WO1994005642A1 - Derives de l'indazole - Google Patents

Derives de l'indazole Download PDF

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Publication number
WO1994005642A1
WO1994005642A1 PCT/EP1993/002203 EP9302203W WO9405642A1 WO 1994005642 A1 WO1994005642 A1 WO 1994005642A1 EP 9302203 W EP9302203 W EP 9302203W WO 9405642 A1 WO9405642 A1 WO 9405642A1
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Prior art keywords
alkyl
hydrogen
formula
phenyl
haloalkyl
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PCT/EP1993/002203
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English (en)
Inventor
Saleem Farooq
Roger Graham Hall
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Ciba-Geigy Ag
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Priority to AU49492/93A priority Critical patent/AU4949293A/en
Publication of WO1994005642A1 publication Critical patent/WO1994005642A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/54—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings condensed with carbocyclic rings or ring systems
    • C07D231/56—Benzopyrazoles; Hydrogenated benzopyrazoles
    • 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
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to compounds of formula
  • R 1 is hydrogen, C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl
  • R 2 is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, benzyl, -CHO, -CH 2 -O-D, -CO-D,
  • R 3 and R 4 are each independently of the other hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or C 1 -C 4 haloalkyl,
  • E is independently of any other halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkyl, C 1 -C 4 alkylthio, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, cyano or nitro,
  • n 0, 1, 2 or 3
  • X is oxygen or sulfur
  • A is phenyl, naphthyl, substituted phenyl or substituted naphthyl
  • D is C 1 -C 10 alkyl, phenyl or substituted phenyl
  • Y is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, , ,
  • Z is hydrogen, C 1 -C 10 alkyl, C 1 -C 4 haloalkyl, C 1 -C 10 alkoxy , phenyl,
  • R 14 and R 15 are each independendy of the other C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl
  • R 16 and R 17 are each independently of the other C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, phenyl or substituted phenyl
  • R 18 is C 1 -C 4 alkyl or C 3 -C 6 cycloalkyl
  • R 19 and R 20 are each independently of the other C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, phenyl or substituted phenyl,
  • Certain 3-carbamoylpyrazole derivatives are proposed in the literature as acaricidal, insecticidal and fungicidal active ingredients in pesticides.
  • the biological properties of those known compounds are not, however, totally satisfactory in the field of pest control, and there is therefore a need to provide further compounds having pesticidal properties, especially for controlling insects, representatives of the order Acarina, nematodes and phytopathogenic fungi. That problem is solved according to the invention by the provision of the present compounds I.
  • Compounds I having at least one basic centre are capable of forming, for example, acid addition salts.
  • Those salts are formed, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C 1 -C 4 alkanecarboxylic acids, for example acetic acid, or saturated or unsaturated dicarboxylic acids, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, or hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted,
  • C 1 -C 4 alkanesulfonic or arylsulfonic acids for example methanesulfonic or p-toluene- sulfonic acid.
  • compounds I having at least one acidic group are capable of forming salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine. Where appropriate, corresponding internal salts may also be formed.
  • metal salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethylamine, diethylamine, trieth
  • agrochemically advantageous salts Preference is given within the scope of the invention to agrochemically advantageous salts, but salts that have disadvantages for agrochemical purposes, for example salts that are toxic to bees or to fish, are also included; the latter salts are used, for example, in the isolation or purification of free compounds I or the agrochemically acceptable salts thereof.
  • any reference to the free compounds I or their salts should be understood as including also the corresponding salts or the free compounds I, respectively, where appropriate and expedient.
  • A is phenyl or naphthyl, or is phenyl or naphthyl each substituted by 0, 1, 2 or 3
  • radicals selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • Y is oxygen, sulfur or a bridge member -SO-, -SO 2 -, -CO-, -CR 6 R 7 - or -NR 8 - or a direct single bond,
  • R 5 is phenyl, naphthyl or pyridyl, or is phenyl, naphthyl or pyridyl each substituted by 0, 1, 2 or 3 radicals selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • R 6 and R 7 are each independently of the other hydrogen or C 1 -C 4 alkyl
  • R 8 is hydrogen, C 1 -C 4 alkyl, formyl, C 1 -C 4 alkylcarbonyl or C 1 -C 4 alkoxycarbonyl.
  • Halogen atoms that are suitable as substituents are both fluorine and chlorine and bromine and iodine, with fluorine, chlorine and bromine being preferred.
  • Halogen in that context is to be understood as being an independent substituent or part of a substituent, as in haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl or haloalkoxycarbonyl.
  • Alkyl, alkylthio and alkoxy radicals that are suitable as substituents may be straightchained or branched.
  • alkyl radicals are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, heptyl and its isomers, n-octyl and n-dodecyl.
  • Suitable alkoxy radicals that may be mentioned are, inter alia: methoxy, ethoxy, propoxy, isopropoxy, butoxy and the isomers thereof, as well as n-hexyloxy and n-octyloxy.
  • alkylthio examples include methylthio, ethylthio, propylthio, isopropylthio and the four butylthio isomers.
  • Alkylsulfinyl and alkylsulfonyl radicals are derived from the corresponding alkylthio radicals and differ from one another only in the oxidation stages of the sulfur atom.
  • alkyl, alkylthio or alkoxy groups suitable as substituents are substituted by halogen, they may be only partially halogenated or perhalogenated.
  • halogen, alkyl, alkylthio and alkoxy apply.
  • alkyl elements of those groups are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF 2 or CF 3 ; ethyl mono- to penta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCl 3 , CF 2 CHCl 2 , CF 2 CHF 2 , CF 2 CFCl 2 , CF 2 CHBr 2 , CF 2 CHClF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl mono- to hepta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 ,
  • cycloalkyl radicals that are suitable as substituents are cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or tert-butoxycarbonyl.
  • Alkylcarbonyl is acyl, propionyl, butyroyl or butylcarbonyl.
  • the compounds of formula I fall into two groups.
  • the first group includes those compounds wherein R 2 is other than hydrogen, C 1 -C 4 alkyl, benzyl or C 3 -C 6 cycloalkyl.
  • R 2 is other than hydrogen
  • C 1 -C 4 alkyl benzyl or C 3 -C 6 cycloalkyl.
  • Special preference is given here to compounds of formula I wherein a) D is C 1 -C 10 alkyl, phenyl, C 1 -C 4 alkylphenyl or halophenyl,
  • Y is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, phenyl, C 1 -C 4 alkylphenyl, halophenyl, , or ,
  • Z is hydrogen, C 1 -C 4 alkyl, phenyl, C 1 -C 4 alkylphenyl, halophenyl, C 1 -C 10 alkoxy, phenoxy, C 1 -C 4 alkylphenoxy, halophenoxy or ,
  • R 16 and R 17 are each independently of the other C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl, phenyl, C 1 -C 4 alkylphenyl or halophenyl and
  • R 19 and R 20 are each independently of the other C 1 -C 4 alkyl, special mention being made of those compounds of that sub-group wherein
  • D is C 1 -C 10 alkyl, phenyl or 4-chlorophenyl
  • Y is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 cyanoalkyl, phenyl, 4-methylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, , or ,
  • Z is hydrogen, C 1 -C 4 alkyl, phenyl, 4-chlorophenyl, C 1 -C 10 alkoxy, phenoxy, 4-chlorophenoxy or ,
  • R 14 and R 15 are each independently of the other C 1 -C 4 alkyl
  • R 16 is C 1 -C 4 alkyl, phenyl or 4-chlorophenyl,
  • R 17 is methyl
  • R 18 is C 1 -C 4 alkyl or cyclopropyl, or b) R 1 is methyl or ethyl and
  • R 3 and R 4 are hydrogen, or c) A is an unsubstituted or substituted phenoxyphenyl group of the formula
  • R 9 , R 10 , R 11 and R 12 are each independently of the others hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy, and
  • R 13 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylthio, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkylsulfonyloxy, haloC 1 -C 4 alkylsulfonyloxy, cyano or nitro, and
  • R 12 and R 13 together are -O-CH 2 -O-;
  • R 9 and R 10 are hydrogen
  • R 11 and R 12 are each independently of the other hydrogen, fluorine, chlorine or trifluoromethyl,
  • R 13 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy,
  • R 12 and R 13 together are -O-CH 2 -O-;
  • R 9 and R 10 are hydrogen
  • R 11 and R 12 are each independently of the other hydrogen, fluorine, chlorine or trifluoromethyl,
  • R 13 is hydrogen, C 1 -C 4 alkyl, fluorine, chlorine, bromine, cyano, methoxy, methylthio, trifluoromethyl, methylsulfonyl, methylsulfonyloxy or trifluoromethylsulfonyloxy and
  • R 12 and R 13 together are -O-CH 2 -O- and
  • n 0, 1 or 2 and
  • the substituents E are each independently of any other halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy,
  • R 1 is methyl or ethyl
  • R 3 and R 4 are hydrogen.
  • a second group includes those compounds of formula I wherein
  • R 2 is hydrogen, C 1 -C 4 alkyl, C 3 -C 6 cycloalkyl or benzyl,
  • A is phenyl or naphthyl, or is phenyl or naphthyl each substituted by 0, 1, 2 or 3
  • radicals selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • R 5 is phenyl, naphthyl or pyridyl, or is phenyl, naphthyl or pyridyl each substituted by 0, 1, 2 or 3 radicals selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl,
  • R 6 and R 7 are each independently of the other hydrogen or C 1 -C 4 alkyl and
  • R 8 is hydrogen, C 1 -C 4 alkyl, formyl, C 1 -C 4 alkylcarbonyl or C 1 -C 4 alkoxycarbonyl, special preference being given to those compounds of that sub-group wherein the naphthyl radicals defined are bonded in the 1- or 2-position and the pyridyl radicals defined are bonded in the 2-, 3- or 4-position.
  • the substituents E are each independently of any other halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy, or e) R 1 is methyl or ethyl and R 2 , R 3 and R 4 are each hydrogen, or f) A is an unsubstituted or substituted phenoxyphenyl group of the formula
  • R 9 , R 10 , R 11 and R 12 are each independently of the others hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy, and
  • R 13 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylthio, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkylsulfonyloxy, haloC 1 -C 4 alkylsulfonyloxy, cyano or nitro.
  • R 9 , R 10 , R 11 and R 12 are hydrogen and
  • R 13 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy,
  • R 13 is hydrogen, halomethyl, haloethyl, cyano, nitro, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxy or trifluoromethylsulfonyloxy.
  • a group of compounds according to the invention that may be given special mention on account of their good biological activity comprises compounds wherein:
  • n 0, 1 or 2
  • the substituents E are each independently of any other halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy,
  • R 1 is methyl or ethyl
  • R 2 , R 3 and R 4 are each hydrogen and
  • A is a group of the formula ,
  • R 9 , R 10 , R 11 and R 12 are each independently of the others hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy or C 1 -C 4 alkoxy, and
  • R 13 is hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyld ⁇ io, C 1 -C 4 alkykhio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfinyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 4 alkylsulfonyloxy, haloC 1 -C 4 alkylsulfonyloxy, cyano or nitro.
  • the substituents E are each independently of any other halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy;
  • R 1 is methyl or ethyl
  • R 2 , R 3 and R 4 are each hydrogen and
  • A is phenyl or naphthyl, or is phenyl or naphthyl each substituted by 0, 1, 2 or 3
  • radicals selected from halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • the substituents E are each independently of any other halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkoxy or C 1 -C 4 alkoxy,
  • R 1 is methyl or ethyl
  • R 2 , R 3 and R 4 are each hydrogen and
  • A is a group of the formula
  • R 13 is hydrogen, halogen, C 1 -C 4 alkyl, halomethyl, haloethyl, C 1 -C 4 alkoxy, halomethoxy, haloethoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, methylsulfonyl, ethylsulfonyl, halomethylsulfonyl, methylsulfonyloxy, trifluoromethylsulfonyloxy, cyano or nitro.
  • R 13 is hydrogen, halomethyl, haloethyl, cyano, nitro, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl.
  • the compounds of formula I according to the invention can be prepared analogously to known processes.
  • compounds of formula I wherein R 2 is hydrogen, C 1 -C 4 alkyl, benzyl or C 3 -C 6 cycloalkyl and R 1 , R 3 , R 4 , A, E, n and X are as defined above are obtained by first either a) condensing a 2H-indazole-3-carboxylic acid of formula II ,
  • R 2 is hydrogen, C 1 -C 4 alkyl, benzyl or C 3 -C 6 cycloalkyl and R 3 , R 4 and A are as defined for formula I, or b) converting the 2H-indazole-3-carboxylic acid of formula II into an acid halide, an imidazolide or an alkyl ester of formula IV ,
  • R 1 , E and n are as defined for formula I and Q is chlorine, bromine, 1-imidazolyl, methoxy or ethoxy, and reacting that activated derivative with an amine of formula III, and if desired converting the resulting 3-carbamoyl-2H-indazole derivative of sub-formula Ia , i
  • R 2 is hydrogen, C 1 -C 4 alkyl, benzyl or C 3 -C 6 cycloalkyl and R 1 , R 3 , R 4 , A, E and n are as defined for formula I, by treatment with a thionating agent, into the compound of sub-formula Ib ,
  • R 2 is hydrogen, C 1 -C 4 alkyl, benzyl or C 3 -C 6 cycloalkyl and R 1 , R 3 , R 4 , A, E and n are as defined for formula I,
  • R 1 , R 3 , R 4 , A, E and n are as defined for formula I, with a compound
  • the reaction is advantageously carried out in the presence of water-removing reagents that are customary for amidation reactions, for example in the presence of a carbodiimide [dicyclohexylcarbodiimide (DCC)] or of a 1-alkyl-2-halopyridinium salt, such as 1-methyl-2-chloropyridinium iodide.
  • a carbodiimide dicyclohexylcarbodiimide (DCC)] or of a 1-alkyl-2-halopyridinium salt, such as 1-methyl-2-chloropyridinium iodide.
  • the reaction is advantageously carried out in the presence of an inert solvent or solvent mixture, at temperatures of from -30°C to +70°C, preferably from -10°C to +50°C.
  • the reaction is preferably carried out in the presence of a base, such as in the presence of an organic amine such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), a morpholine (N-methylmorpholine) or an N,N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline).
  • a base such as in the presence of an organic amine such as a trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), a pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), a morpholine (N-methylmorpholine) or an N,N-dialkylaniline (N,N-dimethyl
  • Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; esters, such as ethyl acetate (acetic acid ethyl ester), propyl acetate or butyl acetate; and mixtures of such solvents with one another.
  • aliphatic and aromatic hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene
  • the first step of converting the free acid of formula II into an activated derivative of formula IV is carried out in accordance with generally customary methods used for the halogenation of carboxylic acids using halogenating agents, such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide or phosgene, for amidation using halogenating agents, such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide or phosgene, for amidation using halogenating agents, such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide or phosgene, for amidation using halogenating agents, such as thionyl chloride, oxalyl chloride
  • 1H-imidazole and for esterification using lower alkyl alcohols.
  • Halogenation is preferred, chlorination with thionyl chloride or phosgene without solvents being especially preferred in practice.
  • solvents are advantageously selected from the group of the hydrocarbons, such as hexane, pentane, cyclohexane, benzene, toluene or xylene;
  • halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethylene- glycol or anisole
  • nitriles such as acetonitrile or propionitrile.
  • the second reaction step of variant b) (IV+III ⁇ Ia) is preferably carried out in an inert solvent that is free of hydroxy groups, in the presence of an organic base, such as pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline, or a bicyclic, non-nucleophilic base, such as 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (1,5-5) (DBU).
  • an organic base such as pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline, or a bicyclic, non-nucleophilic base, such as 1,4-diazabicyclo[2.2.2]oc
  • the reaction is generally carried out at temperatures of from -30°C to +70°C, preferably from -10°C to +50°C.
  • the reaction is advantageously carried out in the presence of an inert solvent or solvent mixture.
  • suitable solvents or solvent mixtures are aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether or hexane; halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane or tetrahydrofuran; nitriles, such as acetonitrile or propionitrile; esters, such as ethyl acetate
  • reaction is carried out in the presence of a strong base, such as sodium hydride, potassium hydride, potassium tert-butoxide, sodium ethoxide, sodium methoxide or butyllithium.
  • a strong base such as sodium hydride, potassium hydride, potassium tert-butoxide, sodium ethoxide, sodium methoxide or butyllithium.
  • the reaction is advantageously carried out in an inert solvent at from -10°C to +60°C, preferably at from 0°C to 30°C.
  • Suitable solvents are aliphatic and aromatic hydrocarbons, such as methylene chloride, ethylene chloride, chlorobenzene or ortho-dichlorobenzene; ethers and ethereal solvents, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane and dimethoxymethane; nitriles, such as acetonitrile and propionitrile; esters, such as ethyl acetate, methyl acetate, propyl acetate and butyl acetate, and mixtures of such solvents with one another.
  • the starting material of formula Ic required for this process is obtainable in accordance with process variants a) and b).
  • the optional conversion of the 2H-indazole-3-carboxylic acid amide of formula Ia into the corresponding 2H-indazole-3-thiocarboxylic acid amide of formula lb is carried out under the conditions customary for this type of reaction.
  • the process according to the invention is preferably carried out in the presence of an inert organic solvent.
  • Suitable solvents are aromatic solvents, such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, pyridine or Tetralin; chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichloroethane or tetrachloroethane; or ethers, such as dioxane, tetrahydrofuran or dimethylethylene glycol.
  • the reaction temperatures are generally from 0°C to +150°C. A range of from +20°C to +120°C is preferred, the boiling range of the reaction mixture being especially preferred.
  • the thionation reaction it is also of advantage to the reaction according to the invention for the thionation reaction to be carried out using ultrasound and at a temperature of from +20°C to the boiling point of the mixture.
  • the use of sources of ultrasound to assist thionation reactions is described in analogous processes in J. Org. Chem. 46, 3558 (1981).
  • a large number of thionating agents have already been described in the literature. Most of those agents can be used in the processes according to the invention. The following have proved especially
  • O-O-diethyldithiophosphoric acid C 2 H 5 O
  • PS 2 H boron sulfide B 2 S 3 or B 2 S 5
  • Hal-CO-D Hal-CO-OD, Hal-CO-CO-D, Hal-CO-CO-O-D, Hal-S-Y, Hal-SO-Y and Hal-SO 2 -Y, wherein Hal is chlorine, bromine or iodine, especially chlorine or bromine, are described in the literature.
  • the novel starting materials can be prepared analogously to known processes. Some products are already commercially available.
  • R 1 , E and n are as defined for formula I, by treatment with alkali metal cyanides in the presence of an organic acid to form the 3-cyano-2H-indazole 1-oxide of
  • R 1 , E and n are as defined for formula I, desoxydising that intermediate and hydrolysing the resulting 3-cyano-2H-indazole of formula IX ,
  • R 1 , E and n are as defined for formula I.
  • an inert organic solvent from the group of the aromatic, aliphatic or cycloaliphatic hydrocarbons, such as benzene, toluene, xylene, hexane or cyclohexane, at temperatures of from 0°C to +150°C, preferably from +25°C to +100°C, but especially at the boiling temperature of the reaction mixture.
  • an acid such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid or methanesulfonic acid
  • a protic, polar, organic solvent from the group of the alcohols or carboxylic acids, such as methanol, ethanol, isopropanol, acetic acid or propionic acid.
  • Suitable alkali metal cyanides are preferably sodium cyanide or potassium cyanide.
  • Equivalent amounts of an organic acid, such as acetic acid or trifluoroacetic acid, are added to those salts in the reaction solution. It may also be advantageous to use the acid in excess, so that it is able to act at the same time as a solvent
  • the reaction temperatures are generally from -15°C to +100°C, preferably from 0°C to +50°C.
  • Phosphorus trichloride and phosphorus tribromide are preferably used as desoxydising reagents for the desoxydising step (VIII ⁇ IX). That reaction step is advantageously carried out in a hydrocarbon or chlorinated hydrocarbon as solvent at temperatures of from 0°C to +150°C, especially from +25°C to +100°C.
  • Suitable solvents are, for example, benzene, toluene, xylene, hexane, cyclohexane, methylene chloride, chloroform or carbon tetrachloride.
  • the hydrolysis step (IX ⁇ II) can be carried out either under acid conditions or under basic conditions in an aqueous medium.
  • Suitable solvents are preferably water, alcohols and water-miscible ethers. It is especially advantageous to use aqueous solvents or solvent mixtures.
  • suitable solvents are water, tetrahydrofuran, dioxane, methanol, ethanol or isopropanol.
  • suitable acid hydrolysis catalysts are sulfuric acid, hydrochloric acid and hydrobromic acid
  • suitable basic hydrolysis catalysts are sodium hydroxide and potassium hydroxide.
  • the reaction temperatures for the hydrolysis reaction are generally from 0°C to +150°C, but especially from +25°C to 100°C.
  • a compound I obtainable in accordance with the process or by a different method can be converted in a manner known per se into a different compound I by replacing one or more substituents of the starting compound I in customary manner by (a) different substituent(s) according to the invention.
  • R 1 and/or R 2 can be replaced by alkyl R 1 and/or R 2 or
  • Salts of compounds I can be prepared in a manner known per se. For example, acid addition salts are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
  • Salts of compounds I can be converted into the free compounds I in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
  • Salts of compounds I can be converted into different salts of compounds I in a manner known per se: acid addition salts, for example, can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydro-chloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and therefore is eliminated from the reaction mixture.
  • a salt of an inorganic acid such as a hydro-chloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • compounds I having salt-forming properties can be obtained in free form or in the form of salts.
  • the compounds I in free form or in salt form, may be, if appropriate, in the form of one of the possible isomers or as a mixture thereof, for example according to the number of asymmetric carbon atoms optionally occurring in the molecule and the absolute and relative configuration thereof and/or according to the configuration of non-aromatic double bonds optionally occurring in the molecule, they may be in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood hereinbefore and hereinafter, even if stereochemical detads are not specifically mentioned in each case.
  • Mixtures of diastereoisomers and mixtures of racemates of compounds I, in free form or in salt form, that are obtainable in accordance with the process depending upon the starting materials and procedures chosen, or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physicochemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.
  • the compounds I in free form or in salt form, can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents used for the crystallisation of compounds in solid form.
  • the invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.
  • the invention relates especially to the preparation processes described in Examples P1 to P5.
  • the invention relates also to starting materials and intermediates used according to the invention for the preparation of the compounds I or the salts thereof, in each case in free form or in salt form, that are novel, to a process for the preparation thereof and to their use as starting materials and intermediates for the preparation of the compounds I.
  • the compounds I according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants.
  • the compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects, nematodes and representatives of the order Acarina, and phytopathogenic fungi.
  • the insecticidal, nematicidal and/or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • the mentioned animal pests include, for example:
  • Otiorhynchus spp. Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
  • Thysanoptera for example,
  • Leptocorisa spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
  • Aleurothrixus floccosus Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
  • Aspidiotus spp. Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
  • Erythroneura spp. Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,
  • Macrosiphus spp. Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,
  • Pemphigus spp. Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,
  • Hymenoptera for example, Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,
  • Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;
  • Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
  • Boophilus spp. Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp.,
  • Dermanyssus gallinae Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,
  • Globodera spp. (cyst-forming nematodes), Meloidogyne spp. (root cyst nematodes),
  • Radopholus spp. Pratylenchus spp., Tylenchulus spp., Longidorus spp., Trichodorus spp. and Xiphinema spp.
  • nematodes that are parasites of stems, e.g. of the genus Ditylenchus spp.,
  • the nematodes that are parasites of leaves e.g. of the genus Aphelenchoides spp.
  • the nematodes that are parasites of blossom e.g. of the genus Anguina spp..
  • the mentioned phytopathogenic fungi include, for example:
  • Botrytis spp. Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp.,
  • Rhizoctonia spp. Hemileia spp. and Puccinia spp.; of the class of the Ascomycetes, for example,
  • Venturia spp. Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and of the class of the Oomycetes, for example,
  • Target crops are especially cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar beet or fodder beet; fruit, such as pomes, drupes or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants, such as marrows, cucumber or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or paprika; lauraceae, such as avocados, cinnamon or camphor, and tobacco, nuts, coffee, auberg
  • the compounds of the invention are suitable especially for controlling insects, nematodes and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, plant-destructive sucking insects, such as Aphis craccivora and Bemisia tabaci, plant-destructive soil insects, such as Diabrotica balteata, soil nematodes that are parasites of roots, such as Meloidogyne incognita and Heterodera glycines, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soybean, rape, citrus and vegetable crops.
  • plant-destructive feeding insects such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostell
  • the invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • pesticides such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • the active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • extenders for example solvents or solid carriers, or surface-active compounds (surfactants).
  • Suitable solvents are, for example: optionally partially hydrogenated aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rape oil, castor oil,
  • the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand.
  • suitable nonsorbent carriers are calcite or sand.
  • a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • the surfactants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethyl-ammonium chloride and benzyldi(2-chloroeti ⁇ yl)ethylammonium bromide.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurin salts.
  • fatty sulfonates especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C 8 -C 22 alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
  • These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanol-ammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
  • compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of active ingredient, and 1 to 99.9 %, preferably 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25 %, preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight).
  • surfactants in each case percentages are by weight.
  • Preferred formulations have especially the following composition (throughout, percentages are by weight):
  • Emulsifiable concentrates are:
  • active ingredient 1 to 90 %, preferably 5 to 20 %
  • surfactant 1 to 30 %, preferably 10 to 20 %
  • solvent 5 to 98 %, preferably 70 to 85 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 1 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • surfactant 1 to 40 %, preferably 2 to 30 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surfactant 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 99 %, preferably 15 to 98 %
  • Granules 5 to 99 %, preferably 15 to 98 %
  • active ingredient 0.5 to 30 %, preferably 3 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal, nematicidal, acaricidal and/or fungicidal active ingredients.
  • suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
  • the compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g.
  • epoxidised coconut oil, rape oil or soybean oil epoxidised coconut oil, rape oil or soybean oil
  • antifoams for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example bactericides, molluscicides or selective herbicides.
  • compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding and/or sieving a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one adjuvant, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvant(s).
  • the invention relates also to that process for the preparation of the compositions according to the invention and to the use of the compounds I for the preparation of those compositions.
  • the invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
  • the control of nematodes is preferably effected by means of soil application.
  • compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit, tubers or grains, or plant cuttings, from fungal infections and animal pests.
  • the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
  • the compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
  • the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to that method f treating plant propagation material and to the plant propagation material thus treated.
  • a mixture of 70 g of 3-cyano-2-methyl-2H-indazole and 1 1 of 75 % sulfuric acid is stirred for 2.5 hours at +110°C (bath temperature).
  • the reaction mixture is men cooled and poured onto 2 kg of ice and extracted with ethyl acetate.
  • the ethyl acetate phase is separated off, washed once with water and once with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation on a rotary evaporator.
  • reaction mixture is stirred for 1 hour at room temperature and diluted with ethyl acetate.
  • the mixture is washed twice with water and once with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation on a rotary evaporator.
  • the crude product is purified by column chromatography over silica gel with ethyl acetate/hexane (1:1) to yield 2-methyl-2H-indazole-3-carboxylic acid [3-(4-fluorophenoxy)-benzyl]-amide having a melting point of 91-93°C.
  • N-(2-ethylhexanoyl)-2-methyl-2H-indazole-3-carboxylic acid [4-(4-trifluoromethylphenoxy)-benzyl]-amide having a melting point of 97-98°C is obtained from 2-methyl-2H-indazole-3-carboxylic acid [4-(4-trifluoromethylphenoxy)- benzyl]-amide and 2-ethylcaproic acid chloride.
  • reaction mixture is then stirred for one hour and then filtered over diatomaceous earth and the filtrate is concentrated by evaporation on a rotary evaporator.
  • the resulting crude product is purified by column chromatography over silica gel with ethyl acetate/hexane (1:3) as eluant to yield N-(tert-butoxyoxalyl)-2-methyl-2H-indazole-3-carboxylic acid [4-(4-trifluoromethylphenoxy)-benzyl]-amide, melting point 107-108°C.
  • N-(3,3-dipropyl-1-methylureido-1-sulfenyl)-2-methyl-2H-indazole-3-carboxylic acid [4-(4-trifluoromethylphenoxy)-benzyl] -amide having a melting point of 110-111°C is prepared from 2-methyl-2H-indazole-3-carboxylic acid [4-(4-trifluoromethylphenoxy)-benzyl]-amide and N,N-dipropyl-N'-methyl-N'-sulfonyl chloride urea.
  • Example P5 The compounds of Tables 1 to 7 can also be prepared in an analogous manner.
  • Example F1 Emulsion concentrates a) b) c) active ingredient no. 5.117 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Example F2 Solutions a) b) c) d) active ingredient no.3.20 80% 10% 5% 95% ethylene glycol monomethyl
  • N-methyl-2-pyrrolidone 20% - epoxidised coconut oil - - 1% 5% petroleum fraction
  • Example F3 Granules a) b) c) d) active ingredient no.4.27 5% 10% 8% 21% kaolin 94% - 79% 54% highly dispersed silicic acid 1% - 13% 7% attapulgite - 90% - 18%
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier, and the solvent is subsequendy evaporated off in vacuo.
  • Example F4 Dusts a) b)
  • Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.
  • Example F5 Wettable powders a) b) c)
  • the active ingredient is mixed with the adjuvants and the mixture is thoroughly ground in a suitable mdl, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
  • Example F6 Emulsifiable concentrate
  • Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
  • Example F7 Dusts a) b)
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill.
  • Example F8 Extruder granules
  • the active ingredient is mixed with the adjuvants, and the mixture is ground and moistened with water.
  • the moistened mixture is extruded and granulated, and the granules are then dried in a stream of air.
  • Example F9 Coated granules
  • polyethylene glycol (mol. wt. 200) 3 %
  • the finely ground active ingredient combination is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • silicone oil in the form of a 75 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • Example B1 Action against Nilaparvata lugens
  • Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound.
  • the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.
  • Example B2 Ovicidal/larvicidal action against Heliothis virescens
  • compounds 1.02, 1.20, 2.05 and 5.706 are more than 80 % effective.
  • Example B3 Action against Heliothis virescens caterpillars
  • Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10
  • Heliothis virescens caterpillars in the first stage and placed in a plastics container.
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • compounds 1.02, 1.20, 2.05 and 5.155 are more than 80 % effective.
  • Example B4 Action against Spodoptera littoralis caterpillars
  • Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B5 Action against Aphis craccivora
  • Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture comprising 400 ppm of test compound, and incubated at 20°C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants. Compounds of Tables 1 to 7 exhibit good activity against Aphis craccivora in this test. In particular, compounds 2.05, 4.04 and 5.706 are more than 80 % effective.
  • Example B6 Action against Crocidolomia binotalis caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Compounds of Tables 1 to 7 are more than 80 % effective against Crocidolomia binotalis in this test. In particular, compounds 1.02 and 1.20 are more than 80 % effective.
  • Example B7 Action against Tetranychus urticae
  • Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion comprising 400 ppm of test compound. The plants are then incubated for 6 days at 25°C and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
  • Compounds of Tables 1 to 7 are more than 80 % effective against Tetranychus urticae in this test.
  • Example B8 Ovicidal action against Heliothis virescens
  • Egg deposits of Heliothis virescens on filter paper are immersed for a short time in an aqueous acetone solution of the test compound having a concentration of 400 ppm. After the test solution has dried, the eggs are incubated in petri dishes. After 6 days, the percentage of eggs which have hatched is evaluated in comparison with untreated controls
  • Dwarf bean plants are placed in gauze cages and populated with adults of Bemisia tabaci
  • Maize seedlings are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the maize seedlings are populated with 10
  • the percentage reduction in the population is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
  • compounds 1.02, 1.20, 2.05, 4.01, 4.03, 5.155 and 5.706 are more than 80 % effective.
  • Example B11 Action against Plutella xylostella caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B12 Action against Anthonomus grandis adults
  • Young cotton plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead beedes and the feeding damage on the treated plants with that on untreated plants.
  • Example B13 Action against Puccinia graminis on wheat
  • Wheat plants are sprayed 6 days after sowing with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100 % relative humidity and about 20°C and then placed in a greenhouse at about 22°C. Evaluation of rust pustule development is made 12 days after infection.
  • a spray mixture 0.02 % active ingredient
  • Wheat plants are watered 5 days after sowing with a spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are then incubated for 48 hours at 95-100 % relative humidity and about 20°C and then placed in a greenhouse at about 22°C.
  • a spray mixture 0.006 % active ingredient, based on the volume of the soil
  • Example B14 Action against Phytophthora infestans on tomato plants
  • tomato plants are sprayed with a spray mixture
  • a spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound is used to water tomato plants. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil.
  • the treated plants are infected 48 hours later with a sporangia suspension of the fungus. The infected plants are then incubated for 5 days at 90-100 % relative humidity and 20°C and then evaluated for fungus infestation.
  • Example B 15 Action against Cercospora arachidicola on groundnut plants
  • Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus.
  • Example B16 Action against Plasmopara viticola on vines
  • Vine seedlings in the 4-5 leaf stage are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation for 6 days at 95-100 % relative humidity and 20°C. b) Curative action:
  • Vine seedlings in the 4-5 leaf stage are infected with a sporangia suspension of the fungus. After incubation for 24 hours in a humidity chamber at 95-100 % relative humidity and 20°C, the infected plants are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After the spray coating has dried, the treated plants are again placed in the humidity chamber. Evaluation of fungus infestation is made 6 days after infection.
  • Example B 17 Action against Pyricularia oryzae on rice plants
  • 2-week-old rice plants are watered with a spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound.
  • the pots are then filled with water so that the lowermost parts of the stems of the rice plants stand in water.
  • the treated plants are infected with a conidia suspension of the fungus.
  • the infected plants are then incubated for 5 days at 95-100 % relative humidity and about 24°C and then evaluated for fungus infestation.
  • Example B18 Residual protective action against Venturia inaequalis on apple shoots
  • Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound.
  • the treated plants are infected 24 hours later with a conidia suspension of the fungus.
  • the plants are then incubated for 5 days at 90-100 % relative humidity and placed in a greenhouse for a further 10 days at 20-24°C. Scab infestation is evaluated 15 days after infection.
  • Compounds of Tables 1 to 7 exhibit good protective activity against Venturia.
  • compound 1.02 is more than 80 % effective.
  • Barley plants about 8 cm in height are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound.
  • the treated plants are dusted with conidia of the fungus after 3 to 4 hours.
  • the infected barley plants are placed in a greenhouse at about 22°C.
  • the fungus infestation is evaluated after 10 days.
  • a spray mixture (0.002 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound is used to water barley plants about 8 cm in height. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are dusted 48 hours later with conidia of the fungus. The infected barley plants are then placed in a greenhouse at about 22°C and evaluation of fungus infestation is made after 10 days.
  • Example B20 Action against Meloidogyne incognita on tomatoes
  • Example B21 Action against Heterodera glycines on soybeans

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Composés de la formule (I) dans laquelle R1 représente l'hydrogène, un alkyle C1-C4 ou un cycloalkyle C3-C6, R2 représente l'hydrogène, un alkyle C1-C4, un cycloalkyle C3-C6, le benzyle, -CHO, -CH2-O-D, -CO-D, -CO-O-D, -CO-CO-O-D, -S-Y, -SO-Y ou -SO2-Y, R3 et R4 représentent chacun indépendamment de l'autre l'hydrogène, un alkyle C1-C4, un cycloalkyle C3-C6 ou un haloalkyle C1-C4, E représente, indépendamment de tout autre halogène, un alcoxy C1-C4, un alkyle C1-C4, un alkylthio C1-C4, un haloalkyle C1-C4, un haloalcoxy C1-C4, un haloalkylthio C1-C4, cyano ou nitro, n vaut 0, 1, 2 ou 3, X représente l'oxygène ou un sulfure, A représente un phényle, un naphtyle, un phényle substitué ou un naphtyle substitué, D représente un alkyle C1-C10, un phényle ou un phényle substitué, Y représente un alkyle C1-C4, (a), (b), (c), un phényle ou un phényle substitué, Z représente l'hydrogène, un alkyle C1-C10, un haloalkyle C1-C4, un alcoxy C1-C10, (d), un phényle, un phénoxy, un phényle substitué ou un phénoxy substitué, R14 et R15 représentent chacun indépendamment l'un de l'autre un alkyle C1-C4 ou un cycloalkyle C3-C6, R16 et R17 représentent chacun indépendamment l'un de l'autre un alkyle C1-C4, un cycloalkyle C3-C6, un phényle ou un phényle substitué, R18 représente un alkyle C1-C4 ou un cycloalkyle C3-C6 et R19 et R20 représentent chacun indépendamment l'un de l'autre un alkyle C1-C4, un cycloalkyle C3-C6, un phényle ou un phényle substitué, sous forme libre ou sous forme de sel. Ces composés peuvent être utilisés comme ingrédients actifs agrochimiques et peuvent être préparés de manière per se.
PCT/EP1993/002203 1992-08-28 1993-08-18 Derives de l'indazole WO1994005642A1 (fr)

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AU49492/93A AU4949293A (en) 1992-08-28 1993-08-18 Indazole derivatives

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CH267492 1992-08-28
CH2674/92-7 1992-08-28

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CN (1) CN1091426A (fr)
AU (1) AU4949293A (fr)
HR (1) HRP931151A2 (fr)
IL (1) IL106735A0 (fr)
MX (1) MX9305171A (fr)
TR (1) TR27142A (fr)
WO (1) WO1994005642A1 (fr)
ZA (1) ZA936305B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0726266A1 (fr) * 1995-02-09 1996-08-14 Mitsubishi Chemical Corporation Dérivés d'indazole et leur utilisation comme fungicides, insecticides et miticides
WO2002083647A1 (fr) * 2001-04-06 2002-10-24 Nihon Nohyaku Co., Ltd. Derive de pyrazole-carboxymide, produit intermediaire pour ce derive et agent antiparasitaire contenant ce derive en tant qu'ingredient actif
FR2845382A1 (fr) * 2002-10-02 2004-04-09 Sanofi Synthelabo Derives d'indazolecarboxamides, leur preparation et leur utilisation en therapeutique
JP2005533809A (ja) * 2002-06-19 2005-11-10 シェーリング　コーポレイション カンナビノイドレセプタアゴニスト
WO2008061688A1 (fr) 2006-11-22 2008-05-29 Aziende Chimiche Riunite Angelini Francesco A.C.R.A.F. S.P.A. Composés de 2-alkyl-indazole pour le traitement de certaines affections liées au snc
US7842711B2 (en) 2004-03-16 2010-11-30 Sanofi-Aventis Indazolecarboxamide derivatives for the treatment and prevention of malaria
WO2012081916A2 (fr) * 2010-12-17 2012-06-21 한국화학연구원 Dérivé d'indazole et composition pesticide le contenant

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PL2310360T3 (pl) * 2008-08-01 2013-07-31 Bayer Ip Gmbh Grzybobójcze pochodne N-cykloalkilo-N-bifenylometylo-karboksamidu
CN102464618B (zh) 2010-11-03 2014-07-23 中国中化股份有限公司 吡唑酰胺类化合物及其应用
CN108203433B (zh) * 2016-12-16 2020-07-03 成都先导药物开发股份有限公司 一种rock抑制剂及其应用
CN112514904B (zh) * 2021-01-26 2021-10-26 青岛农业大学 盐酸苄达明在制备用于防治由植物病原菌引起的植物病害的杀菌剂中的应用
CN113372276B (zh) * 2021-05-25 2022-04-22 三峡大学 吲唑类衍生物及其应用
CN115536586A (zh) * 2021-06-30 2022-12-30 华东理工大学 吡唑酰胺类化合物及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0289879A1 (fr) * 1987-04-24 1988-11-09 Mitsubishi Kasei Corporation Dérivés de pyrazole, composition insecticide et miticide les contenant comme agent actif
EP0307801A1 (fr) * 1987-09-11 1989-03-22 Mitsubishi Kasei Corporation Dérivés de pyrazole et composition insecticide et acaricide la contenant comme ingrédient actif
EP0394043A1 (fr) * 1989-04-19 1990-10-24 Sumitomo Chemical Company, Limited Composés d'amide, leur production et leur usage

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0289879A1 (fr) * 1987-04-24 1988-11-09 Mitsubishi Kasei Corporation Dérivés de pyrazole, composition insecticide et miticide les contenant comme agent actif
EP0307801A1 (fr) * 1987-09-11 1989-03-22 Mitsubishi Kasei Corporation Dérivés de pyrazole et composition insecticide et acaricide la contenant comme ingrédient actif
EP0394043A1 (fr) * 1989-04-19 1990-10-24 Sumitomo Chemical Company, Limited Composés d'amide, leur production et leur usage

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705453A (en) * 1995-02-09 1998-01-06 Mitsubishi Chemical Corporation Indazole compounds and the use thereof
EP0726266A1 (fr) * 1995-02-09 1996-08-14 Mitsubishi Chemical Corporation Dérivés d'indazole et leur utilisation comme fungicides, insecticides et miticides
WO2002083647A1 (fr) * 2001-04-06 2002-10-24 Nihon Nohyaku Co., Ltd. Derive de pyrazole-carboxymide, produit intermediaire pour ce derive et agent antiparasitaire contenant ce derive en tant qu'ingredient actif
JP2005533809A (ja) * 2002-06-19 2005-11-10 シェーリング　コーポレイション カンナビノイドレセプタアゴニスト
FR2845382A1 (fr) * 2002-10-02 2004-04-09 Sanofi Synthelabo Derives d'indazolecarboxamides, leur preparation et leur utilisation en therapeutique
WO2004031158A1 (fr) * 2002-10-02 2004-04-15 Sanofi-Aventis Derives d'indazolecarboxamides, leur preparation et leur utilisation comme inhibiteurs des cdk1, cdk2 et cdk4
US7482342B2 (en) 2002-10-02 2009-01-27 Sanofi-Aventis Indazolecarboxamide derivatives, preparation and use thereof as CDK1, CDK2 and CDK4 inhibitors
US7842711B2 (en) 2004-03-16 2010-11-30 Sanofi-Aventis Indazolecarboxamide derivatives for the treatment and prevention of malaria
WO2008061688A1 (fr) 2006-11-22 2008-05-29 Aziende Chimiche Riunite Angelini Francesco A.C.R.A.F. S.P.A. Composés de 2-alkyl-indazole pour le traitement de certaines affections liées au snc
US8507528B2 (en) 2006-11-22 2013-08-13 Aziende Chimiche Riunite Angelini Francesco A.C.R.A.F. S.P.A. 2-alkyl-indazole compounds for the treatment of certain cns-related disorders
WO2012081916A2 (fr) * 2010-12-17 2012-06-21 한국화학연구원 Dérivé d'indazole et composition pesticide le contenant
WO2012081916A3 (fr) * 2010-12-17 2012-08-16 한국화학연구원 Dérivé d'indazole et composition pesticide le contenant
KR101373185B1 (ko) 2010-12-17 2014-03-13 주식회사경농 인다졸 유도체 및 이를 함유하는 살충제 조성물

Also Published As

Publication number Publication date
MX9305171A (es) 1994-02-28
CN1091426A (zh) 1994-08-31
ZA936305B (en) 1994-02-28
IL106735A0 (en) 1993-12-08
AU4949293A (en) 1994-03-29
TR27142A (tr) 1994-11-09
HRP931151A2 (en) 1996-06-30

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