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WO1997028136A1 - Benzoylisoxazoles et derives de 2-cyano-1,3-dione utilises en tant qu'herbicides - Google Patents

Benzoylisoxazoles et derives de 2-cyano-1,3-dione utilises en tant qu'herbicides Download PDF

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Publication number
WO1997028136A1
WO1997028136A1 PCT/EP1997/000330 EP9700330W WO9728136A1 WO 1997028136 A1 WO1997028136 A1 WO 1997028136A1 EP 9700330 W EP9700330 W EP 9700330W WO 9728136 A1 WO9728136 A1 WO 9728136A1
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Prior art keywords
compound
formula
benzoyl
cyclopropyl
halogen
Prior art date
Application number
PCT/EP1997/000330
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English (en)
Inventor
Atsushi Go
Sachio Kudo
Tetsuya Murata
John Morris
Claude Lambert
Masahito Itoh
Hidesi Mukaida
Neil Geach
Koichi Araki
Takako Brett
Yukiko Oe
Original Assignee
Rhone-Poulenc Agriculture Ltd.
Mitsubishi Chemical Corporation
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Publication date
Priority claimed from GBGB9601766.0A external-priority patent/GB9601766D0/en
Priority claimed from GBGB9626393.4A external-priority patent/GB9626393D0/en
Application filed by Rhone-Poulenc Agriculture Ltd., Mitsubishi Chemical Corporation filed Critical Rhone-Poulenc Agriculture Ltd.
Priority to AU15949/97A priority Critical patent/AU1594997A/en
Publication of WO1997028136A1 publication Critical patent/WO1997028136A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
    • C07C63/68—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings containing halogen
    • C07C63/72—Polycyclic acids
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C225/14—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated
    • C07C225/16—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being unsaturated and containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/24—Sulfones; Sulfoxides having sulfone or sulfoxide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/56—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/782—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic
    • C07C49/792—Ketones containing a keto group bound to a six-membered aromatic ring polycyclic containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/80—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen
    • C07C49/813—Ketones containing a keto group bound to a six-membered aromatic ring containing halogen polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • This invention relates to novel 4-benzoylisoxazole derivatives, 5-phenyiisoxazole derivatives and 2-cyano- 1,3 -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 of the above publications disclose or suggest the presence of a benzene ring linked to a hydrocarbon group as a substituent on the phenyl ring.
  • the present invention provides 4-be ⁇ zoylisoxazole derivatives of formula (Ia), 5-phenyIisoxazole derivatives of formula (Ib) and 2-cyano- 1,3 -dione derivatives of formula (Ic):
  • R represents hydrogen or -CO2 ⁇
  • R.1 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 groups selected from R ⁇ and halogen;
  • R2 represents :- halogen; a straight- or branched- chain alkyl group containing up to six carbon atoms which is substituted by one or more groups -OR-'; a cycloalkyl group containing from three to six carbon atoms; or a group selected from nitro, cyano, -CO2R 5 , -NR 5 R 6 , -S(O) p R 7 ,
  • R 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 , -CO 2 R 5 , -S(O) p R 7 , phenyl and cyano; or phenyl optionally substituted by one or more halogen atoms, -OR 5 or
  • R 5 and R> which may be the same or different, each represents hydrogen or R ⁇ 2 ;
  • R 7 and R 7a independently represent R ⁇ 2 or a cycloalkyl group containing from three to six carbon atoms; or a group -(CH 2 ) w -[phenyl optionally substituted by from one to five groups R 2 ⁇ which may be the same or different]; w represents zero or one;
  • R 13 , R 15 , R l 5a , R 16 and R l6a independently represent:- hydrogen or a straight- or branched- chain alkyl, aikenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • R 14 represents R 5 , cyano, -OR 12 , -S(O)pR 12 or halogen;
  • R' 7 and R ⁇ independently represents hydrogen or R* 2 ;
  • Rl 9 represents a N-linked pyrazole, imidazole or 1,2,4-triazole ring optionally substituted by one or more groups selected from halogen and R 12 ;
  • R 2u represents :- a halogen atom; 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 nitro, cyano, -S(O) p R 21 and -OR 5 ;
  • R 21 represents a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • V represents R 12 , -OR 12 or -SR 12 ;
  • Y represents oxygen or sulphur (preferably Y represents oxygen);
  • Z represents R 12 , -NR 8 R 22 , -NR 8 -NR 22 R 23 , -SR 7 or -OR 7 ;
  • R 22 and R 23 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.
  • R 17 , R 18 , R 20 , R 21 , R 22 , R 23 , X and Z may contribute to optical isomerism and/or stereoisomerism. All such forms are embraced by the present invention.
  • 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 (e.g. 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 of the oxygen atoms of the 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.
  • SUBSTTTUTE SHEET (RULE 26)
  • 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 advantages over known compounds.
  • Compounds of formula (Ia) above are preferred.
  • Compounds in which the 2-position of phenyl is substituted are also preferred.
  • X represents -CH -.
  • 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 cyclopropyl.
  • R 2 represents :- halogen; a straight- or branched- chain alkyl or aikenyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from nitro, cyano, -S(O)pR 7 , -OR 7 and -OH.
  • n represents zero, one or two.
  • R 3 represents phenyl optionally substituted by -S(O) p R 7 or halogen.
  • 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 particularly preferred class of compounds of formula (Ia) above are those having one or more of the following properties: -
  • R represents hydrogen or -CO R 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 -S(O)pR 7 group; or when -XR 3 is attached to the 2- ⁇ osition of the phenyl ring, two groups R 2 together with the carbon atoms at the 3- and 4- positions of the phenyl ring form a 1,3-benzodioxole ring substituted by one or two chlorine or fluorine atoms at the 2-position of the 1,3-benzodioxole ring.
  • n represents zero, one or two;
  • X represents -CHR 14 -, -CHR 14 -CH 2 -, -CH 2 CHR 14 - or
  • R 4 represents a straight- or branched- chain alkyl group containing from one to three carbon atoms;
  • R 5 , R6, R 7 , R 8 and R 2 independently represent methyl or ethyl optionally substituted by one or more halogen atoms;
  • R 17 and R 1 independently represent hydrogen, or methyl or ethyl optionally substituted by one or more halogen atoms;
  • V and Z independently represent methyl, ethyl, methoxy or ethoxy, which may be substituted by one or more halogen atoms;
  • Y represents oxygen
  • Another particularly preferred class of compounds of formula (I) are those wherein: -
  • R 1 represents cyclopropyl
  • R 2 represents:- halogen; methyl or ethyl optionally substituted by one or more halogen atoms; or -S(O) j -,R 7
  • n represents zero, one or two; when present the R 2 groups are attached to the 3 and/or 4 positions of the phenyl ring
  • X represents -CHR 14 , -CH 2 -CHR 14 - or -(CH 2 )3S -XR 3 is attached to the 2-position of the phenyl ring
  • R 3 represents phenyl optionally substituted by a group selected from halogen, methyl optionally substituted by one or more halogen atoms, and -S(O) p R 7a ;
  • R 4 represents methyl or ethyl
  • R 7 represents methyl or ethyl which is optionally substituted by one or more halogen atoms
  • R 7a represents a straight- or branched- chain alkyl group containing from one to three carbon atoms optionally substituted by one or more halogen atoms;
  • R 14 represents hydrogen, methyl or -S(O) p CH3.
  • Another particularly preferred class of compounds of formula (I) are those wherein: -
  • R 1 represents cyclopropyl, 1-methylcyclopropyl or t-butyl
  • R 2 represents :- halogen; methyl or ethyl optionally substituted by one or more halogen atoms; or -S(O)pR 7
  • n represents zero, one or two; when present the R 2 groups being attached to the 3, 4 or 5 -positions of the phenyl ring
  • X represents -CHR 14 -, -CH 2 -CHR 14 - or -(CH ) 3 -;
  • -XR 3 is attached to the 2 or 3 -position of the phenyl ring;
  • R 3 represents phenyl optionally substituted by one to three groups selected from halogen, methyl optionally substituted by one or more halogen atoms, -S(O) p R 7a , -CH 2 S(O)pR 7 , -CH 2 OR 12 and -OR 7 ; or two of the above groups together with adjacent carbon atoms of the 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 of the 1,3-benzodioxole ring;
  • R 4 represents methyl, ethyl or isopropyl;
  • R 7 represents methyl or ethyl which is optionally substituted by one or more halogen atoms;
  • R 7a represents a straight- or branched- chain alkyl group containing from one to three carbon atoms optionally substituted by one or more halogen atoms;
  • R 2 represents optionally halogenated methyl;
  • R 14 represents hydrogen, methyl or -S(O) p CH3-
  • 251 5-cyclopropyl-4-[2-(2-methylsulphonyl-4- trifluoromethoxybenzyl)benzoyl]isoxazole; 252 4-[2-(2-chloro-4-methylsulphinylbenzyl)benzoyl]-5- cyclopropylisoxazole;
  • 253 4-[2-(2-chloro-4-methylsulphonylbenzyl)benzoyl]-5- cyclopropylisoxazole; 254 5-cyclopropyl-4-[2-(2-fluoro-6- methylsulphinylbenzyl)benzoyl]isoxazole;
  • 268 iso-propyl 5-cyclopropyl-4-[2-(2- methylsulphinylbenzyl)benzoyl]isoxazole-3-carboxylate
  • 269 iso-propyl 5-cyclopropyl-4-[2-(2- methylsulphonylbenzyl)benzoyl]isoxazole-3-carboxylate
  • 270 4-[2-(2-methylsulphinylbenzyl)benzoyl]-5-( 1 - methylcyclopropyl)isoxazole
  • 271 4-[2-(2-raethylsulphonylbenzyl)benzoyl]-5-( 1 - methylcyclopropyl)isoxazole;
  • Me means methyl
  • Pr means propyl
  • cPr means cyclopropyl
  • Ph means phenyl
  • Et means ethyl.
  • subscripts do not appear in the Table it is understood that in appropriate cases they are present (for example 'CF3' is understood to mean '-CF3'; 'SO2Me' means '-SO 2 CH 3 ' etc.).
  • 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 of the 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 of the 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 carboxylic acid chloride or carboxylic 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 of the mixture.
  • compounds of formula (Ia) wherein R represents a group -CO 2 R ⁇ 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 (IV):
  • R O 2 CC(Z 1 ) NOH 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 (Ia) in which R represents a group -CO 2 R 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 (N):
  • reaction is generally performed in an inert solvent such as toluene or dichloromethane optionally in the presence of a base such as triethylamine or a catalyst such as a 4 Angstrom molecular sieve or fluoride ion.
  • a base such as triethylamine or a catalyst such as a 4 Angstrom molecular sieve or fluoride ion.
  • the reaction is preferably carried out at a temperature between room temperature and the reflux temperature of the mixture.
  • compounds of formula (Ia) or (Ib) wherein R represents -CO 2 R 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 compounds of formula (NI):
  • 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 of the mixture.
  • the salt of a compound of formula (VI) is generally prepared in situ by treating the compound of formula (VI) with a base. Examples of suitable bases include alkaline earth metal alkoxides such as magnesium methoxide.
  • compounds of formula (Ib) in which R, R 1 , R 2 , R 3 ,X and n are as defined above may be prepared by the metallation of a compound of formula (VE): wherein A is a halogen atom, followed by reaction of the compound thus obtained with an acid chloride of formula R ⁇ OCl.
  • A is bromine or iodine and the reaction performed with for example n-butyllithium in an inert solvent such as ether or tetrahydrofuran at a temperature from -78°C to 0°C.
  • the reaction is generally performed using an appropriate oxidising agent, for example, a mixture prepared from chromium trioxide and aqueous sulphuric acid.
  • compounds of formula (Ib) in which R represents a -CO R 4 group 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 (X):
  • X and n are as defined above may be prepared by the reaction of a compound of formula (XI):
  • the reaction is generally performed using a halogenating agent such as N- bromosuccinimide or N-chlorosuccinimide in an inert solvent, preferably carbon tetrachloride and in the presence of a radical initiator e.g. benzoyi peroxide, with irradiation by light from a Tungsten lamp at a temperature from ambient to the reflux temperature.
  • a halogenating agent such as N- bromosuccinimide or N-chlorosuccinimide
  • an inert solvent preferably carbon tetrachloride
  • a radical initiator e.g. benzoyi peroxide
  • compounds of formula (Ia) or (Ib) in which R, R 1 , R 2 , R 3 , R 13 , R 15 , R 15 R 16 , R 1 ( > a , r, s and n are as defined above and R 14 represents cyano may be prepared by the reaction of the corresponding compound of formula (Ia) or (Ib) in which R 14 represents halogen (preferably bromine or chlorine) with an alkali metal cyanide.
  • the reaction is generally performed using sodium cyanide or potassium cyanide, in an inert solvent e.g. dimethylsulfoxide at a temperature from 10°C to 100°C.
  • compounds of formula (Ia) or (Ib) in which R, R 1 , R 2 , R 3 , R 12 , R 13 , R 15 , R 15a R 16 Rl ⁇ a ⁇ r5 s and n are as defined above, and R 14 represents -OR 12 may be prepared by the reaction of the corresponding compound of formula (Ia) or (Ib) in which R 14 represents halogen (preferably bromine or chlorine) with a compound of formula R 1 OM where M represents hydrogen or an alkali metal (e.g. sodium, potassium or lithium).
  • the reaction is generally performed in an inert solvent e.g.
  • compounds of formula (Ia) or (Ib) in which R, R 1 , R 2 , R 3 , R 12 R 13 , R 15 , R 15a R 1 ⁇ , R ⁇ a rj s and n are as defined above, and R 14 represents -SR 12 may be prepared by the reaction of the corresponding compound of formula (Ia) or (Ib) in which R 1 represents halogen (preferably bromine or chlorine) by the same procedure as used for the compounds above wherein R 14 represents an OR 12 group, by replacing the compound R 12 OM by a compound R 12 SM.
  • R 1 represents halogen (preferably bromine or chlorine)
  • compounds of formula (Ia) or (Ib) in which X represents -CR 13 R 1 -(CR 15a R 16a ) s -, and R, R 1 , R 2 , R 3 , R 12 , R 13 , R 15a , R 16a , n and p are as defined above, s represents one or two, and R 1 represents cyano, -OR 12 or -S(O) R 12 , may be prepared by the reaction of the corresponding compound (Ia) or (Ib) in which XR3 is replaced by a group -CHR 3 R 14 , with a compound of formula Z 1 -(CR 15a R 16a ) s -R 3 in which s represents one or two and Z represents halogen as defined above.
  • the reaction is generally performed in the presence of a base, e.g. sodium hydride, in an inert solvent e.g. N,N-dimethylformamide, at a temperature from
  • the reaction is generally performed using a base, e.g. sodium hydride, in an inert solvent e.g. N,N-dimethylformamide, at a temperature from 0°C to 100°C.
  • a base e.g. sodium hydride
  • an inert solvent e.g. N,N-dimethylformamide
  • compounds of formula (Ic) may be prepared from the corresponding compound of formula (Ia) or (Ib) 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 -CO 2 R 4 , or where R is replaced by amide or nitrile
  • 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 (Ia) or (Ib) in which R is replaced by amide or nitrile are novel and thus constitute a further feature of the invention.
  • 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 benzoyi chloride of formula (XTJ):
  • reaction is generally performed in the presence of a base, in a solvent or solvent mixture.
  • bases include metal hydrides, hydroxides or alkoxides (e.g. sodium or lithium hydride, sodium hydroxide, potassium hydroxide, magnesium ethoxide or magnesium methoxide).
  • Suitable solvents include for example tetrahydrofuran; hydrocarbons such as toluene; or halogenated hydrocarbons such as dichloromethane.
  • the reaction is generally performed at a temperature from 0°C to the reflux temperature.
  • a number of compounds of formula (XII) are novel and thus form a further feature of the invention.
  • 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
  • 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 benzoyi chloride of formula (XH) above wherein R 2 , R 3 , X and n are as hereinbefore defined, with a beta- ketonitrile of formula (X ⁇ l) wherein R 1 is as hereinbefore defined, via an intermediate of formula (XN):
  • the formation of the intermediate of formula (XN) 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 of the mixture.
  • a mild base such as an organic base e.g. triethylamine
  • an inert solvent such as acetonitrile or dichloromethane
  • the rearrangement of the intermediate of formula (XV) 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 ⁇ OCl wherein R 1 is as hereinbefore defined, with a beta-ketonitrile of formula
  • Compounds of formula (II) may be prepared by the reaction of compounds of formula (VI) with either a trialkyl orthoformate such as triethyl orthoformate or a dimethylformamide dialkyi acetal such as dimethylformamide dimethyl acetal.
  • a trialkyl orthoformate such as triethyl orthoformate
  • a dimethylformamide dialkyi 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 of the mixture and the reaction with dialkylformamide dialkyi acetal is carried out optionally in the presence of an inert solvent at a temperature from room temperature to the reflux temperature of the mixture.
  • R 1 C(P 1 H:H2 (XV ⁇ ) wherein R 1 and P 1 are as defined above.
  • R 2 , R 3 , X and n are as hereinbefore defined and R 2 ⁇ represents a lower alkyl group (generally of one to six carbon atoms), with a compound of formula (XXII):
  • SUBSTTTUTE SHEET (RULE 26) 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
  • Acid chlorides of formula (XH) may be prepared by the reaction of a benzoic acid of formula (XXDI):
  • a chlorinating agent for example thionyl chloride at the reflux temperature of the mixture.
  • benzoyi chlorides may also be prepared by reaction of the benzoic acid with oxalyl chloride in a solvent such as 1,2-dichloroethane at from ambient to reflux temperature.
  • Esters of formula (XXI) may be prepared from acids of formula (XXDT) by known methods.
  • Compounds of formula (VOT) may be prepared by metallation of compounds of 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 formula R CHO.
  • Compounds of formula (XXTV) may be prepared by the reaction of a beta-ketonitrile of formula (XIV) above or a ketoester of formula (XXV):
  • Beta-ketonitriles of formula (XIII) may be prepared from acid chlorides of formula R-COC1 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 formula (XIII) may be prepared by the reaction of an ester of formula R 1 -CO 2 Et, 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, 2720.
  • Beta-ketonitriles of formula (XIV) may be prepared from benzoyi chlorides of formula (XII) or from conesponding ethyl benzoates in a manner analogous to the preparation of beta-ketonitriles of formula (XIII) set forth above.
  • Benzoic acids of formula (XXIII) in which R 2 , R 3 , X and n are as defined above, and XR 3 is at the 2- position may be prepared by the reaction of the conesponding compound of formula (XXIII) in which the carboxylic acid is protected preferably as the oxazoline and R 3 is replaced by a fluorine atom, with an organometallic reagent R 3 X-M where M represents a metallic group, preferably magnesium bromide, followed by deprotection by known methods.
  • compounds of formula (I) may be prepared by the interconversion of other compounds of formula (I) and such interconversions constitute yet more features of the present invention.
  • compounds in which p or q is one or two may be prepared by the oxidation of the sulphur atom of the conesponding compounds in which p or q is 0 or 1.
  • the oxidation of the 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.
  • the reaction is generally performed in the presence of an excess of the alcohol (XXX) and a catalytic amount of a base such as R a ONa optionally in the presence of another solvent such as toluene and optionally with distillation to facilitate removal of the undesired alohol component R 4 OH, and at a temperature from 0°C to the reflux temperature.
  • compounds of formula (Ia) or (Ib) in which R, R 1 , R 2 , R 3 and n are as defined above and X represents -CHR 13 - in which R 13 is defined above may be prepared by the reaction of the conesponding compound of formula (Ia) or (Ib) in which -XR 3 is replaced by -CHR 13 -hal in which hal represents bromine or iodine, with a compound of formula (XXXI): R 3 B(OH) 2 (XXXI)
  • the reaction is generally performed in a solvent such as toluene or dimethoxyethane in the presence of a palladium catalyst such as tetrakis triphenylphosphine palladium(0) and a base for example aqueous sodium carbonate at a temperature of from 50 tol20°C.
  • Hydroxylamine hydrochloride (2.44 g) was added to a stined solution of 1 -[2-benzyl-4-(ethylthio)phenyl]-3-cyclopropyl-2- dimethylaminopropan-l,3-dione (11.5 g) in ethanol. The mixture was stirred for 2 hours, water added and the mixture extracted with dichloromethane. The extract was washed (water), dried (magnesium sulphate) and evaporated to give a gum.
  • Hydroxylamine hydrochloride (0.63g) and sodium acetate (0.75g) were added to a stined solution of l-[2-(2-chlorobenzyl)-4- fluorophenyl]-3 -cyclopropyl-2-ethoxymethylenepropan- 1 , 3 -dione (2.33g) in ethanol. After 2 hours water was added and the mixture extracted (dichloromethane), dried (magnesium sulphate) and evaporated to dryness.
  • Hydroxylamine hydrochloride (l.Og) was added to a stined mixture of 1 -[2-benzyl-3-methyl-4-(methylthio)phenyl]-3-cyclopropyl-2- ethoxymethylenepropan- 1,3 -dione (4.68g) and sodium acetate (0.9g) in ethanol. The mixture was stined overnight, diluted with water and extracted (ether). The extract was evaporated to dryness and purified by chromatography eluting with ethyl acetate/hexane to give 5-[2-benzyl-3- methyl-4-(methylthio)phenyl]-4-cyclopropylcarbonyl isoxazole
  • Example 6 A mixture of 4-(2-benzylbenzoyl)-5-cyclopropylisoxazole (5.0g) and triethylamine (1.8g) was stined in dichloromethane for 1.25 hours, then washed with hydrochloric acid (2M). The organic phase was dried (magnesium sulphate) and evaporated to dryness. The residue was dissolved in ether, washed with water, dried (magnesium sulphate) and evaporated. The residue was triturated with hexane to give l-(2- benzylphenyl)-2-cyano-3-cyclopropylpropan-l,3-dione as an orange solid (Compound 85, 0.24g), m.p. 76-77.5°C.
  • Example 7 l-Fluoro-2,4,6-trimethylpyridinium triflate(2.0g) was added to a stined solution of 5-cyclopropyl-4-[(2- methylthiobenzyl)benzoyl]isoxazole(1.0g) in dichloromethane and acetonitrile at room temparatue. The reaction mixture was refluxed for 3 hours, cooled, extracted (dichloromethane), washed (water), dried (magnesium sulfate) and evaporated.
  • Example 11 Using the procedure described in Example 4 above there was obtained from 3-cyclopropyl-l-[2-(2-methylbenzyl)phenyl]propan-l,3- dione: ethyl 5-[2-(2-methylthiobenzyl)phenyl]-4-cyclopropylcarbonyl isoxazole-3 -carboxylate (Compound 290), NMR 0.74-0.8 l(m,2H), 1.1 1- 1.18(m,2H), 1.42(3H,t), 1.8(m,lH), 2.35(s,3H), 2.42(s,3H), 4.12(s,2H), 4.47(2H,q), 6.9-7.5(m,8H).
  • a solution of 2-methylthiobenzylmagnesium bromide was prepared from 2-methylthiobenzyl bromide (1 .5g) and magnesium (1.9g) in dry ether, and added via a cannula to a solution of 2-(4-chloro-2-fluoro-3- methylthiophenyl)-4,4-dimethyl-l,3-oxazoline (9.0g) in dry ether.
  • the reaction mixture was heated under reflux overnight, cooled, and poured onto a mixture of ice and hydrochloric acid (2 M). The mixture was basified with sodium hydroxide solution (5 M) and extracted (ether).
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • a herbicidally effective amount of at least one isoxazole or 2-cyano- 1,3 -dione derivative of formula (I) or an agriculturally acceptable salt thereof is 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 of the weeds above the surface of the soil.
  • post- emergence application application to the aerial or exposed portions of the weeds which have emerged above the surface of the soil.
  • the compounds of formula (I) may be used to control the growth of: broad-leafed weeds, for example, Abutilon theophrasti. Amaranthus retroflexus. Bidens pilosa. Chenopodium album. Galium aparine. Ipomoea spp. e.g. Ipomoea purpurea. Sesbania exaltata. Sinapis arvensis. Solanum nigrum and Xanthium strumarium. and grass weeds, for example Alopecurus mvosuroides. Avena fatua. Digitaria sanguinalis. Echinochloa crus-ga li. Sorghum bicolor. Eleusine indica and Setaria spp. e.g. Setaria faberii or Setaria viridis. and sedges, for example, Cvperus esculentus.
  • broad-leafed weeds for example, Abutilon theophrasti. Amaranthus retroflexus. Bidens pilosa
  • the amounts of compounds of formula (I) appUed vary with the nature of the 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 of the C ⁇ ODS.
  • the rate of application should be sufficient to control the growth of weeds without causing substantial permanent damage to the crop.
  • application rates between 0.01kg and 5kg of active material per hectare give good results. However, it is to be understood that higher or lower application rates may be used, depending upon the particular problem of weed control encountered.
  • 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, carrots, cabbage, oilseed rape, sunflower, sugar beet, and permanent or sown grassland before or after sowing of the crop or before or after emergence of the crop.
  • cereals e.g. wheat, barley, oats, maize and rice
  • soya beans, field and dwarf beans peas, lucerne, cotton, peanuts, flax, onions, carrots, cabbage, oilseed rape,
  • 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 of the trees or plantations at application rates between 0.25kg and 5.0kg, and preferably between 0.5kg and 4.0kg of active material per hectare.
  • 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.
  • the compounds of formula (I) When used to control the growth of weeds by pre-emergence application, the compounds of formula (I) may be inco ⁇ orated 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 of the isoxazole or 2-cyano- 1 ,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 of the type generally accepted in the art as being suitable for use in herbicidal compositions and which are compatible with compounds of formula (I)].
  • the term “homogeneously dispersed” is used to include compositions in which the compounds of formula (I) are dissolved in other components.
  • herbicidal 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.
  • 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 of the 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 carboxylic acid esters of anhydrosorbitols which have been rendered soluble by etherification of the 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 of the 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 of the 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 Uquid 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 of these diluents).
  • Surface-active agents which may be present in the Uquid 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 compositions of the compound of formula (I) may be used in the form of self-emulsifying concentrates containing the active substances dissolved in the emulsifying agents or in solvents containing emulsifying agents compatible with the active substances, the simple addition of water to such concentrates producing 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, stabilisers, sequestering agents, anti-caking agents, colouring agents and conosion inhibitors. These adjuvants may also serve as carriers or diluents. Unless otherwise specified, the following percentages are by weight.
  • Prefened herbicidal compositions 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 8 to 88% of 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;
  • Uquid 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; granules which comprise from 1 to 90%o, e.g. 2 to 10% of one or more compounds of formula (I), from 0.5 to 7%, e.g. 0.5 to 2%, of surface-active agent and from 3 to 98.5%, e.g.
  • 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- benzimidazol-2-yl)carbamate
  • triazoles e.g. l-(4-chloro-phenoxy)- 3,3- dimethyl-l-(l,2,4-triazol-l-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 of the present invention, for example those hereinbefore mentioned, and which are acids, may, if desired, be utilized in the form of conventional derivatives, for example alkaU metal and amine salts and esters.
  • an article of manufacture comprising at least one of the isoxazole or 2-cyano- 1,3 -dione derivatives of formula (I) or, as is prefened, 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 of the 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 of the 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-l,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 normaUy indicate that the contents of the container, after dilution if necessary, are to be appUed to control the growth of weeds at rates of application between 0.01kg 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-Methylpynolidone 25% w/v Calcium dodecylbenzenesulphonate 70%
  • Nonylphenol ethylene oxide propylene oxide condensate (NPEOPO)(Synperonic NPE 1800) 6% w/v Aromatic solvent (Solvesso) to 100 volumes by stirring NMP, active ingredient (Compound 1), CaDDBS,
  • a wettable powder is formed from: Active ingredient (Compound 1 ) 50% w/w
  • a suspension concentrate is formed from:
  • Attaclay (Attagel) 1.5% w/v
  • a water dispersible granule is formed from:
  • Active ingredient 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 of the other ingredients.
  • the compounds of the 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: -
  • the compounds of the invention were applied to the soil surface, containing the seeds, as described in (a). A single pot of each crop and each weed was allocated to each treatment, with unsprayed controls and controls sprayed with acetone alone.
  • the weeds and crops were sown directly into John Innes potting compost in 75 mm deep, 70 mm square pots except for Amaranthus which was pricked out at the seedling stage and transfened to the pots one week before spraying. The plants were then grown in the greenhouse until ready for spraying with the compounds used to treat the plants. The number of plants per pot were as follows :- 1 ) Broad leafed weeds
  • 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 ofEchinochloa orvzicola. Monochoria vaginalis. Lindernia procumbens and Scirpus juncoides respectively, and water was added to a depth of 3 cm.
  • solutions were prepared in 100% 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.
  • Test Method A When applied pre- or post-emergence in Test Method A at lOOOg/ha compounds 1, 2, 4, 6, 7, 10, 17-19, 21, 22, 24-32, 36, 38-54, 57-64, 71-76, 78, 81, 84, 86-97, 106-108, 120-122, 136, 141, 146, 165,
  • 212-299 and 301-303 of the invention gave at least 80% reduction in growth of one or more of the weed species Usted above.

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  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Cette invention se rapporte à des dérivés de 4-benzoylisoxazole représentés par la formule (Ia), à des dérivés de 5-phénylisoxazole représentés par la formule (Ib) et à des dérivés de 2-cyano-1,3-dione représentés par la formule (Ic), où R?1, R2, R3¿, X et n sont définis dans le descriptif de l'invention, de même qu'à leur utilisation en tant qu'herbicides.
PCT/EP1997/000330 1996-01-30 1997-01-24 Benzoylisoxazoles et derives de 2-cyano-1,3-dione utilises en tant qu'herbicides WO1997028136A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU15949/97A AU1594997A (en) 1996-01-30 1997-01-24 Benzoylisoxazoles and 2-cyano-1,3-dione derivatives and their use as herbicides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GBGB9601766.0A GB9601766D0 (en) 1996-01-30 1996-01-30 New herbicides
GB9601766.0 1996-01-30
GBGB9626393.4A GB9626393D0 (en) 1996-12-19 1996-12-19 New herbicides
GB9626393.4 1996-12-19

Publications (1)

Publication Number Publication Date
WO1997028136A1 true WO1997028136A1 (fr) 1997-08-07

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PCT/EP1997/000330 WO1997028136A1 (fr) 1996-01-30 1997-01-24 Benzoylisoxazoles et derives de 2-cyano-1,3-dione utilises en tant qu'herbicides

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Country Link
AU (1) AU1594997A (fr)
ID (1) ID17265A (fr)
WO (1) WO1997028136A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999003856A1 (fr) * 1997-07-18 1999-01-28 Rhone-Poulenc Agriculture Limited Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides
WO2000068204A1 (fr) * 1999-05-08 2000-11-16 Bayer Aktiengesellschaft Cetones de benzoyle substituees, leur procede de preparation et leur utilisation comme herbicides
WO2011012248A2 (fr) 2009-07-29 2011-02-03 Bayer Cropscience Ag Nitriles 2-(3-aminobenzoyl)-3-cyclopropyl-3-oxopropioniques et leur utilisation comme herbicides

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US2765305A (en) * 1952-05-26 1956-10-02 S E Massengill Company Aminoalkyl and quaternary ammonium alkyl esters of o-benzylbenzoic acid
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
EP0580439A1 (fr) * 1992-07-22 1994-01-26 Rhone-Poulenc Agriculture Ltd. Benzoylisoxazols et leur utilisation comme 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

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US2765305A (en) * 1952-05-26 1956-10-02 S E Massengill Company Aminoalkyl and quaternary ammonium alkyl esters of o-benzylbenzoic acid
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
EP0580439A1 (fr) * 1992-07-22 1994-01-26 Rhone-Poulenc Agriculture Ltd. Benzoylisoxazols et leur utilisation comme 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

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CHARLES DUFRAISSE ET AL: "Acide diméthoxy-2',4'benzyl-2benzoique et corps apparentés", BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE, 1947, PARIS FR, pages 701 - 705, XP002028875 *
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FOUCHE J ET AL: "Recherches dans le domaine des produits à activité psychotrope", BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE, no. 8, 1 January 1972 (1972-01-01), pages 3113 - 3130, XP000560355 *
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999003856A1 (fr) * 1997-07-18 1999-01-28 Rhone-Poulenc Agriculture Limited Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme 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
WO2011012248A2 (fr) 2009-07-29 2011-02-03 Bayer Cropscience Ag Nitriles 2-(3-aminobenzoyl)-3-cyclopropyl-3-oxopropioniques et leur utilisation comme herbicides

Also Published As

Publication number Publication date
ID17265A (id) 1997-12-18
AU1594997A (en) 1997-08-22

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