WO1995031446A1 - Derives de 4-benzoylisoxazole et leur utilisation comme herbicides - Google Patents

Derives de 4-benzoylisoxazole et leur utilisation comme herbicides Download PDF

Info

Publication number
WO1995031446A1
WO1995031446A1 PCT/EP1995/001813 EP9501813W WO9531446A1 WO 1995031446 A1 WO1995031446 A1 WO 1995031446A1 EP 9501813 W EP9501813 W EP 9501813W WO 9531446 A1 WO9531446 A1 WO 9531446A1
Authority
WO
WIPO (PCT)
Prior art keywords
optionally substituted
carbon atoms
group containing
branched
straight
Prior art date
Application number
PCT/EP1995/001813
Other languages
English (en)
Inventor
John Morris
Christopher John Pearson
Derek Ian Wallis
Original Assignee
Rhone Poulenc Agriculture Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Agriculture Ltd. filed Critical Rhone Poulenc Agriculture Ltd.
Priority to EP95920033A priority Critical patent/EP0759911A1/fr
Priority to KR1019960706499A priority patent/KR970703328A/ko
Priority to BR9507876A priority patent/BR9507876A/pt
Priority to AU25638/95A priority patent/AU2563895A/en
Priority to JP7529355A priority patent/JPH10500124A/ja
Publication of WO1995031446A1 publication Critical patent/WO1995031446A1/fr

Links

Classifications

    • 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
    • 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
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen

Definitions

  • This invention relates to novel 4-benzoylisoxazole derivatives, compositions containing them, processes for their preparation and their use as herbicides.
  • Herbicidal 4-benzoylisoxazoles are known from the literature, for example in European Patent Publication Nos. 0418175, 0487195, 0524018, 0527036, 0527037, 0560482 and 0580439.
  • none of the above publications disclose or suggest the presence of an alkoxycarbonylaminoalkylene or sulphonylaminoalkylene substituent or substituted aminoalkylidene substituent on the benzoyl ring.
  • the present invention provides 4-benzoylisoxazole derivatives of formula (I):
  • R represents hydrogen or -CC ⁇ R ⁇ ;
  • R! 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 which is optionally substituted by one or more halogen atoms which may be the same or different;
  • R2 represents:- a halogen atom; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; a straight- or branched- chain alkyl group containing up to six carbon atoms which is substituted by a group -OR 6 ; a group selected from nitro, cyano, -CO2R 6 , -S(0)pR 61 , -0(CH 2 ) m OR 61 , -COR 61 , -NR6R7 -CONR8R9 , -OR&, -C ⁇ _2S(0)pR 61 , -NR3R4 and phenyl optionally substituted by from one to five groups R ⁇ l which may be the same or different; R3 represents:- hydrogen; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing
  • E represents an alkylene or alkylidene group containing up to three carbon atoms which is optionally substituted by one or more groups R 5 which may be the same or different;
  • X represents -(CR R 12 ) t .
  • n represents zero or an integer from one or four;
  • R5 represents a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • R 6 and R ⁇ which may be the same or different, each represents:- hydrogen or 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 61 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;
  • R8 and R ⁇ which may be the same or different, each represents:- hydrogen; a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms; or phenyl optionally substituted by from one to five groups R21 which may be the same or different;
  • RlO 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; a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more halogen atoms; or -(CH2 v"(ph en y! optionally substituted by from one to five groups R21 which may be the same or different);
  • R11 and R 12 which may be the same or different, each represents:- hydrogen; a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms; a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more halogen atoms; or -(CH2)w-(phenyl optionally substituted by from one to five groups R21 which may be the same or different);
  • Y represents oxygen or sulphur
  • Z is selected from the group consisting of R 62 , -NR 6 3 64 ;
  • R62 represents:- a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; or
  • R 6 3, R 6 4 and R 65 which may be the same or different, each represents:- hydrogen; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; or
  • R21 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 -OR 5 , nitro, cyano and -S(0)pR 5 ; m represents one, two or three; p represents zero, one or two; q represents zero, one or two, (preferably zero or two); t represents one or two; w represents zero or one; and agriculturally acceptable salts thereof, which possess valuable properties.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 61 , R 62 , R 63 , R 64 , R 65 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 21 may give rise to stereoisomers and geometric isomers. 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 (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.
  • Another preferred class of compounds of formula (I) are those wherein:
  • Rl 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 2 represents:- a halogen atom; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; a group selected from nitro, cyano, -S(0)pR 61 , -COR 61 , -NR 6 R? -CONR 8 R 9 and -OR 6 ;
  • R 3 represents:- hydrogen; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; a cycloalkyl group containing from three to six carbon atoms which is optionally substituted by one or more halogen atoms; -(CH2) w -(phenyl optionally substituted by from one to five groups R 21 which may be the same or different); or -OR 5 ;
  • E represents an alkylene or alkylidene group containing up to three carbon atoms which is optionally substituted by one or more groups R 5 which may be the same or different;
  • R 6 represents:- a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms
  • R7 represents:- hydrogen or a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms
  • R8 and R 9 which may be the same or different, each represents a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • R ⁇ represents:- a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms; a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more halogen atoms; or -(CH2) w -(P nen yl optionally substituted by from one to five groups R 21 which may be the same or different);
  • R 1 and R 12 which may be the same or different, each represents:- hydrogen; a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms;
  • Y represents oxygen
  • Z is selected from the group consisting of R 62 , -NR 63 R 64 , -SR 62 and OR 62 ;
  • R62 represents a straight- or branched- chain alkyl group containing up to four carbon atoms which is optionally substituted by one or more halogen atoms;
  • R 63 , R 64 and R 65 which may be the same or different, each represents a straight- or branched- chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; m represents two; and t represents one.
  • a particularly preferred class of compounds of formula (I) are those wherein:
  • R 1 represents cyclopropyl
  • R 2 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 -S(0) p R 61 ;
  • R 3 represents a straight- or branched- chain alkyl group containing up to three carbon atoms which is optionally substituted by one or more halogen atoms;
  • R 4 represents -S(0) q R 10 ;
  • R 5 represents a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms;
  • R 61 represents methyl or ethyl;
  • R 1 ⁇ represents a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; t represents one; R 11 and R 12 each represent hydrogen; and n is zero, one or two.
  • Particularly important compounds of formula (I) include the following:
  • compounds of formula (I) in which R represents hydrogen may be prepared by the reaction of a compound of formula (II):
  • L is a leaving group and R 1 , R 2 , R 3 , R 4 , 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 0 to 100°C.
  • 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 0 to 100°C.
  • compounds of formula (I) in which R represents hydrogen may be prepared by the reaction of a compound of formula (III):
  • R is as hereinbefore defined and Y 1 represents a carboxyl 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 (I) in which R is hydrogen may be prepared by reaction of a compound of formula (III), as hereinbefore defined, with an appropriate organotin reagent, such as a trialkyltin derivative, optionally using transition metal catalysis such as bis)triphenylphosphine)palladium (II) dichloride, carried out in an inert solvent such as tetrahydrofuran or dioxan at a temperature from 0 to the reflux temperature of the mixture.
  • organotin reagent such as a trialkyltin derivative
  • transition metal catalysis such as bis)triphenylphosphine)palladium (II) dichloride
  • compounds of formula (I) in which R is hydrogen may also be prepared by the oxidation of a compound of formula (Ilia):
  • 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 I in which R represents a group -CO2R 5 , q represents 0 or 2 and R 2 represents a group R 22 as hereinbefore defined may be prepared by the reaction of a compound of formula
  • 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 can be carried out at a temperature between room temperature and the reflux temperature of the mixture.
  • compounds of formula (I) wherein R represents -CO2R 5 , q represents 0 or 2 and R 2 represents a group R 22 as hereinbefore defined may be prepared by the reaction of a salt of a compound of formula (VI):
  • R 5 ⁇ 2CC(Z 1 ) NOH, wherein R 5 and Z 1 are as hereinbefore defined.
  • Preferred salts include sodium or magnesium salts.
  • the reaction may be performed in an inert solvent such as dichloromethane or acetonitrile at a temperature between room temperature and the reflux temperature of the mixture.
  • compounds of formula I may be prepared by the reaction of a compound of formula ( VTI):
  • R, R , R 2 , X and n are as hereinbefore defined and L 1 is a leaving group, with an amine of formula H-NR 3 R 4 , wherein R 3 and R 4 are as hereinbefore defined.
  • L 1 is preferably selected from bromine, chlorine or methylsulphonyloxy (most preferably bromine).
  • the reaction is typically carried out in the presence of a strong base such as potassium tert-butoxide in a polar solvent such as N,N-dimethylformamide at a temperature between -20°C and 100°C
  • a strong base such as potassium tert-butoxide
  • a polar solvent such as N,N-dimethylformamide
  • Compounds of formula (II) in which L represents alkoxy or N,N-dialkylamino may be prepared by the reaction of a compound of formula (VI) with either a trialkyl orthoformate such as triethyl orthoformate or a N,N-dimethylformamide dialkyl acetal such as N,N-dimethylformamide dimethyl acetal.
  • a trialkyl orthoformate such as triethyl orthoformate
  • a N,N-dimethylformamide dialkyl acetal such as N,N-dimethylformamide dimethyl acetal.
  • the reaction with triethyl orthoformate can be carried out in the presence of acetic anhydride at the reflux temperature of the mixture and the reaction with dimethylformamide dialkyl 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.
  • Compounds of formula (Ilia) may be prepared by the treatment of a compound of formula (III) above in which Y 1 represents a carboxyl group such as an aldehyde, treatment with an appropriate organometallic reagent such as a Grignard reagent or organolithium reagent.
  • the reaction is generally carried out in an inert solvent such as ether of tetrahydrofuran at a temperature from 0°C to reflux temperature of the mixture.
  • reaction is generally carried out in the presence of an organic base such as triethylamine in an inert solvent such as toluene or dichloromethane at a temperature between -20°C and room temperature.
  • organic base such as triethylamine
  • inert solvent such as toluene or dichloromethane
  • RiOCH (X) wherein R 1 is as hereinbefore defined, followed by reaction of the metal salt thus obtained with a benzoyl chloride of formula (IX).
  • 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.
  • Compounds of formula (VI) may be prepared by the reaction of an acid chloride of formula (IX) with the metal salt of a compound of formula (XI):
  • reaction to produce the metal salt of a compound of formula (XI) is generally performed in a solvent such as a lower alcohol, preferably methanol.
  • a solvent such as a lower alcohol, preferably methanol.
  • the metal is magnesium.
  • the metal salt of the compound of formula (XI) is subsequently reacted with an acid chloride of formula (IX) in an inert solvent such as toluene or acetonitrile.
  • the decarboxylation is generally performed by refluxing the compound of formula (XII) in the presence of a catalyst, such as para-toluenesulphonic acid, in an inert solvent e.g. toluene.
  • a catalyst such as para-toluenesulphonic acid
  • an inert solvent e.g. toluene.
  • the benzoyl chloride of formula (IX) may be replaced by a compound of formula (XIII):
  • the reaction is generally performed in a solvent such as diethyl ether, tetrahydrofuran or N,N-dimethylformamide, in the presence of a base, preferably an alkali metal base such as sodium hydride or a lithium amide base such as lithium diisopropylamide, at a temperature from 0°C to reflux temperature.
  • a base preferably an alkali metal base such as sodium hydride or a lithium amide base such as lithium diisopropylamide
  • Compounds of formula (VII) may be prepared from the corresponding compound of formula (VII) in which L 1 is replaced by hydrogen. Where L 1 is bromine the reaction is preferably performed using N-bromosuccinimide in an inert solvent such as carbon tetrachloride, optionally in the presence of UV light or a free radical initiator such as azo-bis-isobutyronitrile at a temperature between room temperature and the reflux temperature of the mixture.
  • an inert solvent such as carbon tetrachloride
  • Acid chlorides of formula (IX) in which the group -XNR 3 R 4 is not ortho to the carboxyl group may be prepared by the reaction of a benzoic acid of formula (XVI):
  • Intermediates of formula (XIII) may be prepared by the reaction of the benzoic acids of formula (XVI) with an alkyl chloroformate CICO2R 15 such as ethyl chloroformate.
  • the reaction is carried out in the presence of a base such as an organic base (e.g. triethylamine or pyridine) in an inert solvent such as dichloromethane, N,N-dimethylformamide or tetrahydrofuran at a temperature between -40°C and room temperature.
  • a base such as an organic base (e.g. triethylamine or pyridine)
  • an inert solvent such as dichloromethane, N,N-dimethylformamide or tetrahydrofuran at a temperature between -40°C and room temperature.
  • Compounds of formula (XVI) may be prepared from compounds in which the group XNR 3 R 4 is replaced by a group XL 1 in which L 1 is a leaving group (preferably chlorine or bromine) by reaction with the amino compound HNR 3 R 4 .
  • the reaction is carried out in the presence of a strong base such as potassium tert-butoxide in a polar solvent such as N,N-dimethylformamide at a temperature between -20°C and room temperature.
  • compounds in which p is one or two and/or q is one or two may be prepared by the oxidation of the sulphur atom of the corresponding compounds in which p and/or q is zero or one.
  • 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, or hydrogen peroxide in acetic acid in the presence of acetic anhydride or concentrated sulphuric acid, or using potassium peroxymonosulphate as the oxidising agent.
  • Hydroxylamine hydrochloride (0.38g) was added to a stined solution of l-[4-chloro-3-(N-methyl-N-methylsulphonylamino- methyl)-2-methylsulphenylphenyl]-3-cyclopropyl-2- ethoxymethylenepropan-l,3-dione (2.0g) in ethanol.
  • Sodium acetate (0.43g) was then added.
  • the resultant suspension was stirred at room temperature for 2 hours and left to stand overnight. It was evaporated to dryness and the residue was suspended in ether, washed with water, dried (anhydrous MgS ⁇ 4) and filtered.
  • 3-Chloroperoxybenzoic acid (60%, 0.84g) was added to a solution of 4-[4-chloro-3-(N-methyl-N-methylsulphonyl- aminomethyl)-2-methylsulphenylbenzoyl]-5-cyclopropylisoxazole (0.5g) in dichloromethane. The mixture was stined at room temperature overnight then cooled to -25°C and filtered.
  • Potassium t-butoxide (1.79g) was added to a st ⁇ red, cooled solution of N-methylmethylsulphonamide (1.74g) in N,N-dimethyl formamide at -5°C. The mixture was stirred at 10°C for 1.5 hours then re-cooled to -8°C. A solution of crude ethyl 4-(2- bromomethylbenzoyl)-5-cyclopropylisoxazole-3-carboxylate (6.0g) in N,N-dimethylformamide was added while maintaining the temperature below 0°C. The mixture was stirred at 0°C for 1 hour and at room temperature for 3 hours.
  • Triethylamine (1.34ml) was added to a stined cooled solution of 2-(N-methyl-N-methylsulphonylaminomethyl)-4- trifluoromethylbenzoic acid (3.0g) in N,N-dimethylformamide while maintaining the temperature below 0°C.
  • the mixture was stirred at -10°C for 0.5 hours then ethyl chloroformate (0.92ml) was added.
  • the mixture was again stirred at -10°C for 0.75 hours then a solution of t-butyl 3-cyclopropyl-3-oxopropionate magnesium enolate (1.95g) in N,N-dimethylformamide was added while maintaining the temperature below -5°C.
  • Oxalyl chloride (1.0ml) was added to a solution of 4-chloro-3- (N-methyl-N-methylsulphonylaminomethyl)-2-methylsulphenyl- benzoic acid (2.3g) in dichloromethane containing dimethylformamide (1 drop). The mixture was stined and heated at reflux for 0.75 hours then cooled and evaporated to dryness to give 4-chloro-3-(N-methyl-N-methylsulphonylaminomethyl)-2- methylsulphenylbenzoyl chloride (2.4g) as a brown oil.
  • N-methyl-methylsulphonamide (6.0g) in N,N-dimethylformamide.
  • the mixture was stined for 0.75 hours and methyl 4-bromo-2- bromomethylbenzoate (15.4g) was added. It was stined for 0.25 hours then poured onto a mixture of ice and brine. It was treated with aqueous ammonium chloride solution and extracted with ethyl acetate, washed with water, dried (anhydrous MgS ⁇ 4) and filtered.
  • Potassium carbonate (82.9g) was added to a stined solution of 4-chloro-3-fluoro-2-methylbenzoic acid (112g) in dry acetone. After 1 hour methyl iodide (92. lg) was added and the mixture stined overnight under reflux. The cooled mixture was filtered, washed with acetone and the solvent evaporated.
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • the isoxazole 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 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 myosuroides.
  • the amounts of compounds of formula (I) applied 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 crops.
  • 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.
  • 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. For this purpose 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 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 of the isoxazole 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.
  • compositions are 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 of the ionic or non- ionic types, for example sulphoricinoleates, quaternary ammonium derivatives, products based on condensates of ethylene oxide with alkyl and polyaiyl 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 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 of these 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.
  • 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 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
  • 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 soluble or water dispersible powders which comprise from 10 to 90% of one or more compounds of formula (I), from 2 to 40% of sodium carbonate and from 0 to 88% of solid diluent; liquid water soluble concentrates which comprise from 5 to 50%, e.g. 10 to 30%, of one or more compounds of formula (I), from 5 to 25% of surface-active agent and from 25 to 90%, e.g. 45 to
  • 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
  • organic solvent 10 to 84.9% of organic solvent; 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. 0.5 to 2%, of surface-active agent and from 3 to 98.5%, e.g. 88 to 97.5%, of 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.
  • 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. 0.5 to 2%, of surface-active agent and from 3 to 98.5%, e.g. 88 to 97.5%, of granular carrier and
  • 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, and 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 alkali metal and amine salts and esters.
  • an article of manufacture comprising at least one of the isoxazole 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 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 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 of the container, after dilution if necessary, are to be applied 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.
  • Active ingredient (compound 1) 20% w/v Potassium hydroxide solution 33% w/v 10% v/v
  • a wettable powder is formed from :
  • Active ingredient 50% w/w
  • Active ingredient 50% w/w
  • Crop 1 Broad-leafed
  • 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 :- l) 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. After treatment the pots were placed on capillary matting in a glass house, and watered overhead once after 24 hours and then by controlled sub-irrigation. Visual assessment of crop damage and weed control was made 20-24 days after spraying. The results were expressed as the percentage reduction in growth or damage to the crop or weeds, in comparison with the plants in the control pots.
  • the compounds of the invention used at 1 kg/ha or less, have shown an excellent level of herbicidal activity together with crop tolerance on the weeds used in the foregoing experiments.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

4-benzoylisoxazoles répondant à la formule (I), dans laquelle R, R?1, R2, R3, R4¿, X et n ont les notations définies dans la description, et leur utilisation comme herbicides.
PCT/EP1995/001813 1994-05-17 1995-05-12 Derives de 4-benzoylisoxazole et leur utilisation comme herbicides WO1995031446A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP95920033A EP0759911A1 (fr) 1994-05-17 1995-05-12 Derives de 4-benzoylisoxazole et leur utilisation comme herbicides
KR1019960706499A KR970703328A (ko) 1994-05-17 1995-05-12 4-벤조일이소옥사졸 유도체 및 제초제로서 그의 용도(4-benzoylisoxazole derivatives and their use as herbicides)
BR9507876A BR9507876A (pt) 1994-05-17 1995-05-12 Derivado de 4-benzoilisoxazol composição herbicida método para a controle de ervas daninhas em um local e processo para a preparação de derivado de 4-benzoilisoxasol
AU25638/95A AU2563895A (en) 1994-05-17 1995-05-12 4-benzoylisoxazole derivatives and their use as herbicides
JP7529355A JPH10500124A (ja) 1994-05-17 1995-05-12 ４−ベンゾイルイソオキサゾール誘導体及び該誘導体の除草剤としての使用

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9409944A GB9409944D0 (en) 1994-05-17 1994-05-17 New compositions of matter
GB9409944-7 1994-05-17

Publications (1)

Publication Number Publication Date
WO1995031446A1 true WO1995031446A1 (fr) 1995-11-23

Family

ID=10755337

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/001813 WO1995031446A1 (fr) 1994-05-17 1995-05-12 Derives de 4-benzoylisoxazole et leur utilisation comme herbicides

Country Status (8)

Country Link
EP (1) EP0759911A1 (fr)
JP (1) JPH10500124A (fr)
CN (1) CN1148385A (fr)
AU (1) AU2563895A (fr)
BR (1) BR9507876A (fr)
CA (1) CA2190001A1 (fr)
GB (1) GB9409944D0 (fr)
WO (1) WO1995031446A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000068227A1 (fr) * 1999-05-06 2000-11-16 Bayer Aktiengesellschaft Benzoylisoxazoles substitues et leur utilisation comme herbicides
US6297198B1 (en) 1996-05-14 2001-10-02 Syngenta Participations Ag Isoxazole derivatives and their use as herbicides
WO2003074475A2 (fr) * 2002-03-05 2003-09-12 Bayer Cropscience Aktiengesellschaft Arylcetone substituee
US6777575B2 (en) 1997-07-07 2004-08-17 Rhone-Poulenc Agro Process for the preparation of 2-alkylthio benzoic acid derivatives
WO2011012248A2 (fr) 2009-07-29 2011-02-03 Bayer Cropscience Ag Nitriles 2-(3-aminobenzoyl)-3-cyclopropyl-3-oxopropioniques et leur utilisation comme herbicides
WO2018002437A1 (fr) 2016-06-29 2018-01-04 Orion Corporation Dérivés de benzodioxane et leur utilisation pharmaceutique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7112554B2 (en) 2001-05-09 2006-09-26 Bayer Cropscience Ag Substituted arylketones
DE10206792A1 (de) 2002-02-19 2003-08-28 Bayer Cropscience Ag Substituierte Arylketone
CN110872247A (zh) * 2018-08-29 2020-03-10 上海复星星泰医药科技有限公司 Xofluza含硫杂环化合物、其中间体及制备方法

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
EP0487357A1 (fr) * 1990-11-22 1992-05-27 Rhone-Poulenc Agriculture Ltd. Dérivés de 4-benzoyl isoxazoles
EP0580439A1 (fr) * 1992-07-22 1994-01-26 Rhone-Poulenc Agriculture Ltd. Benzoylisoxazols et leur utilisation comme 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
EP0487357A1 (fr) * 1990-11-22 1992-05-27 Rhone-Poulenc Agriculture Ltd. Dérivés de 4-benzoyl isoxazoles
EP0580439A1 (fr) * 1992-07-22 1994-01-26 Rhone-Poulenc Agriculture Ltd. Benzoylisoxazols et leur utilisation comme herbicides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6297198B1 (en) 1996-05-14 2001-10-02 Syngenta Participations Ag Isoxazole derivatives and their use as herbicides
US6777575B2 (en) 1997-07-07 2004-08-17 Rhone-Poulenc Agro Process for the preparation of 2-alkylthio benzoic acid derivatives
WO2000068227A1 (fr) * 1999-05-06 2000-11-16 Bayer Aktiengesellschaft Benzoylisoxazoles substitues et leur utilisation comme herbicides
AU773634B2 (en) * 1999-05-06 2004-05-27 Bayer Aktiengesellschaft Substituted benzoylisoxazoles and the use thereof as herbicides
US6838415B1 (en) 1999-05-06 2005-01-04 Bayer Aktiengesellschaft Substituted benzoylisoxazoles and the use thereof as herbicides
WO2003074475A2 (fr) * 2002-03-05 2003-09-12 Bayer Cropscience Aktiengesellschaft Arylcetone substituee
WO2003074475A3 (fr) * 2002-03-05 2004-02-05 Bayer Cropscience Ag Arylcetone substituee
US7807703B2 (en) 2002-03-05 2010-10-05 Bayer Cropscience Ag Substituted aryl ketones
WO2011012248A2 (fr) 2009-07-29 2011-02-03 Bayer Cropscience Ag Nitriles 2-(3-aminobenzoyl)-3-cyclopropyl-3-oxopropioniques et leur utilisation comme herbicides
WO2018002437A1 (fr) 2016-06-29 2018-01-04 Orion Corporation Dérivés de benzodioxane et leur utilisation pharmaceutique

Also Published As

Publication number Publication date
CA2190001A1 (fr) 1995-11-23
AU2563895A (en) 1995-12-05
BR9507876A (pt) 1997-08-19
CN1148385A (zh) 1997-04-23
GB9409944D0 (en) 1994-07-06
JPH10500124A (ja) 1998-01-06
EP0759911A1 (fr) 1997-03-05

Similar Documents

Publication Publication Date Title
EP0527036B1 (fr) Dérivés de 4-benzoylisoxazole et leur utilisation comme herbicides
EP0524018B1 (fr) Isoxazoles herbicides
EP0560482B1 (fr) Dérivés de 4-benzoyl isoxazole et leur utilisation comme herbicides
EP0527037B1 (fr) Dérivés de benzoyl isoxazole et leur utilisation comme herbicides
CA2114696C (fr) Herbicides 4-benzoylisoxazole
US5371064A (en) Herbicidal 4-benzoylisoxazole derivatives
US5371063A (en) Herbicidal 4-benzoylisoxazoles
US6013805A (en) Pentafluorothio-substituted isoxazoles
AU666397B2 (en) 4-heteroaroylisoxazole derivatives which are useful as herbicides
AU674050B2 (en) 4-benzoyl isoxazoles derivatives and their use as herbicides
EP0734380B1 (fr) 4-benzoylisoxazoles et leur utilisation en tant qu'herbicides
AU658044B2 (en) New herbicides
EP0759911A1 (fr) Derives de 4-benzoylisoxazole et leur utilisation comme herbicides
AU7497894A (en) 2-oximinomethyl-1-phenyl-1,3-propanedione derivatives as herbicides

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 95193111.3

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN FI HU JP KR NZ RU US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1995920033

Country of ref document: EP

Ref document number: 2190001

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 1997 737463

Country of ref document: US

Date of ref document: 19970116

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 1995920033

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1995920033

Country of ref document: EP