-16 Bayer Aktiengesellschaft Cetones de benzoyle substituees, leur procede de preparation et leur utilisation comme herbicides
WO2000068227A1 (fr) * 1999-05-06 2000-11-16 Bayer Aktiengesellschaft Benzoylisoxazoles substitues et leur utilisation comme herbicides
US6262051B1 (en) * 1997-04-03 2001-07-17 Bayer Aktiengesellschaft Fungicidal methoximinomethyldioxazines
WO2001053275A2 (fr) * 2000-01-17 2001-07-26 Bayer Aktiengesellschaft Arylcetones substituees
WO2002010155A1 (fr) * 2000-07-29 2002-02-07 Bayer Cropscience Ag Arylcetones substituees et leur utilisation en tant qu'herbicides
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US7112554B2 (en) 2001-05-09 2006-09-26 Bayer Cropscience Ag Substituted arylketones
US7153813B2 (en) 2002-02-19 2006-12-26 Bayer Aktiengesellschaft Substituted aryl ketones
US7807703B2 (en) 2002-03-05 2010-10-05 Bayer Cropscience Ag Substituted aryl ketones
JP2013516392A (ja) * 2009-12-30 2013-05-13 ザンナン・サイテック・カンパニー・リミテッド Ｒｏｍｐとｒｃｍ反応に対する高効率複分解触媒
US9199975B2 (en) 2011-09-30 2015-12-01 Asana Biosciences, Llc Biaryl imidazole derivatives for regulating CYP17

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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
EP0524018A1 (fr) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0625505A2 (fr) * 1993-05-18 1994-11-23 Rhone Poulenc Agriculture Ltd. Dérivés de 2-cyano-1,3-dione et leur emploi en tant qu'herbicides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0418175A2 (fr) * 1989-09-11 1991-03-20 Rhone Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0524018A1 (fr) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0625505A2 (fr) * 1993-05-18 1994-11-23 Rhone Poulenc Agriculture Ltd. Dérivés de 2-cyano-1,3-dione et leur emploi en tant qu'herbicides

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6262051B1 (en) * 1997-04-03 2001-07-17 Bayer Aktiengesellschaft Fungicidal methoximinomethyldioxazines
WO2000068227A1 (fr) * 1999-05-06 2000-11-16 Bayer Aktiengesellschaft Benzoylisoxazoles substitues et leur utilisation comme herbicides
US6838415B1 (en) 1999-05-06 2005-01-04 Bayer Aktiengesellschaft Substituted benzoylisoxazoles and the use thereof as herbicides
WO2000068204A1 (fr) * 1999-05-08 2000-11-16 Bayer Aktiengesellschaft Cetones de benzoyle substituees, leur procede de preparation et leur utilisation comme herbicides
US6762152B1 (en) 1999-05-08 2004-07-13 Bayer Aktiengesellschaft Substituted benzoyl ketones, methods for producing them and their use as herbicides
US6610631B1 (en) 1999-09-30 2003-08-26 Bayer Aktiengesellschaft Substituted aryl ketones
US6727206B2 (en) 1999-09-30 2004-04-27 Bayer Aktiengesellschaft Substituted aryl ketones
US6864219B2 (en) 2000-01-17 2005-03-08 Bayer Aktiengesellschaft Substituted aryl ketones
WO2001053275A2 (fr) * 2000-01-17 2001-07-26 Bayer Aktiengesellschaft Arylcetones substituees
WO2001053275A3 (fr) * 2000-01-17 2003-04-17 Bayer Ag Arylcetones substituees
WO2002010155A1 (fr) * 2000-07-29 2002-02-07 Bayer Cropscience Ag Arylcetones substituees et leur utilisation en tant qu'herbicides
US7112554B2 (en) 2001-05-09 2006-09-26 Bayer Cropscience Ag Substituted arylketones
US7456133B2 (en) 2001-05-09 2008-11-25 Bayer Cropscience Ag Substituted arylketones
US7153813B2 (en) 2002-02-19 2006-12-26 Bayer Aktiengesellschaft Substituted aryl ketones
US7807703B2 (en) 2002-03-05 2010-10-05 Bayer Cropscience Ag Substituted aryl ketones
JP2013516392A (ja) * 2009-12-30 2013-05-13 ザンナン・サイテック・カンパニー・リミテッド Ｒｏｍｐとｒｃｍ反応に対する高効率複分解触媒
US9199975B2 (en) 2011-09-30 2015-12-01 Asana Biosciences, Llc Biaryl imidazole derivatives for regulating CYP17

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