+

WO1997023491A1 - Mouveaux herbicides - Google Patents

Mouveaux herbicides Download PDF

Info

Publication number
WO1997023491A1
WO1997023491A1 PCT/EP1996/005667 EP9605667W WO9723491A1 WO 1997023491 A1 WO1997023491 A1 WO 1997023491A1 EP 9605667 W EP9605667 W EP 9605667W WO 9723491 A1 WO9723491 A1 WO 9723491A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
compound
group
carbon atoms
optionally substituted
Prior art date
Application number
PCT/EP1996/005667
Other languages
English (en)
Inventor
Atsushi Go
Takako Brett
Norishige Toshima
Koichi Araki
Yoshie Kirio
Masahito Itoh
Norio Sasaki
Claude Lambert
Michael Gingell
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 AU13736/97A priority Critical patent/AU1373697A/en
Publication of WO1997023491A1 publication Critical patent/WO1997023491A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/653—Five-membered rings
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing aromatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/24—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing heterocyclic radicals
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D261/18—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4056—Esters of arylalkanephosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative

Definitions

  • This invention relates to novel 4-benzoylisoxazole, 5-phenylisoxazole and 2-cyano-l,3-dione derivatives, compositions containing them, processes and intermediates for 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 phosphonate or phosphinate substituent attached to the benzoyl ring via an alkylene grouping.
  • the present invention thus provides 4-benzoylisoxazole derivatives of formula (la), 5-phenylisoxazole derivatives of formula (lb) and 2- cyano-l,3-dione derivatives of formula (Ic):
  • R represents hydrogen or -CO2R 4 ;
  • Rl represents:- a straight- or branched- chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; or a cycloalkyl group containing from three to six carbon atoms optionally substituted by one or more R*2 groups or one or more halogen atoms;
  • 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 5 ; a cycloalkyl group containing from three to six carbon atoms; or a group selected from nitro, cyano, -CO2R 5 , -S(O) p R 7 , -O(CH2) m OR 5 ,
  • R 4 represents a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • R 5 and R*> which may be the same or different, each represents hydrogen or R 12 ;
  • R 7 represents R* 2 or a cycloalkyl group containing from three to six carbon atoms; or a group -(CH2)w-[phenyl optionally substituted by from one to five groups R 2 ⁇ which may be the same or different], wherein w represents zero or one;
  • R 8 represents:-
  • SU ⁇ STITUTE SHEET hydrogen; a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to ten carbon atoms optionally substituted by one or more halogen atoms; a cycloalkyl group containing from three to six carbon atoms;
  • R 9 and R ⁇ independently represent a group selected from: hydrogen; a straight- or branched- chain alkyl group containing up to six (preferably up to three) carbon atoms optionally substituted by one or more halogen atoms;
  • Rl represents a straight- or branched- chain alkyl, alkenyl or alkynyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms
  • R 13 , R 13 ', R 14 ' and R 15 independently represent R 5 ;
  • R 14 represents R 5 , cyano, -OR 12 , -S(O) p R 12 or halogen
  • R 16 represents R 5 , cyano, -OR 12 or -S(O) p R 12 ;
  • R 17 and R 1 independently represent hydrogen or R* 9 ;
  • R* 9 represents:- a straight- or branched- chain alkyl or alkenyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms; or
  • R 2 0 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)pR 21 and -OR 5 ;
  • R 2 1 represents a straight- or branched- chain alkyl group containing up to six carbon atoms optionally substituted by one or more halogen atoms;
  • R24 represents: - a group selected from halogen, R 12 , nitro, cyano, -CO2 , -S(O) p R 5 , -OR 7 , -OH and -NR 5 R 6 ;
  • Y is oxygen or sulphur (preferably oxygen);
  • Z represents a group R 12 , -NR 8 R 22 , -N(R 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.
  • Lower alkyl means a C-l to C-6 straight- or branched- chain alkyl group.
  • agriculturally acceptable salts salts the cations or anions of which are known and accepted in the art for the formation of salts for agricultural or horticultural use.
  • the salts are water-soluble.
  • Suitable salts with bases include alkali metal (eg. sodium and potassium), alkaline earth metal (eg. calcium and magnesium), ammonium and amine (eg. diethanolamine, triethanolamine, octylamine, morpholine and dioctylmethylamine) salts.
  • Suitable acid addition salts formed by compounds of formula (I) containing an amino group, include salts with inorganic acids, for example hydrochlorides, sulphates, phosphates and nitrates and salts with organic acids, for example acetic acid.
  • metal complexes is meant 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.
  • 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 particularly advantageous properties. The following are preferred features of the present invention, due to their herbicidal properties.
  • Compounds of formula (I) in which X is -CH2- are preferred.
  • Preferably the 5- and 6- positions of the phenyl ring are unsubstituted.
  • 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; cyclopropyl or 1-methylcyclopropyl. Most preferably R* represents cyclopropyl.
  • R 2 represents :- halogen; a straight- or branched- chain alkyl or alkenyl group containing up to four carbon atoms optionally substituted by one or more halogen atoms; or a group selected from nitro, cyano, -S(O)pR 7 , -OR 7 and -OH.
  • n represents zero, one or two.
  • R 7 represents a straight- or branched- chain alkyl group containing up to six carbon atoms which is optionally substituted by one or more halogen atoms.
  • R 17 and R 1 independently represent hydrogen or a straight- or branched- chain alkyl group containing up to four carbon atoms which is optionally substituted by one or more halogen atoms.
  • a particularly preferred class of compounds of formula (la) are those wherein: -
  • R represents hydrogen or -CO2R 4 ;
  • Rl 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) p R 7 group;
  • n represents zero, one or two;
  • X represents -CH2-;
  • R 4 represents a straight- or branched- chain alkyl group containing from one to three carbon atoms
  • R 7 represents a methyl or ethyl group which is optionally substituted by one or more halogen atoms
  • R 17 and R* 8 independently represent:- a straight- or branched- chain alkyl group containing from one to four carbon atoms optionally substituted by one or more halogen; or phenyl, benzyl or allyl; and R 19 represents methyl, ethyl or phenyl.
  • Another particularly preferred class of compounds of formula (la) are those wherein:-
  • R represents hydrogen, or -CO2R 4 ;
  • Rl represents cyclopropyl
  • R 2 represents:- halogen; a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or a -S(O) p R 7 group
  • n represents zero, one or two; when present the R 2 groups being attached to the 3 and/or 4 positions of the phenyl ring;
  • X represents -CH2-
  • R 4 represents methyl or ethyl;
  • R 7 represents a methyl or ethyl group which is optionally substituted by one or more halogen atoms; 1 7 and R* 8 independently represent a straight- or branched- chain alkyl group containing up to three carbon atoms.
  • Another particularly preferred class of compounds of formula (la) and (Ic) are those wherein:-
  • R in the case of compounds of formula la, represents hydrogen or -CO 2 R 4 ;
  • Rl represents cyclopropyl
  • R 2 represents: - halogen; a straight- or branched- chain alkyl group containing up to three carbon atoms optionally substituted by one or more halogen atoms; or two groups R 2 , 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
  • n represents zero, one or two; when n is one or two the R 2 groups are attached to the 3 and/or 4 positions of the phenyl ring;
  • X represents -CH2- or -CH(CH3 ;
  • R 4 represents methyl or ethyl
  • 17 and R* 8 independently represent a straight- or branched- chain alkyl group containing up to four carbon atoms.
  • the Compounds numbered from 1 to 391 are compounds of formula (Al); Compounds 451 to 498 are of formula (A2) below; Compounds 501 to 550 are of formula (A3) below; Compounds 601 to 699 are of formula (A4) below; Compounds 700 to 704 are of formula (A5) below; and Compounds 705 to 712 are of formula (A6) below. -9-
  • Particularly important compounds of formula (I) include the following:
  • compounds of formula (la) or (lb) in which R represents hydrogen and R , R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of formula (II):
  • L is a leaving group and l, 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
  • a base or acid acceptor such as triethylamine or sodium acetate
  • compounds of formula (la) in which R represents hydrogen 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 (III):
  • compounds of formula (la) wherein R represents a group -CO2R 4 and K , R 2 , R 3 , X and n are as defined above, may be prepared by the reaction of a compound of formula (IV):
  • 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 (la) in which R represents a group -CO2R 4 and R 1 , R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of formula (V):
  • 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 (la) or (lb) wherein R represents -CO2R 4 and R l , R 2 , R 3 , X and n are as defined above, may be prepared by the reaction of a salt of compounds of formula (VI):
  • 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.
  • suitable bases include alkaline earth metal alkoxides such as magnesium methoxide.
  • compounds of general formula (lb) in which R, R 1 , R 2 , R 3 ,X and n are as defined above, may be prepared by the metallation of compounds of general formula (VII):
  • R 2 , R 3 , X and n are as defined above and D 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 solvent.
  • compounds of general formula (lb) in which R represents a -CO2R 4 group and Rl, R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of general formula (X):
  • Z 1 is chlorine or bromine.
  • the reaction is preferably 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 general formula (lb) in which R represents a group -CO2R 4 and R , R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of general formula (XI):
  • compounds of formula (la) and (lb) wherein R, Rl, R 2 , R 3 , X and n are as defined above may be prepared by the reaction of a compound of formula (XII) and (XIII) respectively:
  • reaction is generally performed by heating in the presence or absence of an inert solvent e.g. xylene at a temperature from 80°C to 200°C.
  • inert solvent e.g. xylene
  • compounds of formula (la) and (lb) wherein R, Rl, R 2 , R 3 and n are as defined above, X represents a -C(R1 3 R1 )- group wherein Rl is defined above and Rl represents a halogen atom may be prepared by the reaction of the corresponding compound of formula (la) or (lb) wherein X represents a -CHR! 3 - group, with a halogenating agent e.g. N-bromosuccinimide or N-chlorosuccinimide in an inert solvent, preferably carbon tetrachloride and in the presence of a radical initiator, e.g. benzoyl peroxide with irradiation by light from a Tungsten lamp at a temperature from ambient to the reflux temperature.
  • a halogenating agent e.g. N-bromosuccinimide or N-chlorosuccinimide in an inert solvent, preferably carbon tetrachloride
  • compounds of formula (la) and (lb) in which R, Rl, R 2 , R 3 and n are as defined above, X represents a -C(R1 3 'R1 ')-C( 1 5 R1 6 )- group and Rl 3 ', Rl 4 ', R! 5 and Rl 6 are as defined above may be prepared by the reaction of the corresponding compound of formula (XII) or (XIII) wherein X represents a -C(Rl 3 )(Rl 4 )- group and Z' represents a halogen group as defined above, preferably bromine or chlorine, with a compound of formula HC (R ⁇ RI ⁇ )R 3 .
  • the reaction is generally performed in the presence of a base e.g. sodium hydride and in an inert solvent e.g. N,N- dimethylformamide at a temperature from 0°C to 100°C.
  • compounds of formula (la) or (lb) in which R, Rl, R 2 , R 3 and n are as defined above, and X represents a group -C(Rl )(CN)- wherein Rl is as hereinbefore defined, may be prepared by the reaction of the corresponding compound of formula (la) or (lb) in which X is
  • halogen preferably sodium cyanide or potassium cyanide
  • an alkali metal cyanide preferably sodium cyanide or potassium cyanide
  • an inert solvent e.g. dimethylsulfoxide at a temperature from 10°C to 100°C.
  • the halogen is bromine or chlorine.
  • compounds of formula (la) or (lb) in which R, Rl , R 2 , R 3 and n are as defined above, and X represents a group -C(R1 3 )(0R12)- wherein R ⁇ 2 and R 13 is as hereinbefore defined may be prepared by the reaction of the corresponding compound of formula (la) or (lb) in which X is -C(Rl 3 )(halogen), with a compound of formula R 1 2 OM where M represents hydrogen or an alkali metal (e.g. sodium, potassium or lithium).
  • the halogen is bromine or chlorine.
  • the reaction is generally performed in an inert solvent e.g.
  • compounds of formula (la) or (lb) in which R, Rl, R 2 , R 3 and n are as defined above, and X represents a group -C(R1 3 )(SR1 2 )- wherein Rl 2 and R* 3 are as hereinbefore defined may be prepared by the reaction of the corresponding compound of formula (la) or (lb) wherein X is -C(R 1 3 )(halogen), by the same procedure as used for the compounds above wherein X represents a group -C(R1 3 )(0R1 2 )-, by replacing the compound R 2 OM by a compound R ⁇ 2 SM.
  • compounds of formula (Ic) may be prepared from the corresponding compound of formula (la) or (lb) in which R is as defined above, or in which R is replaced by an amide or nitrile.
  • R represents a hydrogen atom
  • the reaction is preferably carried out by treatment with a base.
  • suitable bases include alkali or alkaline earth metal hydroxides, alkoxides such as sodium ethoxide or organic bases such as triethylamine.
  • R represents -CO2R 4 , or where R is replaced by amide or nitrile
  • the conversion is generally carried out by a hydrolytic reaction.
  • the hydrolytic reaction may be performed in the presence of an acid or base.
  • Acidic hydrolysis may be achieved for example using aqueous hydrochloric acid.
  • Basic hydrolysis may be achieved for example using sodium hydroxide in a mixture of alcohol and water.
  • the reactions are preferably carried out at a temperature between room temperature and the reflux temperature of the mixture.
  • Compounds of formula (la) or (lb) 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 Rl, R 2 , R 3 , X and n are as defined above may also be prepared by the reaction of a benzoyl chloride of formula (XVII): O
  • 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.
  • compounds of formula (Ic) in which Rl, 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 COCl, wherein Rl is as hereinbefore defined, with a beta-ketonitrile of formula
  • compounds of formula (Ic) in which R , R 2 , R 3 , X and n are as defined above may be prepared by the reaction of an acid chloride of formula R COCl wherein Rl is as hereinbefore defined, with a beta-ketonitrile of formula (XIX) wherein R 2 , R 3 , X and n are as hereinbefore defined via an intermediate of fo
  • 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 dialkyl acetal such as dimethylformamide dimethyl acetal.
  • a trialkyl orthoformate such as triethyl orthoformate
  • a dimethylformamide dialkyl acetal such as dimethylformamide dimethyl acetal.
  • reaction with a trialkyl orthoformate can be carried out in the presence of acetic anhydride at the reflux temperature of the mixture and the reaction with dialkylformamide dialkyl acetal is carried out optionally in the presence of an inert solvent at a temperature from room temperature to the reflux temperature 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
  • reaction is generally performed in a solvent such as ether, tetrahydrofuran or
  • N,N-dimethylformamide in the presence of a base, preferably an alkali metal base such as sodium hydride, at a temperature from 0°C to the reflux temperature.
  • a base preferably an alkali metal base such as sodium hydride
  • Acid chlorides of formula (XVII) may be prepared by the reaction of a benzoic acid of formula (XXVIII):
  • XXVUI XXVUI
  • R 2 , R 3 , X and n are as defined above
  • a chlorinating agent for example thionyl chloride at the reflux temperature of the mixture.
  • benzoyl 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.
  • Acid chlorides of formula (XVII) and benzoic acids of formula (XXVIII) in which R 2 , R 3 and X are as hereinbefore defined and n is an integer from one to three are novel with the exclusion of compounds in which:
  • (a) -XR 3 is 3-CH 2 PO 3 H and (R 2 ) n is 5-OCH 2 CO 2 H or 5-OH;
  • Esters of formula (XXVI) may be prepared from acids of formula (XXVIII) by known methods.
  • Compounds of general formula (VIII) may be prepared by metallation of compounds of general formula (VII) with for example n- butyllithium in an inert solvent such as ether or tetrahydrofuran at a temperature from -78°C to 0°C, followed by reaction with an aldehyde of general formula RlCHO.
  • Beta-ketonitriles of formula (XVIII) may be prepared from acid chlorides of formula RlCOCl 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, Var, 736.
  • beta- ketonitriles of formula (XVIII) may be prepared by the reaction of an ester of formula Rl-CO2Et, wherein Rl 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 (XLX) may be prepared from benzoyl chlorides of formula (XVII) or from corresponding ethyl benzoates in a manner analogous to the preparation of beta-ketonitriles of formula (XVIII) set forth above.
  • benzoic acids of formula (XXVIII) in which R 2 , R 3 , X and n are as defined above may be prepared by the reaction of the corresponding compound of formula (XXVIII) in which R 3 is replaced by a halogen atom, preferably bromine or chlorine, with a phosphite or phosphonite of formula (XIV), (XV) or (XVI) by the same procedure as used for the preparation of compounds of formula (la) and (lb) from compounds of formula (XII) and (XIII).
  • 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 and q is one or two may be prepared by the oxidation of the sulphur atom of the corresponding compounds in which p 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.
  • a method for controlling the growth of weeds i.e. undesired vegetation
  • a method for controlling the growth of weeds which comprises applying to the locus 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.
  • the isoxazole or 2-cyano- 1,3 -dione derivatives are normally used in the form of herbicidal compositions (i.e. in association with compatible diluents or carriers and/or surface active agents suitable for use in herbicidal compositions), for example as hereinafter described.
  • the compounds of formula (I) show herbicidal activity against dicotyledonous (i.e. broad-leafed) and monocotyledonous (i.e. grass) weeds by pre- and/or post-emergence application.
  • pre-emergence application application to the soil in which the weed seeds or seedlings are present before emergence 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, pqrpqrea, Sespama ex jM , Sjqapis arvensis. Solanum nigrum and Xanthium strumarium. and grass weeds, for example Alopecurus mvosuroides. Avena fatua. Digitaria sanguinalis. Echinochloa crus-galli. Sorghum bicolor. Eleusine indica and Setaria spp.
  • 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. In general, taking these factors into account, 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,
  • weeds at a locus of weed infestation which is an area used, or to be used, for growing of crops, e.g. the crops hereinbefore mentioned
  • application rates between 0.01kg and 4.0kg, and preferably between 0.01kg and 2.0kg, of active material per hectare are particularly suitable.
  • 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.
  • they may be applied in a directional or non- directional fashion (e.g.
  • 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. Where especially prolonged weed control is required, the application of the compounds of formula (I) may be repeated if required.
  • 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.
  • 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 polyaryl phenols, e.g.
  • the herbicidal compositions according to the present invention may comprise up to 10% by weight, e.g.
  • 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.
  • 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 corrosion inhibitors. These adjuvants may also serve as carriers or diluents.
  • Preferred herbicidal compositions according to the present invention are: aqueous suspension concentrates which comprise from 10 to 70% of one or more compounds of formula (I), from 2 to 10% of surface- active agent, from 0.1 to 5% of thickener and from 15 to 87.9% of water; wettable powders which comprise from 10 to 90% of one or more compounds of formula (I), from 2 to 10% of surface-active agent and from 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.
  • liquid emulsifiable suspension concentrates which comprise from
  • granular carrier and emulsifiable concentrates which comprise 0.05 to 90%, and preferably from 1 to 60% of one or more compounds of formula (I), from 0.01 to 10%, and preferably from 1 to 10%, of surface-active agent and from 9.99 to 99.94%, and preferably from 39 to 98.99%, of organic solvent.
  • Herbicidal compositions according to the present invention may also comprise the compounds of formula (I) in association with, and preferably homogeneously dispersed in, one or more other pesticidally active compounds and, if desired, one or more compatible pesticidally acceptable diluents or carriers, surface-active agents and conventional adjuvants as hereinbefore described.
  • synthetic pyrethroids e.g. permethrin and cypermethrin
  • fungicides e.g. carbamates, e.g. methyl N-(l -butyl-carbamoyl- benzimidazol-2-yl)carbamate, and triazoles e.g. l-(4-chloro-phenoxy)- 3,3- dimethyl- 1 -( 1 ,2,4-triazol- 1 -yl)-butan-2-one.
  • Pesticidally active compounds and other biologically active materials which may be included in, or used in conjunction with, the herbicidal compositions 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 or 2-cyano-l,3-dione derivatives of formula (I) or, as is preferred, a herbicidal composition as hereinbefore described, and preferably a herbicidal concentrate which must be diluted before use, comprising at least one of the isoxazole or 2-cyano- 1,3 -dione derivatives of formula (I) within a container for the aforesaid derivative or derivatives of formula (I), or a said herbicidal composition, and instructions physically associated with the aforesaid container setting out the manner in which the aforesaid derivative or derivatives of formula (I) or herbicidal composition contained therein is to be used to control the growth of weeds.
  • the containers will normally be 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.
  • the following non-limiting Examples illustrate herbicidal compositions according to the present invention. In the description that follows the following are trademarks: Aiylan, Arkopon, Sopropon, Tixosil, Soprophor.
  • An emulsifiable concentrate is formed from: Active ingredient (Compound 1) 20% w/v
  • NMP N-Methylpyrrolidone
  • CaDDBS Calcium dodecylbenzenesulphonate 70% (Arylan CA) 4% w/v
  • 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, NPEOPO and 90% Aromatic solvent until a clear solution is formed, and adjusting to volume with Aromatic solvent.
  • NPEOPO Nonylphenol ethylene oxide propylene oxide condensate
  • Solvesso Aromatic solvent
  • a wettable powder is formed from:
  • Active ingredient 50% w/w Sodium dodecylbenzenesulphonate
  • a water dispersible granule is formed from:
  • Active ingredient 50% w/w
  • 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 transferred 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; oshihikari), that had been grown in advance in a greenhouse to a stage of two leaves, were transplanted to each pot (two seedlings per pot). Then in each pot there were sown predetermined amounts of seeds of Echinochloa orvzicola. Mo ⁇ ochoria vaginalis. Lindernia procumbens and Scirpus iuncoides respectively, and water was added to a depth of 3 cm. After having grown the plants in a greenhouse until Echinochloa orvzicola reached a stage of 1.5 leaves, 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (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)

Abstract

L'invention concerne des composés herbicides de la formule (Ia), (Ib) et (Ic), dans lesquelles R, R1, R2 et n sont tels que définis dans la description, X représente -C(R13R14)- ou -C(R?13'R14')-C(R15R16¿)-; et R3 représente -P(=O)(OR17)(R19), -P(=O)(OR?17)(OR18¿); ou un groupe (g); l'invention décrit également l'utilisation de ces composés en tant qu'herbicides.
PCT/EP1996/005667 1995-12-22 1996-12-17 Mouveaux herbicides WO1997023491A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU13736/97A AU1373697A (en) 1995-12-22 1996-12-17 New herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9526435.4 1995-12-22
GBGB9526435.4A GB9526435D0 (en) 1995-12-22 1995-12-22 New herbicides

Publications (1)

Publication Number Publication Date
WO1997023491A1 true WO1997023491A1 (fr) 1997-07-03

Family

ID=10786016

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/005667 WO1997023491A1 (fr) 1995-12-22 1996-12-17 Mouveaux herbicides

Country Status (4)

Country Link
AU (1) AU1373697A (fr)
GB (1) GB9526435D0 (fr)
WO (1) WO1997023491A1 (fr)
ZA (1) ZA9610716B (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2037771A (en) * 1978-11-10 1980-07-16 Sandoz Ltd ???-substituted benzyl phosphonic acid ester derivatives
EP0503410A1 (fr) * 1991-03-14 1992-09-16 BASF Aktiengesellschaft Amides d'acides isoxazole et isothiazole-5-carboxyliques
EP0524018A1 (fr) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0560483A1 (fr) * 1992-03-12 1993-09-15 Rhone-Poulenc Agriculture Ltd. Dérivés du 4-benzoyl isoxazole et leur utilisation comme herbicides
WO1995025099A1 (fr) * 1994-03-17 1995-09-21 Rhone-Poulenc Agriculture Ltd. Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2037771A (en) * 1978-11-10 1980-07-16 Sandoz Ltd ???-substituted benzyl phosphonic acid ester derivatives
EP0503410A1 (fr) * 1991-03-14 1992-09-16 BASF Aktiengesellschaft Amides d'acides isoxazole et isothiazole-5-carboxyliques
EP0524018A1 (fr) * 1991-07-17 1993-01-20 Rhone-Poulenc Agriculture Ltd. Isoxazoles herbicides
EP0560483A1 (fr) * 1992-03-12 1993-09-15 Rhone-Poulenc Agriculture Ltd. Dérivés du 4-benzoyl isoxazole et leur utilisation comme herbicides
WO1995025099A1 (fr) * 1994-03-17 1995-09-21 Rhone-Poulenc Agriculture Ltd. Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides

Also Published As

Publication number Publication date
ZA9610716B (en) 1997-06-23
AU1373697A (en) 1997-07-17
GB9526435D0 (en) 1996-02-21

Similar Documents

Publication Publication Date Title
AU655648B2 (en) Substituted benzoyl isoxazoles and herbicidal compositions
AU647874B2 (en) New 2-cyano-1,3-diones, processes for their preparation, compositions containing them and their use as herbicides
CA2074155C (fr) Herbicides 4-acyl-5-arylisoxazoles
AP432A (en) "Benzoyl isoxazoles and their use as herbicides".
EP0527037B1 (fr) Dérivés de benzoyl isoxazole et leur utilisation comme herbicides
EP1160244B1 (fr) Dérivés d'isoxazole et leur utilisation comme herbicides
US5371064A (en) Herbicidal 4-benzoylisoxazole derivatives
US5849928A (en) Herbicidal isoxazole and 2-cyano-1,3-dione compounds
US5371063A (en) Herbicidal 4-benzoylisoxazoles
EP1156048B1 (fr) Hétéroaroyl-isoxazoles et leur utilisation comme herbicides
WO1995025099A1 (fr) Derives de 2-cyano-1,3-dione utiles en tant qu'herbicides
AU658044B2 (en) New herbicides
WO1997027187A1 (fr) Derives de l'isoxazole et de 2-cyano-1,3-diones et leur utilisation comme desherbants
WO1999003856A1 (fr) Derives de 4-benzoyl-isoxazole- et de 4-benzoyl-pyrazole et derives de 2-cyano 1,3-dione utilises comme herbicides
WO1995031446A1 (fr) Derives de 4-benzoylisoxazole et leur utilisation comme herbicides
EP0918056A1 (fr) Herbicides
WO1997023491A1 (fr) Mouveaux herbicides
WO1995025105A1 (fr) Derives d'isoxazole et leur utilisation en tant qu'herbicides
WO1999003845A1 (fr) Derives de 2-benzoylcyclohexane-1,3-dione servant d'herbicides, et intermediaires correspondants
WO1997028136A1 (fr) Benzoylisoxazoles et derives de 2-cyano-1,3-dione utilises en tant qu'herbicides
AU7497894A (en) 2-oximinomethyl-1-phenyl-1,3-propanedione derivatives as herbicides
GB2311288A (en) Herbicidal pentafluorosulfanyl compounds

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AU BA BB BG BR CA CN CU CZ EE GE HU IL IS JP KP KR LC LK LR LT LV MG MK MN MX NO NZ PL RO SG SI SK TR TT UA US UZ VN AM AZ BY KG KZ MD RU TJ TM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE LS MW SD SZ UG AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

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
NENP Non-entry into the national phase

Ref country code: JP

Ref document number: 97523289

Format of ref document f/p: F

122 Ep: pct application non-entry in european phase
点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载