WO1996015115A1 - Composes de pyrazole herbicides - Google Patents

Composes de pyrazole herbicides Download PDF

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Publication number
WO1996015115A1
WO1996015115A1 PCT/GB1995/002458 GB9502458W WO9615115A1 WO 1996015115 A1 WO1996015115 A1 WO 1996015115A1 GB 9502458 W GB9502458 W GB 9502458W WO 9615115 A1 WO9615115 A1 WO 9615115A1
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Prior art keywords
compound
reaction
compounds
general formula
alkyl
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PCT/GB1995/002458
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English (en)
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Ewan James Turner Chrystal
Susan Patricia Barnett
Kevin Beautement
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Zeneca Limited
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Priority to AU36599/95A priority Critical patent/AU3659995A/en
Publication of WO1996015115A1 publication Critical patent/WO1996015115A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms

Definitions

  • This invention relates to chemical compounds useful as herbicides, to processes for preparing them, and to herbicidal compositions and processes utilising them.
  • Herbicidal compounds based upon aryl pyrazoles are known, for example from J03072460 and WO92/06962.
  • R 1 is hydrogen or alkyl, alkenyl, alkynyl, benzyl, cycloalkyl or cycloalkenyl, any of which may optionally be substituted;
  • R 2 is alkyl, alkenyl or alkynyl, any of which may optionally be substituted, or halo, OR 5 , SO m R 5 , O(alkyl)CO 2 R 5 or O(alkyl)COR 5 ;
  • n 0, 1 or 2;
  • R 3 is H, halogen, cyano, alkyl, alkenyl or alkynyl, any of which may optionally be substituted, or SO 2 Z, COR 5 , CO 2 R 5 or OR 5 ;
  • R 4 is H, alkyl, alkenyl or alkynyl, any of which may optionally be substituted, or cyano, nitro, halogen, NR 5 R 6 , OR 5 , SOpR 5 , CO 2 R 5 , CONR 5 R 6 , NR 5 SO R 6 , COR 5 , C(NOR 5 )R 6 , OSO p R 5 ,
  • Each X is independently halogen, cyano, nitro, alkyl, alkenyl or alkynyl, any of which may optionally be substituted, OR 5 , NR 5 R 6 , NR 5 SO 2 R 6 , OSO 2 R 5 , SO p R 5 , CO.R 5 , COR 5 ,
  • Z is halogen
  • p 0, 1 or 2;
  • n 0, 1, 2 or 3;
  • Y is halogen, cyano or optionally substituted alkoxy;
  • R 5 and R 6 are each independently H, alkyl, alkenyl or alkynyl, any of which may optionally be substituted.
  • alkyl refers to straight or branched fully saturated hydrocarbon chains having up to 10 carbon atoms.
  • lower used in relation to “alkyl” means that the chains have from 1 to 4 carbon atoms.
  • alkenyl refers to a straight or branched hydrocarbon chain having at least one double bond and having up to ten carbon atoms
  • alkynyl refers to a straight or branched hydrocarbon chain having at least one triple bond and up to ten carbon atoms.
  • lower used in relation to alkenyl and alkynyl means that the chains have from two to four carbon atoms.
  • alkoxy alkyl, alkenyl and alkynyl.
  • alkyl alkenyl and alkynyl.
  • Such groups have up to ten carbon atoms unless used in conjuction with the term “lower” when they have up to four carbon atoms.
  • cycloalkyl refers to a saturated hydrocarbon ring having from three to eight ring carbon atoms. Examples of such groups include cyclopropyl, cyclobutyl and cyclohexyl.
  • cycloalkenyl refers to a hydrocarbon ring having from three to eight ring carbon atoms and containing at least one double bond. Examples of such groups include cyclohexenyl.
  • halogen used herein includes fluorine, chlorine, bromine and iodine.
  • Suitable optional substituents for alkyl, alkenyl, alkynyl, alkoxy, benzyl, cycloalkyl and cycloalkenyl, groups described herein include cyano; nitro; halogen such as chlorine, fluorine and bromine; haloalkyl such as trifluoromethyl; carboxylic ester groups such as carboxymethyl or carboxyethyl; substituted and unsubstituted carboxamides such as N,N-dimethylamido; alkoxy, in particular haloalkoxy such as trifluoromethoxy; aryl such as phenyl or naphthyl; cycloalkyl for examples containing up to 7 ring atoms; or heterocyclyl containing for example up to 10 ring atoms, up to three of which are selected from oxygen, nitrogen and sulphur, such as tetrahydrofuryl.
  • the formula (I) given above is intended to include tautomeric forms of the structure drawn, as well as physically distinguishable modifications of the compounds which may arise, for example, from different ways in which the molecules are arranged in a crystal lattice, or from the inability of parts of the molecule to rotate freely in relation to other parts, or from geometrical isomerism, or from intra-molelcular or inter-molecular hydrogen bonding, or otherwise.
  • Preferred compounds of the present invention include those in which, independently or in any combination:
  • R 1 is lower alkyl, particularly methyl or ethyl
  • R 2 is a haloalkoxy or haloalkyl group
  • R 3 is chlorine or bromine
  • Y is chlorine or fluorine
  • R 4 is cyano, bromo, methoxy, nitro or methylsulphonyl.
  • R 2 is a halogen-substituted alkyl or alkoxy group.
  • Halogen-substituted methyl, ethyl, methoxy and ethoxy groups appear to be most suitable and it is also preferred that there is more than one halogen substituent.
  • suitable R 2 substituents include di- and tri- halomethoxy and di- and tri- halomethyl groups with specific examples being
  • dichloromethoxy trifluoromethyl and, especially, difluoromethoxy.
  • Compounds of formula (I) may be prepared by similar routes to those set out in J03072460.
  • R 1 , R 2 , R 4 , X, Y and n are as defined in relation to formula (I).
  • a solvent such as a halogenated hydrocarbon (for example dichloromethane, chloroform or carbon tetrachloride); an aromatic hydrocarbon (such as benzene, toluene or xylene); an ester such as ethyl acetate; a nitrile such as acetonitrile or benzonitrile, a chain-like ether such as diethyl ether or methylcellosolve; a cyclic ether such as dioxane and
  • a solvent such as a halogenated hydrocarbon (for example dichloromethane, chloroform or carbon tetrachloride); an aromatic hydrocarbon (such as benzene, toluene or xylene); an ester such as ethyl acetate; a nitrile such as acetonitrile or benz
  • solvents may be used individually, or they can be used in the form of mixtures.
  • a particularly preferred solvent is acetonitrile.
  • Suitable halogenating agents include chlorinating agents such as chlorine, phosphorus trichloride, phosphorus pentachloride and sulphuryl chloride, as well as other halogenating agents such as bromine and iodine.
  • the reaction temperature should be selected in the range from -30°C to 150°C, preferably from 10°C to 25°C which may be maintained by either the controlled addition of the chlorinating agent or cooling or both.
  • Compounds of general formula (I) in which R 3 is other than halogen may be synthesised from compounds of general formula (I) in which R 3 is halogen, especially bromine.
  • Compounds of general formula (I) in which R 3 is SO 2 Z may be prepared from compounds of general formula (I) in which R 3 is bromine in a three step procedure as follows. Firstly, the compound of general formula (I) in which R 3 is halogen is converted to a compound of general formula (XXI):
  • R 1 , R 2 , R 4 , Y, X and n are as defined in general formula (I) and M is a metal, typically an alkali metal such as lithium or an alkaline earth metal halide such as a magnesium halide.
  • M is a metal, this conversion may be achieved by a transmetallation reaction with a compound of general formula (XXII):
  • R 13 is an optionally substituted alkyl, alkenyl, alkynyl or aryl group, preferably a lower alkyl such as n-butyl, and M is a metal, typically an alkali metal such as lithium.
  • the transmetallation reaction may be conducted in an aprotic solvent, for example an ether such as diethyl ether or tetrahydrofuran, typically under dry inert conditions such as a nitrogen or argon atmosphere.
  • the reaction temperature may be between -100°C and 100°C, more usually between -90°C and 0°C.
  • Compounds of general formula (XXI) as defined above in which M is a metal halide, particularly a magnesium halide, may be prepared by the reaction of compounds of general formula (I) in which R 3 is bromine with magnesium in a dry aprotic solvent, for example an ether such as tetrahydrofuran or 1,2-dimethoxyethane.
  • a dry aprotic solvent for example an ether such as tetrahydrofuran or 1,2-dimethoxyethane.
  • the reaction may be conducted at a temperature of between about 0°C and 200°C, usually between about 15°C and 100°C. It is often advantageous to carry out this reaction under an inert atmosphere such as nitrogen or argon and, under some circumstances, the reaction may be assisted by the presence of a catalytic amount of iodine or by the use of ultrasound.
  • R 1 , R 2 , R 4 , Y, X and n are as defined in general formula (I) and M is as defined for general formula (XXI).
  • reaction solvent will, of course, be the same solvent as was used for the transmetallation reaction.
  • the reaction is preferably carried out under similar conditions to the transmetallation reaction.
  • the compound of general formula (XXIII) may be converted to a compound of general formula (I) in which R 3 is SO 2 Z and Z is chloro by reaction with a chlorinating agent such as thionyl chloride, sulphuryl chloride or oxalyl chloride.
  • a chlorinating agent such as thionyl chloride, sulphuryl chloride or oxalyl chloride.
  • This chlorination reaction may be conducted in an inert solvent, typically an ether such as diethyl ether, a chlorinated solvent such as dichloromethane, an aromatic solvent such as 1,2-dichlorobenzene or a nitrile such as acetonitrile. It is preferable to carry out the reaction under a dry inert atmosphere such as nitrogen or argon and at a temperature of from -50°C to 200°C, more usually between 0°C and 100°C.
  • R 3 is SO 2 Z and Z is other than chloro
  • Z is chloro by a halogen exchange reaction
  • the starting material may be dissolved in a water miscible solvent, for example an ether such as tetrahydrofuran or 1,4-dioxane and then reacted with an aqueous solution of an inorganic or organic halide salt.
  • suitable halide salts include alkali or alkaline earth metal halides such as potassium fluoride.
  • the halogen exchange reaction may take place at a temperature of from 0°C to 200°C, for example from about 50°C to 150°C. In some cases, it is preferable also to conduct the reaction under an inert atmosphere such as nitrogen or argon.
  • the halogen exchange may be achieved by dissolving the compound of general formula (I) in which R 3 is SO 2 Z in a water immiscible solvent, for example a haloalkane such as dichloromethane, an aromatic solvent such as 1,2-dichlorobenzene or an ether such as diethyl ether, and reacting the solution with a halide salt which may, but will not necessarily, be in aqueous solution.
  • a water immiscible solvent for example a haloalkane such as dichloromethane, an aromatic solvent such as 1,2-dichlorobenzene or an ether such as diethyl ether
  • Typical inorganic halide salts are as mentioned above and include, for example, potassium fluoride.
  • the reaction takes place in the presence of a phase transfer catalyst such as a t etraalkyl ammonium or tetraalkyl phosphonium salt, for example tetra-n-butylammonium bromide, or a crown ether and may be conducted at a temperature of from about -50oC to 200°C, usually from about 0°C to 150°C. In some cases, it is preferable to conduct the reaction under an inert atmosphere such as nitrogen or argon.
  • a phase transfer catalyst such as a t etraalkyl ammonium or tetraalkyl phosphonium salt, for example tetra-n-butylammonium bromide, or a crown ether and may be conducted at a temperature of from about -50oC to 200°C, usually from about 0°C to 150°C. In some cases, it is preferable to conduct the reaction under an inert atmosphere such as nitrogen or argon.
  • Suitable acid solutions include aqueous solutions of mineral acids, for example dilute hydrochloric acid, or, alternatively, aqueous solutions of salts of weak bases, for example aqueous ammonium chloride.
  • the reaction may be conducted at a temperature of from -80°C to 50°C, typically -10°C to 30°C.
  • R 1 , R 2 , R 4 , Y, X and n are as defined in general formula (I).
  • Compounds of general formula (XXIV) may be synthesised from compounds of general formula (I) in which R 3 is CO 2 H by chorination using an agent such as thionyl chloride or oxalyl chloride.
  • the reaction may be carried out in the presence of a base, typically an inorganic base and in an inert solvent or mixture of solvents.
  • Suitable solvents include chlorinated solvents such as dichloromethane; ethers such as diethyl ether; aromatic solvents such as 1,2-dichlorobenzene; and amides such as dimethylformamide.
  • the reaction will generally be from -20°C to 150°C, more usually from 10°C to 80°C.
  • R 5 is as defined for general formula (I) except that it is not hydrogen to give the required compound of general formula (I) in which R 3 is CO 2 R 5 and R 5 is other than H.
  • the reaction may be carried out in the presence of a base, which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium carbonate, or an organic base such as a tertiary amine (for example triethylamine), an optionally substituted pyridine or a salt of an appropriate alkoxide.
  • a base which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium carbonate, or an organic base such as a tertiary amine (for example triethylamine), an optionally substituted pyridine or a salt of an appropriate alkoxide.
  • a base which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium
  • the reaction may be carried out in an inert solvent, for example a halogenated solvent such as dichloromethane or an aromatic or heterocyclic solvent such as 1,2-dichlor Tavernzene or pyridine.
  • a nucleophilic catalyst for example a substituted pyridine, typically 4-N,N-dimethylaminopyridine may be employed and the reaction may be conducted at a temperature of from 0°C to 100°C, typically from 10°C to 40°C in an inert atmosphere.
  • a base may also be present and suitable bases are inorganic bases such as alkali and alkaline earth metal hydroxides or carbonates, typically potassium carbonate.
  • an organic base may be used and suitable examples include tertiary amines such as
  • triethylamine or heterocyclic bases such as pyridine.
  • phase transfer catalyst may also be used.
  • Suitable phase transfer catalysts include quaternary ammonium salts, for example tetrabutylammonium iodide, quaternary phosphonium salts, such as tetrabutyl phosphonium bromide, and crown ethers, for example 18-crown-6.
  • R 4 , X, Y and n are as defined in general formula (I), R 8 is as defined in general formula (IV) and R 3 is optionally substituted alkyl, alkenyl or alkynyl.
  • Compounds of general formula (IVa) may be prepared from compounds of general formula (IV) with an alkylating agent of formula:
  • R 3 is as optionally substituted alkyl, alkenyl or alkynyl and U is a leaving group, for example a halogen, particularly chlorine or iodine, a sulphonate ester such as tosylate, mesylate or triflate, or a sulphate half ester, particularly a dialkylsulphate such as
  • the reaction should be conducted in the presence of a base, typically an alkali or alkaline earth metal carbonate, hydroxide or alkoxide although organic bases may also be used.
  • Solvents suitable for this reaction include ethers such as tetrahydrofuran, amides such as N,N-dimethylformamide, nitriles such as acetonitrile, alcohols such as ethanol, esters such as ethyl acetate or other solvents such as dimethyl sulphoxide.
  • R 1 , R 4 , X, Y and n are as defined in relation to formula (I), by reaction with compounds of formula (R c Z), where R c is R 5 (except when R 5 is H), (alkyl)CO 2 R 5 or (alkyl)COR 5 and Z is a leaving group, in the presence of a base as described in the art.
  • a particularly preferred compound of formula (R c Z) is chlorodifluoromethane.
  • the reaction is suitably effected in the presence of a solvent or mixtures of solvents, in the presence or absence of a base and optionally in the presence of a catalyst at a temperature between -10 and 100°C.
  • this reaction is preferably undertaken as a stirred biphasic phase transfer reaction in the presence of an organic solvent and aqueous base solution in the presence of a phase transfer catalyst, preferably at room temperature.
  • Suitable organic solvents are not miscible with water and include chlorinated solvents, for example, dichloromethane, aromatic solvents, for example, toluene, ethers, for example, diethyl ether and esters, for example, ethyl acetate.
  • Dichloromethane is a preferred solvent.
  • Suitable phase transfer catalysts include tetraalkylammonium or
  • Suitable bases are water soluble and include, but are not limited to, alkali and alkaline earth carbonates, bicarbonates and hydroxides, for example, sodium hydroxide.
  • the compound of formula (III) is dissolved in an organic solvent such as dichloromethane with the phase transfer catalyst and the solution is saturated with the compound of formula (R c Z), usually by bubbling this compound in the form of a gas through the solution.
  • the reaction is then initiated by the addition of an aqueous solution of base such as a 50% solution of aqueous sodium hydroxide and the mixture stirred vigorously at room temperature.
  • Compounds of general formula (II) in which R 2 is chloro may be synthesised from compounds of general formula (II) in which R 2 is OH by reaction with a chlorinating agent such as phosphorus oxytrichloride.
  • the reaction may be carried out with or without a solvent and at a temperature of from 0°C to 200°C, preferably 20°C to 150°C.
  • R 4 , X, Y and n are as defined in relation to formula (I) and R 8 is lower alkyl
  • R 1 is as defined in relation to formula (I).
  • the reaction is carried out in the presence or absence of solvent, and optionally in the presence of a catalyst at temperatures of from -10°C to 150°C, in particular at the reflux temperature of any solvent present.
  • Suitable solvents are those which dissolve both reactants and include alcohols, in particular the alcohol
  • reaction may be carried out in the absence of any solvent.
  • a suitable alkylhydrazine such as methylhydrazine
  • R 4 , X, Y and n are defined in relation to formula (I) and R 9 is hydrogen, lower alkyl, hydroxy or a leaving group, for example halo such as chloro.
  • R 8 is as defined above, and R 10 is an activating group, or R 8 and R 10 together form a cyclic activating group.
  • activating group in compounds of formula (VII) means a group which increases the acidity of the hydrogen atoms on the adjacent carbon and is removable by acid catalysed hydroysis, or by base catalysed hydrolysis, or by alcholysis.
  • activating groups R 10 include carboxylic ester groups, in particular alkyl ester groups, salts of carboxylate groups, nitriles and optionally N-substituted amides.
  • R 10 is either a carboxylate ester of formula CO 2 R 11 or a carboxylate salt of formula CO 2 R 12+ .
  • Suitable groups R 11 are optionally substituted alkyl groups such as ethyl, or R 11 together with R 8 may be joined to form a cyclic structure.
  • Suitable cations for R 12+ are organic or inorganic cations.
  • R 12+ is an inorganic cation such as an alkali metal cation, suitably potassium.
  • cyclic activating groups include compounds where R 10 is a group of formula CO 2 R 11 and R 11 with R 8 together form a group >C(CH 3 ) 2 .
  • the compound of formula (VII) is Meldrum's acid.
  • the reaction may be carried out in the presence of solvents or mixtures of solvents.
  • suitable solvents include chlorinated solvents such as dichloromethane, aromatic solvents such as toluene, ether solvents such as diethyl ether and tetrahydrofuran and nitriles such as acetonitrile.
  • Preferred solvents are acetonitrile and ethyl acetate.
  • reaction is carried out optionally in the presence of a base, and in the presence of a nucleophilic catalyst.
  • An inert atmosphere such as nitrogen or argon may be employed.
  • Temperatures of from -70° to 200°C, preferably from -10° to 100°C, and most preferably from 0° to 100°C, are suitably employed.
  • the reaction conditions which give optimal results will vary depending upon the specific nature of the compounds of formulae (VI) and (VII). However the skilled chemist would be able to determine these readily.
  • Suitable bases for use in the reaction include inorganic bases such as alkali or alkaline earth metal hydroxides, bicarb onates, carbonates, hydrides or alcholates, in particular potassium carbonate, sodium hydroxide or sodium ethoxide.
  • organic bases such as tertiary amines, pyridine, substituted pyridines, Hunig's base and diazobicycloundecane may be used.
  • Suitable nucleophilic catalysts include pyridine, substituted pyridine, for example 4-N,N-dimethylaminopyridine, tertiary amines such as trialkylamines, N-hydroxysuccinimide and optionally substituted imidazoles.
  • the reaction may also require the presence of a non basic inorganic salt.
  • Suitable salts include, but are not limited to, magnesium salts, in particular magnesium halides such as magnesium chloride.
  • the compound of formula (IV) is preferably prepared using a base-mediated reaction as described above but additionally in the presence of a dehydrating agent such as
  • carbonyldiimidazole or a carbodiimide for example N,N-dicyclohexylcarbodiimide.
  • preferred temperatures are from -60° to 150°C, typically from 20° to 40°C; a preferred solvent is dichloromethane and a preferred base is triethylamine.
  • 4-N,N-Dimethylaminopyidine is a typical nucleophilic catalyst for this reaction.
  • the reaction is suitably effected in the presence of a base and in particular Hunig's base. Temperatures of from -60° to 100°C and in particular about 0°C are preferred in these circumstances, and
  • dichloromethane is a preferred solvent.
  • Compound (VI) is typically an acid chloride (i.e. R 9 is chloride).
  • a typical process comprises the pre-formation of a slurry of the malonate half ester salt, a magnesium salt, preferably magnesium chloride, and a base, preferably triethylamine.
  • the process is effected in an inert solvent, preferably acetonitrile, under an inert atmosphere of, for example, nitrogen, with vigorous stirring and cooling, typically to about 10°C.
  • the reaction is typically initiated by the careful addition of the compound of formula (VI) where R 9 is chloro to the cooled reaction mixture, usually at about 0°C.
  • the mixture is then stirred at a temperature between 0°C to 100°C, generally at room temperature, for an extended period, conveniently overnight.
  • Other compounds of formula VI in which R 4 , Y, X and n are as defined in formula (I) and R 9 is hydrogen, halogen, hydroxy or lower alkyl, particularly methyl, may also be prepared by standard literature procedures.
  • R 4 is OR 5 and R 5 is an alkyl, alkenyl or alkynyl group (any of which may optionally be substituted) may be synthesised from compounds of general formula (lb):
  • R 5 is as defined in general formula (la) and U is a leaving group.
  • suitable leaving groups include halogen, such as chlorine or iodine, sulphonate esters such as tosylate, mesylate and triflate, and sulphate half esters, particularly as in dialkylsulphates such as dimethylsulphate.
  • suitable solvents include ketones, especially dialkyl ketones such as acetone; ethers such as diethyl ether; chlorinated alkyanes such as chloromethane; nitriles such as acetonitrile; amides such as
  • dimethylformamide and aromatic solvents such as 1,2-dichlorobenzene.
  • bases include inorganic bases such as alkali or alkaline earth metal hydroxides, hydrides or carbonates. Specific examples of such bases include potassium carbonate, sodium hydride and potassium hydroxide.
  • an organic base for example a tertiary amine such as triethylamine or a heterocyclic base such as pyridine may be used.
  • a catalyst such as an iodide salt, for example potassium iodide.
  • a phase transfer catalyst may be preferred and examples of such catalysts include quaternary ammonium salts such as tetra n-butyl ammonium bromide, quaternary phosphonium salts such as tetra n-butyl phosphonium bromide and crown ethers such as 18-crown-6.
  • a suitable reaction temperature is from -30°C to 200°C, more usually from 0°C to
  • R 1 , R 2 , R 3 , Y, X and n are as defined in general formula (I) and A- is a suitable counter ion, typically tetrafluoroborate or halide, especially chloride, by reaction with an aqueous solution or suspension of an inorganic salt .
  • suitable inorganic salts are, for example, copper salts and typically a mixture of such salts is used.
  • cuprous oxide may be mixed with cupric nitrate.
  • the reaction will be carried out at a temperature of 5°C to 30°C and cooling may be required to control the reaction.
  • reaction may be carried out using standard literature procedures, for example, the reaction of the compound of the formula (Ic) with an inorganic nitrite or an organic nitrite of general formula (XII):
  • R 11 is typically an alkyl group.
  • the reaction may be carried out in aqueous solution in the presence of an acid such as hydrochloric acid, at a reaction temperature of from 0°C to 10°C, preferably 0°C.
  • the inorganic nitrite will preferably be an alkali metal nitrite such as sodium nitrite.
  • the product of general formula (X) may be used without further isolation or may be purified before further reaction.
  • a compound of formula (Ic) is reacted with the nitrite of formula (XII) in an inert solvent.
  • suitable solvents include chlorinated alkanes, for example dichloroethane, and aromatics, for example 1,2-dichloro benzene. Warming may be required to initiate the reaction and the reaction temperature is typically copntrolled by the rate of addition of a solution of Compound (XII) and a solution of Compound (Ic).
  • Suitable temperatures for the reaction are from -30°C to 200°C, typically 20°C to
  • R 4 is NO 2 , by reduction.
  • Methods for the reduction of nitro compounds to give amines are well known in the literature and, for example, the compound of general formula (Id) may be reduced using a transition metal salt such as titanium trichloride, usually in a solvent, for example a ketonic solvent such as acetone.
  • a transition metal salt such as titanium trichloride
  • a solvent for example a ketonic solvent such as acetone.
  • a reaction will be carried out between 0°C and 100°C, more typically, between 10°C and 40°C.
  • An alternative reduction method uses a dissolving metal such as tin or zinc in an acid.
  • the acid will be a mineral acid, such as aqueous hydrochloric acid, and a co-solvent, for example an alcohol such as methanol, may also be used.
  • the reaction temperature will generally be between 0°C and 100°C and, preferably, will be between 10°C and 50°C.
  • Yet another method for the reduction of the nitro compounds (Id) is the use of a catalytic hydrogenation reaction which may be carried out at a pressure equal to or greater than one atmosphere and at a temperature of from 0°C to 200°C typically from 10 °C to 50°C.
  • the reaction will generally be carried out in an alcoholic solvent such as ethanol or methanol in the presence of a transition metal catalyst such as palladium or platinum or one of their oxides, which may be on inert support such as charcoal.
  • R 4 is SO p R 5 may be prepared by the oxidation of the compounds of general formula (If):
  • R 4 is SR 5 .
  • Suitable oxidising agents for this conversion include peracids such as n-chloroperbenzoic acid, dioxiranes such as dimethyldioxirane, periodate salts such as potassium periodate and salts of higher oxidation states transition metals including potassium permanganate.
  • the reaction will usually be carried out in a solvent such as a ketone, for example acetone; a chlorinated alkane such as dichloromethane or chloroform; an ether such as tetrahydrofuran; an aromatic solvent such as 1,2-dichlorobenzene or a heterocyclic solvent such as pyridine.
  • the reaction may be conducted at a temperature of from -30°C to 200°C, typically from 0°C to 40°C. It is generally preferable for the reaction to be carried out in an inert atmosphere such as argon or nitrogen.
  • R 5 is as defined for general formula (I).
  • the reaction may be carried out under an inert atmosphere such as nitrogen or argon at a temperature of from -30°C to 100°C, typically 0°C to 70°C.
  • Suitable solvents include halogenated alkanes such as 1,2-dichloroethane or dichloromethane; ethers such as diethyl ether and tetrahydrofuran; and aromatic solvents such as 1,2 -dichlorobenzene.
  • Compounds of general formula (X) may be prepared as specified above.
  • R 4 is SO 2 Z and Z is halo
  • typically chloro or bromo may alos be prepared from compounds of general formula (X) by reaction with sulphur dioxide in the presence of an inorganic salt or mixture of salts.
  • Suitable inorganic salts include copper salts especially copper (I) salts such as copper (I) halides, in particular cuprous chloride.
  • the sulphur dioxide will often be in solution with typical solvents being organic acids, espeically alkanoic acids such as acetic acid.
  • a preferred experimental procedure involves saturating the solvent with sulphur dioxide piror to initiation of the reaciton with the compound of general formula (X).
  • the addition of the sulphur dioxide to the compound of general formula (X) may take place at reduced temperature, for example about -40°C to 30°C, more usually from about -5 °C to 15°C with the reaction mixture subsequently being allowed to warm to room temperature.
  • the product of this reaction is a compound of general formula (Iq) in which R 4 is chloro. If compounds in which R 4 is halo other than chloro are required, these may be synthesised from compounds of general formula (Iq) in which R 4 is chloro by a halogen exchange reaction with an organic or inorganic halide salt, typically a salt such as potassium fluoride.
  • the starting compound of general formula (I) may either be dissolved in a water miscible solvent such as 1,4-dioxane or tetrahydrofuran and reacted with an aqueous solution of the salt or it may be dissolved in a solvent such as dichloromethane which is not water miscible and reacted with the salt or an aqueous solution of the salt in the presence of a phase transfer catalyst.
  • the halogen exchange reaction may take place at a temperature of from 0°C to 200°C, for example from about 50°C to 150°C. In some cases, it is preferable also to conduct the reaction under an inert atmosphere such as nitrogen or argon.
  • R 4 is R 5 SO 2 O- and R 5 is as defined in general formula (I) may be prepared by the reaction of a compound of general formula (lb) with a sulphonyl chloride of general formula (XIII):
  • R 5 is as defined in general formula (I).
  • the reaction may be carried out in a suitable solvent for example a halogenated alkane, such as dichloromethane; an ether such as tetrahydrofuran; a nitrile such as acetonitrile; an amide such as dimethylformamide; an aromatic solvent such as 1,2-dichlorobenzene; or a heterocyclic solvent such as pyridine.
  • a suitable solvent for example a halogenated alkane, such as dichloromethane; an ether such as tetrahydrofuran; a nitrile such as acetonitrile; an amide such as dimethylformamide; an aromatic solvent such as 1,2-dichlorobenzene; or a heterocyclic solvent such as pyridine.
  • a suitable solvent for example a halogenated alkane, such as dichloromethane; an ether such as tetrahydrofuran; a nitrile such as ace
  • the reaction will usually be conducted in the presence of a base which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium carbonate; or an organic base, suitably a tertiary amine such as triethylamine or a heterocyclic base such as pyridine or imidazole.
  • a nucleophilic catalyst will often be required and suitable catalysts include heterocycles, for example a pyridine such as 4-N,N-dimethylaminopyridine or an imidazole.
  • the reaction will be carried out under an inert atmosphere such as nitrogen or argon.
  • R 4 is NHCOR 5 and R 5 is as defined in general formula (I)
  • R 4 is NHCOR 5 and R 5 is as defined in general formula (I)
  • R 4 is NHCOR 5 and R 5 is as defined in general formula (I)
  • R 4 is NHCOR 5 and R 5 is as defined in general formula (I)
  • R 4 is NHCOR 5 and R 5 is as defined in general formula (I)
  • R 4 is NHCOR 5 and R 5 is as defined in general formula (I)
  • R 5 is as defined in general formula (I)
  • a dehydrating agent such as carbodiimide
  • N.N'-dicyclohexylcarboiimide N.N'-dicyclohexylcarboiimide.
  • Alternative dehydration agents include disubstituted carbonyl derivatives of formula COQQ', where Q and Q' are leaving groups, for example
  • 1,1'-carbonyldiimidazole 1,1'-carbonyldiimidazole.
  • the compound of general formula (Ic) may be reacted with a methyl ester in the presence of a trialkylaluminium species such as trimethylaluminium.
  • the reaction will, in most cases, be carried out in the presence of a base which may be an inorganic base such as an alkali or alkine earth metal hydroxide, carbonate or bicarbonate, typically potassium carbonate; or an organic base, for an example a tertiary amine such as triethylamine.
  • a heterocyclic base such as pyridine or imidazole may also be used.
  • a nucleophilic catalyst will often be required and suitable catalysts include heterocycles such as 4-N,N-dimethylaminopyridine or imidazole.
  • the reaction may be carried out under an inert atmosphere such as nitrogen or argon at a temperature of -30°C to 200°C, more typically, 0°C to 100°C.
  • R 4 is -NHSO 2 R 5 and R 5 is as described in formula (I)
  • R 4 may also be prepared from compounds of general formula (Ic) by reaction with a sulphonyl chloride of general formula (XIII) in which R 5 is as defined in general formula (I).
  • the reaction may be carried out in a solvent such as a halogenated alkane for example dichloromethane; an ether such as tetrahydrofuran; a nitrile such as acetonitrile; an amide such as dimethylformamide; an aromatic solvent such as 1,2-dichlorobenzene; a heterocyclic solvent such as pyridine; or a polar solvent such as dimethylsulphoxide.
  • a solvent such as a halogenated alkane for example dichloromethane; an ether such as tetrahydrofuran; a nitrile such as acetonitrile; an amide such as dimethylformamide; an aromatic solvent such as 1,2-d
  • a nucleophilic catalyst such as those defined above may be used and the reaction will usually be carried out in an anhydrous inert atmosphere at a temperature of from -30°C to 200°C, typically from 0°C to 100°C.
  • the reaction will usually be conducted in the presence of an organic or an inorganic base and, suitable bases are those listed above for the conversion of compound of general formula (Ic) to the compound of general formula (Ih).
  • R 4 is CO 2 R 5 and R 5 is hydrogen
  • R 4 is CO 2 R 5 and R 5 is hydrogen
  • the hydrolysis may be either acid or base catalysed and may be carried out in either an aqueous or a non-aqueous medium.
  • an organic solvent will be used and the reaction temperature will be between 0°C and 200°C, typically 50°C to 120°C.
  • Suitable acid catalysts include mineral acids such as hydrochloric or sulphuric acid and base catalysts include alkaline and alkaline earth metal hydroxides or carbonates, for example potassium hydroxide.
  • the reaction solvent may be an alcohol such as ethanol; an ether such as tetrahydrofuran; or a nitrile such as acetonitrile; or water.
  • a mixture of solvents may be used.
  • a phase transfer catalyst may be required and suitable agents include crown ethers, tetraalkylammonium salts or tetraalkylphosphonium salts.
  • R 4 is CO 2 R 5 and R 5 is other than hydrogen
  • R 5 is other than hydrogen
  • R 5 is as defined for general formula (I) except that it is not hydrogen.
  • the reaction may be carried out in the presence of a base, which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium carbonate, or an organic base such as a tertiary amine (for example triethylamine), an optionally substituted pyridine or a salt of an appropriate alkoxide.
  • a base which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium carbonate, or an organic base such as a tertiary amine (for example triethylamine), an optionally substituted pyridine or a salt of an appropriate alkoxide.
  • a base which may be an inorganic base such as an alkali or alkaline earth metal hydroxide or carbonate, typically potassium carbonate, or an organic base such as a tertiary amine (for example triethylamine
  • 4-N,N-dimethylaminopyridine may be employed and the reaction may be conducted at a temperature of from 0°C to 100°C, typically from 10°C to 40°C in an inert atmosphere.
  • Compounds of general formula (XV) may be synthesised from a compound of general formula (Il) by chorination using an agent such as thionyl chloride or oxalyl chloride.
  • the reaction may be carried out in the presence of a base, typically an inorganic base and in an inert solvent or mixture of solvents.
  • Suitable solvents include chlorinated solvents such as dichloromethane; ethers such as diethyl ether; aromatic solvents such as 1,2 -dichlorobenzene; and amides such as dimethylformamide.
  • the reaction will generally be from -20°C to 150°C, more usually from 10°C to 80°C.
  • An alternative synthesis for compounds of general formula (Ij) is the reaction of compounds of (II) with compounds of formula (XIV) in the presence of a dehydrating agent such as a carbodiimide, typically N.N-dicyclohexylcarbodiimide, or a di-substituted carbonyl derivative of formula COQQ' where Q and Q' are leaving groups such as in
  • a nucleophilic catalyst may also be present and the reaction should preferably be conducted in a dry inert atmosphere and in a solvent such as a halogenated solvent, for example dichloromethane; an ether, for example tetrahydrofuran; a nitrile, for example acetonitrile; an aromatic solvent, for example dichlorobenzene; or a heterocyclic solvent, for example pyridine.
  • a base may also be present and suitable bases are inorganic bases such as alkali and alkaline earth metal hydroxides or carbonates, typically potassium carbonate. Alternatively, an organic base may be used and suitable examples include tertiary amines such as triethylamine or heterocyclic bases such as pyridine.
  • phase transfer catalyst may also be used.
  • Suitable phase transfer catalysts include quaternary ammonium salts, for example tetrabutylammonium iodide, quaternary phosphonium salts, such as tetrabutyl phosphonium bromide, and crown ethers, for example 18-crown-6.
  • R 4 is CONR 5 R 6 may also be prepared from compound (Il) or compound (XV) by reaction with a compound of general formula XVI:
  • R 5 and R 6 are as defined in general formula (I).
  • the reaction may be carried out in the presence of a base which may be either organic or inorganic.
  • Suitable inorganic bases include alkali or alkaline earth metal carbonates and bicarbonates, for example potassium carbonate; and organic bases include tertiary amines, for example triethylamine, and pyridine.
  • Suitable solvents for the reaction include chlorinated solvents such as dichloromethane; ethers such as tetrahydrofuran; nitriles such as acetonitrile; and amides such as dimethylformamide.
  • a mixture of solvents may also be employed and, in some cases, the mixture may be heterogenous with organic and aqueous phases. It is often preferable to employ a
  • nucleophilic catalyst such as 4-N,N-dimethylaminopyridine, pyridine or imidazole.
  • the reaction may be carried out in an inert atmosphere at a temperature of -20°C to 150°C, typically 10°C-80°C.
  • a dehydrating agent such as N,N'-dicycIohexylcarbodiimide or a di-substituted carbonyl derivative of general formula
  • QCOQ' where Q and Q' are leaving groups which may be the same or different.
  • Examples of such disubstituted carbonyl derivatives include 1,1-carbonyldiimidazole.
  • An alternative route for the production of compounds of general formula (Ik) is by the reaction of compounds (Im), in which R 4 is nitrile, by controlled hydrolysis. This is appropriate for compounds of general formula (Ik) in which R 5 and R 6 are both hydrogen.
  • the reaction may be carried out under either acidic or basic conditions, optionally in an aqueous solvent.
  • the reaction temperature will generally be between 0°C and 200°C, more typically between 50°C and 120°C.
  • Suitable acids are hydrochloric acid and sulphuric acid while for base catalysed reactions, suitable bases include alkali and alkaline earth metal hydroxides and carbonates.
  • Suitable solvents for the reaction include ethers such as tetrahydrofuran, nitriles such as acetonitrile, amides such as N,N-dimethylformamide, water and mixtures of these.
  • R 1 , R 2 , R 3 , Y, X and n are as defined in general formula I and R t is an alkyl group, for example a tertiary alkyl group such as tertiary butyl, with an amine of general formula (XVI).
  • the reaction may be carried out in the presence of a nucleophilic catalyst in an inert atmosphere at a temperature of -20°C to 200°C, more typically from 0°C to 100°C.
  • Suitable reaction solvents include chlorinated aliphatic solvents such as dichloromethane; ethers such as tetrahydrofiiran; aromatic solvents such as 1,2-dichlorobenzene; nitriles such as
  • Suitable nucleophilic catalysts include pyridines, such as 4-N,N-dimethylaminopyridine, and imidazoles.
  • R t is an alkyl, typically a tertiary alkyl, group for example tertiary butyl.
  • the reaction may be carried out in the presence of a base and/or a nucleophilic catalyst.
  • a base and/or a nucleophilic catalyst may be employed in the presence of a base and/or a nucleophilic catalyst.
  • an anhydrous inert atmosphere such as nitrogen or argon and the temperature may be from -20°C to 200°C, typically from 0°C to 100°C.
  • the solvent may be a chlorinated alkane, an ether, a nitrile, an aromatic or heterocyclic solvent or an amide.
  • the base may be either an inorganic or an organic base and the nucleophilic catalyst may be a heterocyclic catalyst such as a
  • compounds of general (Ik) may be synthesised directly from compounds of general formula (Ij), wherein R 5 is alkyl, in particular methyl, by reaction with an amine of general formula (XVI).
  • a catalyst particularly an aluminium based derivative.
  • examples of these include trialkyl aluminiums, and especially lower alkylaluminiums such as trimethylaluminium.
  • Appropriate reaction solvents include fluorinated alkanes, ethers and aromatic solvents.
  • the reaction is preferably carried out in an inert atomosphere at a temperature of from -20°C to 200°C, more typically from 0 °C to 50°C.
  • the synthesis of Compounds (Ij), (Ik), (Il), and (Im) is summarised in Reaction Scheme II.
  • R 1 , R 3 , R 4 , Y, X and n are as defined for general formula (I) and in which R 2 is SOR 5 and SO 2 R 5 respectively (with R 5 as defined for general formula (I)) may be synthesised using previously defined methods from corresponding compounds of general formulae (IIn) and (IIo):
  • R 1 , R 3 , R 4 , R 5 , Y, X and n are as defined for general formula (I).
  • Suitable oxidising agents include peracids, such as m-chloroperbenzoic acid; periodate salts such as potassium periodate; and salts of higher oxidation state transistion metals, for example potassium permanganate.
  • the amount and type of oxidising agent used may be chosen by the chemist according to whether a compound of general formula (IIn) or (IIo) is required.
  • the reaction may be carried out in an anhydrous inert atmosphere and an anhydrous solvent such as a halogenated alkane, ether or an aromatic solvent may be used. Specific solvents include chloromethane, chloroform, diethyl ether and 1,2-dichlorobenzene.
  • reaction temperature will generally be between -20°C and 200°C, more suitably between 0°C and 100°C.
  • Compounds of general formula (IIa) in which R 5 is other than hydrogen may be prepared as described above from compounds of general formula (IIb):
  • R 2 is SH using analagous methods to those described above for the synthesis of compounds of compounds of general formula D from compounds of general formula III.
  • Compounds of general formula (IIb) may be synthesised from compounds (III) using a suitable thionating agent such as Lawesson's reagent 2,4-bis(4-methyloxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulphide.
  • the reaction may be conducted at a temperature of from -30°C to 200°C, usually from 50°C to 200°C.
  • suitable solvents include chlorinated alkanes, ethers and aromatics. Specific examples of solvents are chloroform, tetrahydrofuran, xylene and 1,2-dichlorobenzene.
  • An alternative route for the synthesis of compounds of general formula (IIa) is by the reaction of general formula (XIX):
  • R 4 , R 5 , Y, X and n are as defined for general formula (I), with a compound of general formula (V) under similar conditions to those employed in the conversion of compounds of general formula (IV) to compounds of general formula (III).
  • Compounds of general formula (XIX) may be prepared by the sequential reaction of a compound of general formula (VI) as defined above in which R 9 is lower alkyl, in particular methyl, with carbondisulphide and then an alleviating agent of general formula (IX):
  • R 5 is as defined in general formula (I) and U is a leaving group.
  • Typical leaving groups, U include halogen, particularly iodide, sulphonate esters such as tosylate and sulphate half esters as in, for example, dimethylsulphate.
  • the reaction may be carried out in a solvent or a mixture of solvents and suitable solvents are chosen from aromatic solvents, amides, ethers and chlorinated alkanes. Specific examples of suitable solvents include toluene, dimethylacetamide, tetrahydrofuran and dichloromethane.
  • an organic or inorganic base will be present in the reaction mixture.
  • inorganic bases include alkali or alkaline earth metal hydrides, hydroxides or carbonates typically sodium hydroxide.
  • organic bases are alkali metal alkoxides, particularly sodium ethoxide, and tertiary amines such as diazobicycloundecane.
  • the reaction temperature will typically be -30°C to 200°C , more probably from 0oC to 50°C.
  • the compounds of formula (I) above are active as herbicides and the invention therefore provides, in a further aspect, a process for severely damaging or killing unwanted plants, which process comprises applying to the plants, or to the growth medium of the plants, a herbicidally effective amount of a compound of formula (I) as hereinbefore defined.
  • the compounds of formula (I) are active against a broad range of weed species including monocotyledonous and dicotyledonous species. They show some selectivity towards certain species; they may be used, for example, as selective heibicides in soya crops.
  • the compounds of formula (I) may be applied directly to unwanted plants (post-emergence application) but they are preferably applied to the soil before the unwanted plants emerge (pre-emergence application).
  • the compounds of formula (I) may be used on their own to kill or severely damage plants, but are preferably used in the form of a composition comprising a compound of formula (I) in admixture with a carrier comprising a solid or liquid diluent.
  • compositions containing compounds of formula (I) include both dilute compositions, which are ready for immediate use, and concentrated compositions, which require to be diluted before use, usually with water.
  • the compositions Preferably contain from 0.01% to 90% by weight of the active ingredient.
  • Dilute compositions ready for use preferably contain from 0.01 to 2% of active ingredient, while concentrated compositions may contain from 20 to 90% of active ingredient, although from 20 to 70% is usually preferred.
  • the solid compositions may be in the form of granules, or dusting powders wherein the active ingredient is mixed with a finely divided solid diluent, e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum. They may also be in the form of dispersible powders or grains, comprising a wetting agent to facilitate the dispersion of the powder or grains in liquid. Solid compositions in the form of a powder may be applied as foliar dusts.
  • a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth and gypsum.
  • a finely divided solid diluent e.g. kaolin, bentonite, kieselguhr, dolomite
  • Liquid compositions may comprise a solution or dispersion of an active ingredient in water optionally containing a surface-active agent, or may comprise a solution or dispersion of an active ingredient in a water-immiscible organic solvent which is dispersed as droplets in water.
  • Surface-active agents may be of the cationic, anionic, or non-ionic type or mixtures thereof.
  • the cationic agents are, for example, quaternary ammonium compounds (e.g.
  • Suitable anionic agents are soaps; salts of aliphatic mono ester of sulphuric acid, for example sodium lauryl sulphate; and salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium, and ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalenesulphonic acid.
  • Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol and cetyl alcohol, or with alkylphenols such as octyl- or nonyl- phenol (e.g. Agral 90) or octyl-cresol.
  • Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, for example sorbitan monolaurate; the condensation products of the partial ester with ethylene oxide; the lecithins; and silicone surface active agents (water soluble surface active agents having a skeleton which comprises a siloxane chain e.g. Silwet L77).
  • a suitable mixture in mineral oil is Atplus 411F.
  • aqueous solutions or dispersions may be prepared by dissolving the active ingredient in water or an organic solvent optionally containing wetting or dispersing agent(s) and then, when organic solvents are used, adding the mixture so obtained to water optionally containing wetting or dispersing agent(s).
  • organic solvents include, for example, ethylene di-chloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene.
  • compositions for use in the form of aqueous solutions or dispersions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, and the concentrate is then diluted with water before use.
  • the concentrates are usually required to withstand storage for prolonged periods and, after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Concentrates conveniently contain 20-90%, preferably 20-70%, by weight of the active ingredient(s).
  • Dilute preparations ready for use may contain varying amounts of the active ingredient(s) depending upon the intended purpose; amounts of 0.01% to 10.0% and preferably 0.1% to 2%, by weight of active ingredients) are normally used.
  • a preferred form of concentrated composition comprises the active ingredient which has been finely divided and which has been dispersed in water in the presence of a
  • suspending agents are hydrophilic colloids and include, for example polyvinylpyrrolidone and sodium carboxymethylcellulose, and vegetable gums, for example gum acacia and gum tragacanth.
  • Preferred suspending agents are those which impart thixotropic properties to, and increase the viscosity of the concentrate.
  • preferred suspending agents include hydrated colloidal mineral silicates, such as montmorillonite, beidellite, nontronite, hectorite, saponite, and saucorite. Bentonite is especially preferred.
  • Other suspending agents include cellulose derivatives and polyvinyl alcohol.
  • the rate of application of the compounds of the invention will depend on a number of factors including, for example, the compound chosen for use, the identity of the plants whose growth is to be inhibited, the formulations selected for use and whether the compound is to be applied for foliage or root uptake. As a general guide, however, an application rate of from 0.001 to 20 kilograms per hectare is suitable while from 0.025 to 1 kilograms per hectare may be preferred.
  • compositions of the invention may comprise, in addition to one or more compounds of the invention, one or more compounds not of the invention but which possess biological activity. Accordingly in yet a still further embodiment the invention provides a herbicidal composition comprising a mixture of at least one herbicidal compound of formula (I) as hereinbefore defined with at least one other herbicide.
  • the other herbicide may be any herbicide not having the formula (I). It will generally be a herbicide having a complementary action in the particular application.
  • Examples of useful complementary herbicides include:
  • B. hormone herbicides particularly the phenoxy alkanoic acids such as MCPA, MCPA-thioethyl, dichlorprop, 2,4,5-T, MCPB, 2,4-D, 2,4-DB, mecoprop, trichlopyr, clopyralid, and their derivatives (eg. salts, esters and amides);
  • D Dinitrophenols and their derivatives (eg. acetates) such as dinoterb, dinoseb and its ester, dinoseb acetate;
  • dinitroaniline herbicides such as dinitramine, trifluralin, ethalflurolin,
  • arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron,
  • uracil herbicides such as lenacil, bromacil and terbacil;
  • J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine,
  • prometryn dimethametryn, simetryne, and terbutryn
  • K. phosphorothioate heibicides such as piperophos, bensulide, and butamifos;
  • L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate * , EPTC * , tri-allate, di-allate, esprocarb, tiocarbazil, pyridate, and dimepiperate;
  • N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
  • O. anilide herbicides such as pretilachlor, butachlor, alachlor, propachlor,
  • P. dihalobenzonitrile herbicides such as dichlobenil, bromoxynil and ioxynil
  • Q. haloalkanoic herbicides such as dalapon, TCA and salts thereof
  • R diphenylether herbicides such as lactofen, flurogiycofen or salts or ester
  • S. phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof, quizalofop and esters thereof and fenoxaprop and esters thereof such as the ethyl ester;
  • T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, tralkoxydim, and clethodim;
  • U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfliron and esters thereof; benzsulfuron and esters thereof such as DPX-M6313, chlonmuron and esters such as the ethyl ester thereof pirimisulfuron and esters such as the methyl ester thereof, 2-[3-(4-methoxy-6-methyl-1,3,5- triazin-zyl)-3-methylureidosulphonyl) benzoic acid esters such as the methyl ester thereof (DPX-LS300) and pyrazosulfuron;
  • V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
  • arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
  • X. amino acid herbicides such as glyphosate and glufosinate and their salts and esters, sulphosate and bialaphos;
  • Y. organoarsenical herbicides such as monosodium methanearsonate (MSMA);
  • herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide and naptaiam;
  • miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulphate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, flurochloridone, quinchlorac, mefanacet, and triketone herbicides such as sulcotrione;
  • Examples of useful contact herbicides include:
  • bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat;
  • NMR spectrum nuclear magnetic resonance spectrum which were recorded at 270 or
  • Step a Preparation of 2-fluoro-4-nitrobenzoylchloride.
  • Step b Preparation of ethyl 3-(2-fluoro-4-nitrophenyl)-3-oxoproprionate.
  • Triethylamine (9.7g) and magnesium chloride (11.4g) were added with vigorous stirring to a mixture of potassium ethyl malonate (17.95g) in acetonitrile (75 ml) already cooled to less than 10°C under an inert atmosphere of nitrogen. The mixture was allowed to warm to room temperature and stirred for a further 21 ⁇ 2 hours. The slurry was then cooled to 0°C and 2-fluoro-4-mtrobenzoylchlor.de (10g), prepared as described in Step a, in acetonitrile was added dropwise over 15 minutes. A further portion of triethylamine (0.97g) was added and the mixture allowed to warm to room temperature, then stirred overnight.
  • reaction mixture was concentrated under vacuo to remove the acetonitrile, suspended in toluene and reconcentrated under vacuo.
  • the residue was suspended in ethyl acetate and the mixture cooled to 10°C.
  • Aqueous 13% hydrochloric acid 50 ml was added carefully to the mixture with vigorous stirring while maintaining the temperature at less than 25°C.
  • the reaction mixture was allowed to stand and separated into two layers. The layers were separated and the aqueous phase was extracted with ethyl acetate.
  • the organic phase and ethyl acetate extracts were combined, washed with 13% aqueous hydrochloric acid and water, dried over anhydrous magnesium sulphate and concentrated under vacuo to give a pale orange gum which solidified on standing
  • ⁇ H(CDCl 3 ) 1.25(3H,t); 4.05(2H,d); 4.2(2H,q); 1.35(3H,t); 4.3(2H,q); 5.75(1H,s);
  • Step d Preparation of 5-difluoromethoxy-3-(2-fluoro-4-nitrophenyl)-1-methylpyrazole.
  • Chlorodifluoromethane gas was bubbled through a mixture of
  • 3-(2-fluoro-4-nitrophenyl)-5-hydroxy-1-methypyrazole prepared as described in Step c, (15g) suspended in dichloromethane (200ml) until the mixture was saturated. 50% Aqueous sodium hydroxide solution (150ml) was added dropwise with vigorous stirring. The mixture was stirred for approximately 1 hour at room temperature and then 1 hour at 30°C. After cooling, the mixture was diluted with water. Two layers were separated and the aqueous phase extracted with dichloromethane.
  • Step e Preparation of 4-chloro-5-difluoromethoxy-3-(2-fluoro-4-nitrophenyl)-1-methylpyrazole, (Compound 1 of Table I).
  • Titanium trichloride (30ml of 30% w/v solution in aqueous hydrochloric acid) was added dropwise to a stirred solution of Compound 1 in Table I, prepared as described in Example 1, (6.2g) in acetone (60 ml) while the internal temperature was maintained at less than 30°C.
  • the progress of the reaction was monitored by the thin layer chromatography (TLC). On completion, when no more starting material remained in the reaction mixture, water was added and the mixture extracted with ethyl acetate (3 ⁇ 100ml).
  • Compound 6 was prepared by a similar process using appropriate starting materials and reagents.
  • Oxalyl chloride (0.4ml) was added to a vigorously stirred suspension of Compound 5 from Table I, prepared as described in Example 4, (0.600g) in dichloromethane (2.0ml). A drop of dimethylformamide was added and the reaction mixture stirred for 3 hours at room temperature. The mixture was concentrated under vacuo. Concentrated aqueous ammonia solution was added to a stirred solution of the residue in dichloromethane and the reaction mixture was stirred for a further 2 hours at room temperature, during which time a precipitate formed. The precipitate was collected by filtration, washed with dichloromethane and dried to give the desired product
  • Methanesulphonylchloride (0.240g) was added to a solution of Compound 2 in Table I, prepared as described in Example 2, (0.583g) and triethylamine (0.212g) in chloroform (5.0ml) and the mixture heated at reflux for 2 hours.
  • Step a Preparation of 3-fluoro-4-(4-chloro-5-difluoromethoxy-1-methylpyrazol-3-yl)-phenyldiazonium tetrafluoroborate salt.
  • Step b
  • the diazonium salt, prepared as described in Step a, (6.5g) was added to a vigorously stirred solution of copper (II) nitrate trihydrate (92.35g) in water (170ml) and the resulting mixture was stirred at room temperature for 1 hour. Copper (I) oxide (0.924g) was added to the reaction mixture, which became frothy. After stirring for a further hour at room temperature, the reaction mixture was extracted with dichloromethane (2 ⁇ 150ml). The organic extracts were washed with water, dried over anhydrous magnesium sulphate, filtered and concentrated under vacuo to give a brown gum (4.4g, 88%) which could be used in other reactions without further purification. A sample of the residue (1g) was further purified by column chromatography on SorbsilTM silica eluting with hexane:ethyl acetate : : 1:1.
  • Step a Preparation of 3-(4-chloro-2-fluorophenyl)-1-methyl-5-thiopyrazole.
  • Step b Preparation of 5-difluoromethylsulphide-3-(4-chloro-2-fluorophenyl)-1-methylpyrazole.
  • This compound was prepared from the product of Step a of this Example (5.7g) in a similar process to that described in Example 1, Step d using appropriate reagents and starting materials, as a pale yellow solid, (2.14g, 35%), m.p. 60-62°C.
  • Step c Preparation of 4-chloro-5-difluoromethylsulphide-3-(4-chloro2-fluorophenyl)-1-methyl-pyrazole, Compound 18 in Table I.
  • the compound was prepared from the product of Step b above (1.56g) by a similar process to that described in Step e of Example 1, using appropriate reagents and starting materials.
  • the product was obtained as a pale yellow viscous gum (1.49g).
  • Compound 23 was prepared by a similar process using appropriate starting materials, reagents and conditions.
  • m-Chloroperbenzoic acid (0.356g) was added to a stirred solution of Compound 13 in Table I, prepared as described in Example 7, (0.555g) in dichloromethane (45ml) and the mixture heated at reflux for 3 hours. After cooling, the mixture was washed with aqueous sodium bisulphite solution and then with aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulphate, filtered and concentrated under vacuo to give a gum which was purified by column chromatography on SorbsilTM silica gel eluting with hexane:ethyl acetate:: 1 :2. Concentration of the appropriate fractions under vacuo, gave the desired product as a pale yellow gum (0.238g,, 41%).
  • This compound was prepared from Compound 15 in Table I, prepared as described in
  • Example 9 (0.8g) by an analogous process to that described in Step d of Example 1, using appropriate starting materials and reagents, to give a pale yellow viscous gum (0.474mg, 51%).
  • Step a Preparation of Methyl 2-fluoro-4-(2-trimethysilylethynyl)-benzoate.
  • Step c Preparation of 4-ethynyl-2-fluorobenzoyl chloride.
  • Step d Preparation of ethyl 3-(4-ethynyl-2-fluorophenyl)-3-oxopropionate.
  • Triethylamine (14.91g) and magnesium dichloride (15.93g) were added successively to a vigorously stirred solution of potassium ethyl malonate (23.95g) in acetonitrile (110ml) at 10°C under an inert atmosphere of nitrogen. After stirring for a further 21 ⁇ 2 hours at room temperature the mixture was cooled to 0°C, and the crude 4-ethynyl-2-fluorobenzoyl chloride, prepared as described in Step c of this example, (11.0g) was added dropwise over approximately 15 minutes. After the addition of the benzoyl chloride was complete, triethylamine (1.49g) was added and the mixture allowed to warm to room temperature.
  • Step e Preparation of 3-(4-ethynyl-2-fluorophenyl)-5-hydroxyl-1-methylpyrazole.
  • Methylhydrazine (4.52g) was added dropwise over a period of approximately 15 minutes to a solution of crude ethyl 3-(4-ethynyl-2-fluorophenyl)-3-oxopropionate, prepared as described in Step d of this example, (23.0g) in ethanol (10ml) with the internal
  • Step f Preparation of 5-difluoromethoxy-3-(4-ethynyl-2-fluorophenyl)-1-methylpyrazole.
  • Aqueous sodium hydroxide solution 50ml was added dropwise with vigorous stirring to a suspension of crude 3-(4-ethynyl-2-fluorophenyl)-5-hydroxy-1-methylpyrazole, prepared as described in Step e of this example, (5.0g) in dichloromethane (50ml) containing tetraphenyl phosphonium bromide (5.04g) and saturated with chlorodifluoromethane gas. After stirring for 1 hour at room temperature, the reaction mixture was diluted with water the aqueous and organic phases separated and the aqueous phase extracted with dichloromethane.
  • Step g Preparation of Compound 26 in Table I.
  • Step a Preparation of ethyl 2-(3-(4-chloro-2-fluorophenyl)-1-methylpyrazol-5-yloxy)-acetate.
  • Ethyl bromoacetate (0.200g) was added to a stirred mixture containing 3-(4-chloro-2-fluorophenyl)-5-hydroxy-1-methylpyrazole (0.266g), prepared in a similar manner to that described in Step c of Example 1 using appropriate reagents, and potassium carbonate (0.276g) in 2-butanone (5ml).
  • the reaction mixture was heated at 90°C for 1 hour until analysis by thin layer chromatography indicated that no starting pyrazole remained. After cooling, the reaction mixture was diluted with diethyl ether and filtered. The filtered solid was washed with diethyl ether and the combined filtrates concentrated under vacuo.
  • Step b Preparation of Compound 31 in Table I.
  • N-Bromosuccinimide (0.217g) was added to a solution of ethyl 2-(3-(4-chloro-2-fluorophenyl)-1-methylpyrazol-5-yloxy)-acetate, prepared as described in Step a of this example, (0.380g) at room temperature.
  • the reaction mixture was heated at reflux by illumination with a tungsten lamp and the reaction progress monitored by GLC.
  • a further portion of N-bromosuccinimide (approximately 0.044g) was required to force the reaction to completion. After cooling, the reaction mixture was concentrated under vacuo and the residue dissolved in ethyl acetate.
  • Step a Preparation of 5-chloro-3-(4-chloro-2-fluorophenyl)-1-methylpyrazole.
  • Step b Preparation of Compound 34 in Table I.
  • Step a Preparation of 4-chloro-3-(4-dibromomethyl-2-fluorophenyl)-5-difluoromethoxy-1-methylpyrazole.
  • N-Bromosuccinimide (1.35g) and a catalytic amount of benzoyl peroxide were added to a solution of 4-chloro-5-difluoromethoxy-1-methyl-3-(4-methyl-2-fluorophenyl)pyrazole, compound 32 in Table I, prepared as described in Example 1, (1.0g) in carbon tetrachloride (15ml) and the resulting mixture heated at reflux for 5 hours. After cooling, the mixture was fihered and the filtrate concentrated under vacuo to give the crude product which was used directly without further purification.
  • Step b Preparation of 4-chloro-5-difluoromethoxy-3-(4-formyl-2-fluorophenyl)-1-methylpyrazole.
  • Step c Preparation of Compound 40.
  • Step a Preparation of 4-chloro-3-(4-chloro-5-chlorosulphonyl-2-fluorophenyl)-5-difluoromethoxy-1-methoxypyrazole.
  • Step b Preparation of Compound 43.
  • Step a Preparation of 4-bromo-5-difluoromethoxy-3-(4-fluoro-2-methoxyphenyl)-1-methylpyrazole.
  • Step b Preparation of 4-chlorosulphonyl-5-difluoromethoxy-3-(4-fluoro-2-methoxyphenyl) 1-methylpyrazole.
  • the solid (1.1g) was taken up into diethyl ether (25ml) at room temperature under nitrogen and thionyl chloride (0.48g) added dropwise. After stirring for 2 hours at room temperature, the reaction mixture was washed with water, twice with saturated aqueous sodium bicarbonate solution, then with water, 2M aqueous hydrochloric acid solution, twice with water, and with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulphate, filtered and concentrated under vacuo to a waxy solid (0.6g), which was used directly without further purification.
  • Step c Preparation of compound 44.
  • Step a Preparation of 4-chloro-5-difluoromethoxy-3-(4-chlorosulphonyl-2-fluorophenyl) -1-methylpyrazole.
  • Step a Preparation of 4-carboxy-3-(4-chloro-2-fluorophenyl-5-difluoromethoxy-1-methylpyrazole.
  • Step b Preparation of Compound No. 46.
  • each chemical was formulated in one of two ways. Either the chemical was dissolved in an appropriate amount of water, dependent on the amount of solvent/surfactant blend required such that the total volume is 5cm 3 . Then a solvent sufficient blend comprised 78.2 gm/litre of T ween 20 and 21.8 gm/litre of Span 80 adjusted to 1 litre using methylcyclohexanone was added to the solution. Alternatively, the chemical was dissolved in water to the required concentration and 0.1% Tween added. Tween 20 is a Trade Mark for a surface-active agent comprising a condensate of 20 molar proportions of ethylene oxide with sorbitan laurate.
  • Span 80 is a Trade Mark for a surface-active agent comprising sorbitan mono-laurate. If the chemical did not dissolve, the volume was made up to 5cm 3 with water, glass beads were added and this mixture was then shaken to effect dissolution or suspension of the chemical, after which the beads were removed. In all cases, the mixture was then diluted to the required spray volume. If sprayed independently, volumes of 25cm 3 and 30cm 3 were required for post-emergence tests; if sprayed together, 45cm 3 was required. The sprayed aqueous emulsion contained 4% of the initial solvent/surfactant mix and the test chemical at an appropriate concentration.

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Abstract

L'invention porte sur des composés de la formule générale (I). Dans cette formule, R1 est un hydrogène ou un alkyle, un alcényle, un alcynyle, un benzyle, un cycloalkyle ou un cycloalcényle, n'importe lequel d'entre eux pouvant éventuellement être substitué. R2 est un alkyle, un alcényle ou un alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué, ou un halo, un OR5, un SO¿mR?5, un O(alkyle)CO¿2R?5 ou un O(alkyle)COR5, m étant égal à 0, 1 ou 2. R3 est un hydrogène, un halogène, un cyano, un alkyle, un alcényle ou un alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué, ou un SO¿2?Z, COR?5, CO¿2R5 ou un OR5. R4 et un hydrogène, un alkyle, un alcényle ou un alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué, ou un cyano, un nitro, un halogène, un NR?5R6, un OR5¿, un SO¿pR?5, un CO¿2R?5, un CONR?5R6, un NR5SO¿2R6, un COR5, un C(NOR5)R6, un OSO¿p?R?5, un NR5COR6¿, un O(alkyle)COR5, un O(alkyle)CO¿2R?5 ou un SO¿2?Z. Chaque X est indépendamment un halogène, un cyano, un nitro, un alkyle, un alcényle, ou un alcynyle, n'importe lequel d'entre eux pouvant éventuellement être substitué, un OR?5, un NR5R6, un NR5SO¿2R6, un OSO¿pR?5, un SO¿pR?5, un CO¿2R?5, un COR?5, un NR5COR6, un R5OR6¿, un CONR5R6, un SO¿2?Z ou un hétérocyclyle ou, selon un autre mode de réalisation, deux groupes X ou un seul groupe X et R?4¿ peuvent former ensemble un autre cycle; Z étant un halogène, p étant égal à 0, 1 ou 2 et n à 0, 1, 2 ou 3. Y est un halogène, un cyano ou un alcoxy éventuellement substitué. R5 et R6 sont chacun d'entre eux indépendamment un hydrogène, un alkyle, un alcényle, un alcynyle, n'importe lequel pouvant éventuellement être substitué. Lesdits composés sont actifs en tant qu'herbicides et efficaces lorsqu'ils sont appliqués avant ou après la levée de la plante.
PCT/GB1995/002458 1994-11-10 1995-10-18 Composes de pyrazole herbicides WO1996015115A1 (fr)

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WO1997000246A1 (fr) * 1995-06-15 1997-01-03 Novartis Ag Nouveaux herbicides
WO1997012884A1 (fr) * 1995-10-04 1997-04-10 Fmc Corporation Derives de la 6-heterocyclyl-indazole, comme herbicides
WO1997015559A1 (fr) * 1995-10-26 1997-05-01 Basf Aktiengesellschaft 4,5-di(trifluoromethyl)pyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes
WO1997018195A1 (fr) * 1995-11-15 1997-05-22 Basf Aktiengesellschaft 1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes
WO1997040018A1 (fr) * 1996-04-18 1997-10-30 Bayer Aktiengesellschaft 3-cyanoarylpyrazoles et leur utilisation comme herbicides
WO1997046535A1 (fr) * 1996-06-03 1997-12-11 Bayer Aktiengesellschaft 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
WO1998020000A2 (fr) * 1996-11-04 1998-05-14 Basf Aktiengesellschaft 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang
WO1998027090A2 (fr) * 1996-12-16 1998-06-25 Basf Aktiengesellschaft Pyrazol-3-ylbenzazoles substitues
FR2773153A1 (fr) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie Nouveaux composes fongicides
FR2773155A1 (fr) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie Nouveaux composes fongicides
WO1999055702A1 (fr) * 1998-04-29 1999-11-04 Basf Aktiengesellschaft (4-brompyrazol-3-yl)benzazoles substitues
US6096689A (en) * 1995-07-06 2000-08-01 Basf Aktiengesellschaft 5-pyrazolylbenzoic acid derivatives as herbicides
US6100218A (en) * 1996-02-16 2000-08-08 Basf Aktiengesellschaft Substituted 2-phenylpyridines
US6103667A (en) * 1995-06-15 2000-08-15 Novartis Corporation Phenylpyrazole herbicides
US6197973B1 (en) 1996-08-01 2001-03-06 Basf Aktiengesellschaft Substituted 3-phenylpyrazoles
WO2001016138A1 (fr) * 1999-08-27 2001-03-08 Abbott Laboratories Composes sulfonylphenylpyrazoles utiles en tant qu'inhibiteurs de cox-2
WO2001087863A1 (fr) * 2000-05-15 2001-11-22 Basf Aktiengesellschaft 3-arylisothiazoles et leur utilisation en tant qu'herbicides
US6613718B2 (en) 2001-10-01 2003-09-02 Ishihara Sangyo Kaisha, Ltd. Aryl ether derivatives and processes for their preparation and herbicidal and desiccant compositions containing them
WO2006125370A1 (fr) 2005-05-26 2006-11-30 Sinochem Corporation Composes ether aromatiques, leur preparation et leur utilisation
USRE39708E1 (en) 1998-08-07 2007-06-26 Chiron Corporation Estrogen receptor modulators
WO2011042389A2 (fr) 2009-10-09 2011-04-14 Bayer Cropscience Ag Phenylpyri(mi)dinylazoles
US20150105252A1 (en) * 2013-10-15 2015-04-16 E I Du Pont De Nemours And Company Substituted pyrazoles as herbicides

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WO1992006962A1 (fr) * 1990-10-18 1992-04-30 Monsanto Company Composes herbicides d'haloalkylpyrazoles aryle substitue

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US6103667A (en) * 1995-06-15 2000-08-15 Novartis Corporation Phenylpyrazole herbicides
WO1997000246A1 (fr) * 1995-06-15 1997-01-03 Novartis Ag Nouveaux herbicides
US6096689A (en) * 1995-07-06 2000-08-01 Basf Aktiengesellschaft 5-pyrazolylbenzoic acid derivatives as herbicides
WO1997012884A1 (fr) * 1995-10-04 1997-04-10 Fmc Corporation Derives de la 6-heterocyclyl-indazole, comme herbicides
WO1997015559A1 (fr) * 1995-10-26 1997-05-01 Basf Aktiengesellschaft 4,5-di(trifluoromethyl)pyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes
US5962694A (en) * 1995-11-15 1999-10-05 Basf Aktiengesellschaft Substituted 1-methyl-3-phenylpyrazoles and the use thereof as herbicides and for the desiccation or defoliation of plants
WO1997018195A1 (fr) * 1995-11-15 1997-05-22 Basf Aktiengesellschaft 1-methyl-3-phenylpyrazoles substitues et leur utilisation comme herbicides et pour la dessiccation/defoliation de plantes
US6100218A (en) * 1996-02-16 2000-08-08 Basf Aktiengesellschaft Substituted 2-phenylpyridines
WO1997040018A1 (fr) * 1996-04-18 1997-10-30 Bayer Aktiengesellschaft 3-cyanoarylpyrazoles et leur utilisation comme herbicides
WO1997046535A1 (fr) * 1996-06-03 1997-12-11 Bayer Aktiengesellschaft 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
US6197973B1 (en) 1996-08-01 2001-03-06 Basf Aktiengesellschaft Substituted 3-phenylpyrazoles
WO1998020000A3 (fr) * 1996-11-04 1998-10-29 Basf Ag 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang
WO1998020000A2 (fr) * 1996-11-04 1998-05-14 Basf Aktiengesellschaft 3-benzylpyrazoles substitues et leur utilisation comme herbicides et pour abaisser la teneur en sucre du sang
US6451734B1 (en) 1996-11-04 2002-09-17 Basf Aktiengesellschaft Substituted 3-benzylpyrazoles and their use as herbicides
EA002350B1 (ru) * 1996-12-16 2002-04-25 Басф Акциенгезельшафт Замещенные пиразол-3-илбензазолы
WO1998027090A3 (fr) * 1996-12-16 1998-09-17 Basf Ag Pyrazol-3-ylbenzazoles substitues
WO1998027090A2 (fr) * 1996-12-16 1998-06-25 Basf Aktiengesellschaft Pyrazol-3-ylbenzazoles substitues
US6232470B1 (en) 1996-12-16 2001-05-15 Basf Aktiengesellschaft Substituted pyrazol-3-ylbenzazoles, their use as herbicides or desiccants/defoliants, and their preparation
FR2773155A1 (fr) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie Nouveaux composes fongicides
WO1999033813A1 (fr) * 1997-12-29 1999-07-08 Aventis Cropscience S.A.; Derives 3-hydroxy-pyrazole fongicides
FR2773153A1 (fr) * 1997-12-29 1999-07-02 Rhone Poulenc Agrochimie Nouveaux composes fongicides
US6482774B1 (en) 1998-04-29 2002-11-19 Basf Aktiengesellschaft Substituted (4-brompyrazole-3-yl) benzazoles
WO1999055702A1 (fr) * 1998-04-29 1999-11-04 Basf Aktiengesellschaft (4-brompyrazol-3-yl)benzazoles substitues
AU758553B2 (en) * 1998-04-29 2003-03-27 Basf Aktiengesellschaft Substituted (4-brompyrazole-3-yl)benzazoles
USRE39708E1 (en) 1998-08-07 2007-06-26 Chiron Corporation Estrogen receptor modulators
WO2001016138A1 (fr) * 1999-08-27 2001-03-08 Abbott Laboratories Composes sulfonylphenylpyrazoles utiles en tant qu'inhibiteurs de cox-2
WO2001087863A1 (fr) * 2000-05-15 2001-11-22 Basf Aktiengesellschaft 3-arylisothiazoles et leur utilisation en tant qu'herbicides
US6613718B2 (en) 2001-10-01 2003-09-02 Ishihara Sangyo Kaisha, Ltd. Aryl ether derivatives and processes for their preparation and herbicidal and desiccant compositions containing them
US6927193B2 (en) 2001-10-01 2005-08-09 Ishihara Sangyo Kaisha, Ltd. Aryl ether derivatives and processes for their preparation and herbicidal and desiccant compositions containing them
WO2006125370A1 (fr) 2005-05-26 2006-11-30 Sinochem Corporation Composes ether aromatiques, leur preparation et leur utilisation
WO2011042389A2 (fr) 2009-10-09 2011-04-14 Bayer Cropscience Ag Phenylpyri(mi)dinylazoles
EP2784072A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
EP2784071A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
EP2784073A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
EP2784070A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
US20150105252A1 (en) * 2013-10-15 2015-04-16 E I Du Pont De Nemours And Company Substituted pyrazoles as herbicides

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