WO1997047610A1 - Derives de benzazole - Google Patents

Derives de benzazole Download PDF

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Publication number
WO1997047610A1
WO1997047610A1 PCT/EP1997/002731 EP9702731W WO9747610A1 WO 1997047610 A1 WO1997047610 A1 WO 1997047610A1 EP 9702731 W EP9702731 W EP 9702731W WO 9747610 A1 WO9747610 A1 WO 9747610A1
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Prior art keywords
compound
alkyl
formula
alkoxy
haloalkoxy
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PCT/EP1997/002731
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English (en)
Inventor
Olivier Tinembart
Marc-Olivier Bevierre
David John Wadsworth
Christof Hildenbrand
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Novartis Ag
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Priority to AU29623/97A priority Critical patent/AU2962397A/en
Publication of WO1997047610A1 publication Critical patent/WO1997047610A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2

Definitions

  • the present invention relates to novel benzazole derivatives of formula
  • R t is C ⁇ -C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl;
  • R 2 is H or C ⁇ -C 6 alkyl;
  • R 3 and R 4 are each independently of the other H, halogen, d-C 6 alkyl, C 3 -C 7 cycloalkyl, d-Cghaloalkyl, C,-C 6 alkoxy, C r C 6 haloalkoxy, d-Cealkylthio, d-C 6 haloalkylthio, d-C 6 alkyl- sulfinyl, d-C 6 haloalkylsulfinyl, d-Cealkylsulfonyl, C ⁇ -C 6 haloalkylsulfonyl, nitro, cyano, C ⁇ -C 2 haloalkoxycarbonyl or, with the proviso that the other radical R 3 or R 4l as the case may be, is other than H, Ci-Cedialkylamino; or
  • R 3 and R 4 together form a -0(CH 2 ) m O- bridge wherein m is 1 or 2, with the proviso that R 3 and R 4 are bonded to adjacent carbon atoms;
  • R 5 is hydroxy, amino, carboxy-d-C ⁇ alkylamino, C ⁇ -C 6 alkylamino, C ⁇ -C 6 dialkylamino, C ⁇ -C 6 alkoxy, C 2 -C 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, or benzyloxy that is unsubstituted or substituted by from one to three substituents from the group consisting of halogen, nitro, cyano, d-C 6 alkyl, CrC 6 haloalkyl, C r C 6 alkoxy, d-C 6 haloalkoxy, C 3 -C 7 cyclo- alkyl, d-C 6 alkylthio, C r C 6 haloalkylthio, d-C 6 alkylsulfinyl, d-C 6 haloalkylsulfinyl, d-C 6 alkyl
  • Some of the compounds I may be in the form of tautomers.
  • R 2 is H
  • the compounds I and, where appropriate, their tautomers may be in the form of salts.
  • Compounds I having at least one basic centre may, for example, form acid addition salts.
  • Such salts are formed, for example, with strong inorganic acids, such as mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, d-dalkane- carboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, for example oxalic, malonic, maleic, fumaric or phthalic acid, 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, d-C 4 alkane- or
  • 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 ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy- lower alkylamine, for example mono-, di- or tri-ethanolamine. Where appropriate it is also possible for corresponding internal salts to 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 ethyl-, diethyl-, tri
  • any reference to the free compounds I or their salts is to be understood as including also the corresponding salts or free compounds I, respectively, as appropriate and expedient.
  • carbon-containing groups and compounds each contain from 1 up to and including 6, preferably from 1 up to and including 4 and especially 1 or 2, carbon atoms.
  • Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Alkyl - as a group perse and as a structural unit of other groups and compounds, such as of haloalkyl, alkoxy and alkylthio, - is, in each case giving due consideration to the number of carbon atoms present in the group or compound in question, either straight-chain, that is to say methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Alkenyl - as a group per se and as a structural unit of other groups and compounds, such as of alkenyloxy and haloalkenyloxy, - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds present in the group or compound in question, either straight-chain, for example allyl, 2-butenyl, 3-pentenyl, 1 - hexenyl or 1 ,3-hexadienyl, or branched, for example isopropenyl, isobutenyl, isoprenyl or tert-pentenyl.
  • Halogen - as a group perse and as a structural unit of other groups and compounds, such as of haloalkyl, halocycloalkyl and haloalkenyl - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
  • Halo-substituted carbon-containing groups and compounds such as haloalkyl, halocyclo ⁇ alkyl, haloalkenyl, haloalkoxy, haloalkenyloxy, haloalkoxycarbonyl, haloalkylthio, haloalkyl- sulfinyl or haloalkylsulfonyl, may be partially halogenated or perhalogenated, and in the case of multiple halogenation the halogen substituents may be identical or different.
  • haloalkyl - as a group per se and as a structural unit of other groups and compounds, such as of halocycloalkylalkyl, haloalkenyl, haloalkoxy, haloalkenyloxy, haloalkoxycarbonyl, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl - are methyl substituted from one to three times by fluorine, chlorine and/or by bromine, such as CHF 2 or CF 3 ; ethyl substituted from one to five times by fluorine, chlorine and/or by bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl
  • fluorine, chlorine and/or by bromine such as (CH 2 ) conflictCHBrCH 2 Br, CF 2 (CHF) 4 CF 3 , CH 2 (CF 2 ) 4 CF 3 or C(CF 3 ) 2 (CHF) 2 CF 3 .
  • the alkylene chain in the carboxyalkylamino groups is, in each case giving due considera ⁇ tion to the number of carbon atoms present in the groups in question, either straight-chain, for example NHCH 2 COOH, NHCH 2 CH 2 COOH or NHCH 2 CH 2 CH 2 CH 2 COOH, or branched, for example NHCH(CH 3 )COOH, NHCH 2 CH 2 (CH 2 CH 3 )COOH, NHC(CH 3 ) 2 CH 2 COOH or NHCH 2 CH(CH 3 )CH(CH 3 )CH 2 COOH.
  • Physiologically tolerable addition compounds are complexes and salts of compounds of formula I with an inorganic or organic base that are formed by the addition of one or two equivalent amounts of a salt-forming base to the basic molecule of formula I.
  • Suitable inorganic bases are, for example, oxides, hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals (e.g. CaO, BaO, NaOH, KOH, Ca(OH) 2 , KHCO 3 , NaHCO 3> K 2 CO 3 or Na 2 CO 3 ).
  • Typical representatives of suitable organic bases are tetra- butylammonium hydroxide, trialkylamines, such as triethylamine, or dialkylamines, such as diethyl- or dipropyl-amine.
  • Ri is C ⁇ -C 4 alkyl, d-C 2 haloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 cycloalkyl, preferably d-C 4 alkyl or C 3 -C 6 cycloalkyl, especially Ci-dalkyl or C 5 -C 6 cycloalkyl;
  • R 2 is H or d-dalkyl, preferably H or C r C 2 alkyl, especially H or methyl;
  • R 3 is halogen, C ⁇ -C 4 alkyl, C 3 -C 6 cycloalkyl, d-dhalo- alkyl, d-C 4 alkoxy, C ⁇ -C 4 haloalkoxy, d-C 4 alkylthio, C ⁇ -C 4 haloalkylthio, C 1 -C 4 alkylsulfinyl, d- C 4 haloalkylsulfinyl, d-C 4 alkylsulfonyl, d-C 4 haloalkylsulfonyl, nitro, cyano or d-C 2 halo- alkoxycarbonyl, preferably halogen, C ⁇ -C 4 alkyl, C ⁇ -C 2 haloalkyl, C ⁇ -C 2 alkoxy, d-C 2 halo- alkoxy, d-C 2 alkylthio, d-C 2 haloal
  • R 4 is H, halogen, d-C 4 alkyl, C 3 -C 6 cycloalkyl, d-C 4 - haloalkyl, d-C 4 alkoxy, Ci-dhaloalkoxy, C ⁇ -C 4 alkylthio, d-C 4 haloalkylthio, d-dalkyl- sulfinyl, d-C 4 haloalkylsulfinyl, d-dalkylsulfonyl, C ⁇ -C 4 haloalkylsulfonyl, nitro, cyano or d-C 2 haloalkoxycarbonyl, preferably H, halogen, C ⁇ -C 2 alkyl, d-C 2 haloalkyl, d-C 2 alkoxy, d-C 2 haloalkoxy, d-C 2 alkylthio, C ⁇ -C 2 halo
  • R 5 is hydroxy, amino, carboxy-d-C 4 alkylamino, d-C 4 - alkylamino, C ⁇ -C 4 dialkylamino, C r C 4 alkoxy, C 2 -C 4 haloalkoxy or benzyloxy, preferably hydroxy, amino, carboxy-C ⁇ -C 4 alkylamino, d-C 2 alkylamino, d-C 2 dialkylamino, d-C 2 alkoxy or d-C 2 haloalkoxy, especially hydroxy, amino, carboxy-d-C 2 alkylamino, methylamino, dimethylamino or C ⁇ -C 2 alkoxy; (8) a compound of formula I wherein R 6 is d-C 4 alkyl, d-C 4 haloalkyl or C ⁇ -C 6 alkoxy, prefer ⁇ ably d-C 4 alkyl, C ⁇ -C 4 haloalkyi or
  • R is d-C 4 alkyl or C 3 -C 6 cycloalkyl
  • R 2 is H or d-d ⁇ alkyl
  • R 3 is halogen, d-C 4 alkyl, C ⁇ -C 2 haloalkyl, d-C 2 alkoxy, d-C 2 haloalkoxy, C ⁇ -C 2 alkylth ⁇ o, d-C 2 haloalkylthio, d-C 2 alkylsulfinyl, C r C 2 haloalkylsulfinyl, d-C 2 alkylsulfonyl, d-C 2 - haloalkylsulfonyl, nitro or cyano
  • R 4 is H, halogen, d-C 2 alkyl, C 1 -C 2 haloalkyl, C r C 2 alkoxy, d-C 2 haloalkoxy, d-C
  • Ri is C ⁇ -C 4 alkyl or C 5 -C 6 cycloalkyl
  • R 2 is H or d-d ⁇ alkyl
  • R 3 is halogen, d-C 4 alkyl, C ⁇ -C 2 haloalkyl, d-dalkoxy, d-C 2 haloalkoxy, C ⁇ -C 2 alkylthio, C ⁇ -C 2 haloalkylthio, C ⁇ -C 2 alkylsulfinyl, C ⁇ -C 2 haloalkylsulfinyl, C ⁇ -C 2 alkylsulfonyl, C r C 2 - haloalkylsulfonyl, nitro or cyano
  • R 4 is H, halogen, d-C 2 alkyl, C 1 -C 2 haloalkyl, d-C 2 alkoxy, C ⁇ -C 2 haloalkoxy, C ⁇ -C 2 alky
  • R is C ⁇ -C 4 alkyl or C 5 -C 6 cycloalkyl
  • R 2 is H or methyl
  • R 3 is fluorine, chlorine, d-dalkyl, d-dalkoxy, C ⁇ -C 2 haloalkoxy, C r C 2 alkylthio, d-dalkyl- sulfinyl or d-dhaloalkylsulfinyl
  • R 4 is H, halogen, d-C 2 alkyl, d-C 2 haloalkyl, C r C 2 alkoxy, d-C 2 haloalkoxy, C r C 2 alkylthio, d-C 2 haloalkylthio, d-C 2 alkylsulfinyl, d-C 2 haloalkylsulfinyl, d-dalkylsulfonyl, C ⁇ -C 2 haloal
  • Ri is d-dalkyl or C 5 -C 6 cycloalkyl
  • R 2 is H or methyl
  • R 3 is fluorine, chlorine, C ⁇ -C 2 alkyl, C r C 2 alkoxy, d-C 2 haloalkoxy, d-dalkylthio, d-dalkyl- sulfinyl or d-C 2 haloalkylsulfinyl
  • R 4 is H, C ⁇ -C 2 alkyl, d-C 2 alkoxy, nitro or cyano
  • R 5 is hydroxy, amino, carboxy-d-C 2 alkylamino, methylamino, dimethylamino or C ⁇ -C 2 alkoxy
  • R 6 is C ⁇ -C 2 alkyl or d-C 2 haloalkyl
  • R is d-C 4 alkyl or C 5 -C 6 cycloalkyl
  • R 2 is H or methyl
  • R 3 is fluorine, chlorine, d-C 2 alkyl, C ⁇ -C 2 alkoxy, C ⁇ -C 2 haloalkoxy, C ⁇ -C 2 alkylthio, d-C 2 - alkylsulfinyl or C ⁇ -C 2 haloalkylsulfinyl
  • R 4 is H, d-C 2 alkyl or nitro
  • R 5 is hydroxy, amino, carboxy-d-C 2 alkyiamino, methylamino, dimethylamino or d-C 2 alkoxy
  • R 6 is d-C 2 alkyl
  • n 1
  • Rt is d-C 4 alkyl or C 5 -C 6 cycloalkyl
  • R 2 is H or methyl
  • R 3 is fluorine, chlorine, d-dalkyl, d-C 2 alkoxy, C r C 2 haloalkoxy, d-C 2 alkylthio, C ⁇ -C 2 alkylsulfinyl or C ⁇ -C 2 haloalkylsulfinyl
  • R 4 is H, d-C 2 alkyl or nitro
  • R 5 is hydroxy, amino, carboxy-d-C 2 alkylamino, methylamino, dimethylamino or d-dalkoxy
  • R 6 is d-C 2 alkyl
  • a compound of formula I wherein n is 1 , X is S, R, is C ⁇ -C 4 alkyl or C 5 -C 6 cycloalkyl, R 2 is H or methyl, R 3 is fluorine, chlorine, C ⁇ -C 2 alkyl, C ⁇ -C 2 alkoxy, C r C 2 haloalkoxy, d-C 2 alkylthio, d-dalkylsulfinyl or d-C 2 haloalkylsulfinyl, R 4 is H, C ⁇ -C 2 alkyl or nitro, R 5 is hydroxy, amino, carboxy-C ⁇ -C 2 alkylamino, methylamino, dimethylamino or C ⁇ -C 2 alkoxy, and R 6 is C ⁇ -C 2 alkyl;
  • a compound of formula I wherein n is 1 , X is S, Ri is C ⁇ -C 4 alkyl or d-dcycloalkyl, R 2 is H or methyl, R 3 is fluorine, chlorine, C ⁇ -C 2 alkyl, C ⁇ -C 2 alkoxy, C ⁇ -C 2 haloalkoxy, d-dalkylthio, C 1 -C 2 alkylsulfinyl or C ⁇ -C 2 haloalkylsulfinyl, R 4 is H, d-dalkyl or nitro, R 5 is hydroxy, amino, carboxy-d-dalkylamino, methylamino, dimethylamino or d-C 2 a!koxy, R 6 is d-C 2 alkyl and the dithiocarbamate substituent is in the 4-, 5- or 6-position, preferably in the 6-position; ⁇ n each case including the physiologically tolerable addition compounds
  • the invention relates also to the process for the preparation of the compounds of formula I and where appropriate their tautomers, taking into consideration the proviso given above, in each case in free form or in salt form, which process comprises, for example,
  • NCS which is known or can be prepared analogously to corresponding known compounds and in which X, Ri, R 3 and R 4 are as defined for formula I, in free form or in salt form, with a compound of formula
  • R3 and R 4 are as defined for formula I and Z is an ammonium ion of a tertiary amine, for example of triethylamine or 1 ,4-diazabicyclo[2.2.2]octane, or is an alkali metal ion, or where appropriate a tautomer thereof, in free form or in salt form, with a compound of formula III, which is known or can be prepared analogously to corresponding known compounds and in which n, R 5 and R 6 are as defined for formula I and Y is a leaving group, for example bromine, chlorine, iodine, alkylsulfonyl or p-toluenesulfonyl, preferably bromine, or where appropriate a tautomer thereof, in free form or in salt form, and in each case, if desired, a compound of formula I or a tautomer thereof obtainable in accordance
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • solvents and diluents include aromatic, aliphatic and ahcyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralm, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, tnchloromethane, tetra- chloromethane, dichloroethane, tnchloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, dnsopropyl ether, dibutyl ether, tert- butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy
  • the reaction is advantageously carried out in a temperature range of from approximately -10°C to approximately +150°C, preferably from approximately -5°C to approximately +50°C.
  • a compound of formula II is reacted with a com ⁇ pound of formula III at from 0° to 40°, preferably 20°, in an amide, preferably dimethyl- formamide, under an inert atmosphere, preferably under argon gas.
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert- butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethy
  • the reaction is advantageously carried out in a temperature range of from approximately -10°C to approximately +150°C, preferably from approximately -5°C to approximately +50°C.
  • a compound of formula IV is reacted with a compound of formula III at from -5° to 40°, preferably 20°, in an amide, preferably dimethylformamide, under an inert atmosphere, preferably under argon gas.
  • the invention relates also to the process for the preparation of compounds of formula IV, and where appropriate the tautomers thereof, taking into consideration the proviso given above, in each case in free form or in salt form, which process comprises, for example, reacting a compound of formula which is known or can be prepared analogously to corresponding known compounds and in which X, Ri, R 2 , R 3 and R 4 are as defined for formula I, or where appropriate a tautomer thereof, in free form or in salt form, with carbon disulfide in the presence of an ammonium ion of a tertiary amine, for example of triethylamine or 1 ,4-diazabicyclo[2.2.2]octane, or an alkali metal ion and in each case, if desired, a compound of formula IV or a tautomer thereof obtainable in accordance with the process or by another route, in each case in free form or in salt form, is converted into a different compound of formula IV or a tautomer thereof,
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in molten form.
  • a solvent or diluent for example in molten form.
  • solvents and diluents include aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert- butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethy
  • reaction is carried out in the presence of an organic base
  • bases used in excess such as triethylamine, pyndme, N- methylmorpholine, 1 ,4-d ⁇ azabicyclo[2.2.2]octane or N,N-d ⁇ ethylan ⁇ l ⁇ ne, to act as solvent or diluent.
  • the reaction is advantageously carried out in a temperature range of from approximately -10°C to approximately +150°C, preferably from approximately -5°C to approximately +50°C.
  • a compound of formula V is reacted with carbon disulfide at from 0° to 40°, preferably 20°, in a hydrocarbon, preferably toluene, in the presence of a tertiary amine, preferably 1 ,4-d ⁇ azab ⁇ cyclo[2.2.2]octane, under an inert atmosphere, preferably under argon gas
  • Salts of compounds I can be prepared in a manner known per se. For example, acid addition salts of compounds I 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 other salts of compounds I in a manner known per se; acid addition salts, for example, can be converted into other acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochlo ⁇ de, 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 that forms, for example silver chloride, is insoluble and is therefore precipitated out of the reaction mixture
  • the compounds I having salt- forming properties may be obtained in free form or in the form of salts.
  • the compounds I and IV may be in the form of one of the possible isomers or in the form of a mixture thereof, for example according to the number of asymmetric carbon atoms present and the absolute and relative configuration thereof, they may be in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of isomeric mixtures, such as enantiomeric mixtures, for example racemates, diastereoisomeric mixtures or mixtures of racemates; the invention relates both to the pure isomers and to all possible isomeric mixtures and that is to be understood accordingly hereinabove and hereinbelow even if stereochemical details are not specifically mentioned in every case.
  • Diastereoisomeric mixtures and mixtures of racemates of compounds I and IV obtainable in accordance with the process - depending upon the starting materials and procedures chosen - or by another route can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.
  • Enantiomeric mixtures such as racemates, so obtainable can be separated into the optical antipodes in accordance with known methods, for example by recrystallisation from an optically active solvent, by chromatography on chiral adsorbents, for example high pressure liquid chromatography (HPLC) on acetyl cellulose, with the aid of suitable microorganisms, by cleavage with specific immobilised enzymes, or via the formation of inclusion compounds, for example using chiral crown ethers, in which case only one enantiomer is complexed.
  • HPLC high pressure liquid chromatography
  • the invention relates to all those embodiments of the process according to which a com ⁇ pound obtainable as starting material or intermediate at any stage of the process is used as starting material and some or all of the remaining steps are carried out or a starting material is used in the form of a derivative or 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 P4.
  • the invention relates also to starting materials and intermediates used according to the invention for the preparation of compounds I and their salts, in each case in free form or in salt form, that are novel, to their use and to processes for their preparation.
  • the compounds I according to the invention are valuable active ingredients in the field of pest control while being well tolerated by warm-blooded animals, fish and plants. They have a broad spectrum of action against helminths that parasitise the animal organism, especially mammals, such as nematodes, cestodes and trematodes, their action being directed espe ⁇ cially against nematodes (roundworms). They are effective against all or individual stages of development of normally sensitive and also resistant species of helminth.
  • novel compounds of formula I are suitable, for example, for controlling parasitic nematodes of the orders (according to K.I. Skrajabin)
  • Trichocephalida or for controlling cestodes of the orders (according to Wardle & McLeod)
  • Digenea in domestic animals and productive livestock such as cattle, sheep, goats, horses, pigs, red deer, cats, dogs and fowl. They can be administered to the animals either as a single dose or repeatedly, the single doses preferably being from 1 to 50 mg per kg of body weight, depending upon the species of animal. In many cases, protracted administration may result in an improved action or may permit the use of smaller total doses.
  • the present invention relates also to the preparation of those compositions, which comprises intimately mixing and/or grinding the active ingredient with one or more substances or groups of substances described herein.
  • the formulation stages may be supplemented by kneading, granulation (in the case of granules) and if necessary compressing (in the case of pellets).
  • a prophylactic and/or curative method of controlling helminths in mammals which comprises the application of the compounds of formula I according to the invention or the compositions according to the invention to the habitat of the pest.
  • Target animals for use as anthelmintics are all warm-blooded animals, especially mammals and birds, liable to be affected by helminths, but especially domestic animals, productive livestock and game, such as cows, horses, donkeys, sheep, goats, llamas, camels, red deer, pigs, dogs, cats, rabbits, chickens, turkeys, ducks, geese, pheasants, partridges, etc., and also all animals bred for their fur. It will be understood that the successful treatment of infested zoo animals is also possible. It is generally known that of the endoparasites occurring in warm-blooded animals it is particularly the helminths that cause great damage to the animals infested by them.
  • worm-related disorders in herds of animals, such damage caused by helminthiases can assume serious economic proportions. In the animals affected, the damage manifests itself inter alia as losses of productivity, reduced resistance to other diseases and increased mortality. Especially dangerous worm- related disorders are caused by helminths parasitising the gastro-intestinal tract and other organs and, despite numerous prophylactic measures, still occur relatively frequently in ruminants, such as cattle, sheep and goats, as well as in horses, pigs, fowl, red deer, dogs and cats.
  • helminths is to be understood as meaning especially parasitic worms that belong to the Platyhelminthes (cestodes, trematodes) and Nemathelminthes (nematodes and related species), that is to say tape worms, sucker worms and roundworms of the gastro-intestinal tract and other organs (for example liver, lungs, kidneys, lymph vessels, blood, etc.).
  • the good pesticidal action of the compounds of formula I according to the invention corres ⁇ ponds to a mortality of at least 50-60 % of the mentioned pests.
  • Suitable additives include, for example, representatives of the following classes of active ingredient: organo- phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.
  • the compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or a combination of that active ingredient with other agrochemical active ingredients, and, as appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingre ⁇ histones with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • extenders for example with solvents, solid carriers, and optionally surface-active compounds (surfactants).
  • Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as xylene mixtures or alkylated naphthalenes; aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols, such as ethanol, propanol or butanol, and glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide or water, vegetable oils, such as rape, castor, coconut or soybean oil; and optionally also silicone oils.
  • aromatic hydrocarbons preferably the fractions containing 8 to 12 carbon
  • the solid carriers used are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • calcite calcite
  • talcum kaolin
  • montmorillonite kaolin
  • attapulgite a highly dispersed silicic acid or highly dispersed absorbent polymers.
  • Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable non-sorbent carriers are calcite or sand.
  • a great number of granulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactant is also to be understood as including mixtures of surfactants.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C ⁇ 0 -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 methyltaurine salts as surfactants.
  • 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, the alkyl moiety of acyl radicals also being included, e.g. 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 two sulfonic acid groups and one fatty acid radical containing about 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine 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.
  • 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 the 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, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxy- ethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as N- 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, e.g. stearyltnmethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the surfactants customarily employed in formulation technology are described, for example, in the following publications-
  • Preferred forms of administration for use in warm-blooded animals for controlling helminths include solutions, emulsions, suspensions (drenches), feed additives, powders, tablets, including effervescent tablets, boll, capsules and microencapsulations, with attention being paid to the physiological tolerability of the formulation adjuvants
  • Suitable binders for tablets and boll are chemically modified natural polymer substances that are soluble in water or alcohol, such as starch derivatives, cellulose derivatives or protein derivatives (e.g methyl cellulose, carboxymethylcellulose, ethylhydroxyethylcellulose, proteins, such as zein, gelatin and the like) and synthetic polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, etc
  • the tablets also contain fillers (e.g. starch, microcrystalhne cellulose, sugar, lactose, etc.), glidants and disintegrators
  • the carriers used are, for example, performance feed, feed grain or protein concentrates.
  • feed concentrates or compositions may comprise additives, vitamins, antibiotics, chemotherapeutic agents or other pesticides, especially bacte ⁇ o- statics, fungistatics or coccidiostatics, or hormone preparations, substances having an anabolic activity or substances that promote growth, influence the meat quality of animals for slaughter or are useful to the organism in some other way.
  • compositions or the compounds of formula I contained therein are added directly to the feed or to animal drinks, then the prepared feed or the prepared drink preferably contains the active ingredients in a concentration of approximately from 0.0005 to 0.02 % by weight (5-200 ppm).
  • the compositions according to the invention can be administered to the animals to be treated perorally, parenterally or subcutaneously, the compositions being in the form of solutions, emulsions, suspensions (drenches), powders, tablets, boh and capsules.
  • the anthelmintic compositions according to the invention generally comprise from 0.1 to 99 % by weight, preferably from 0.1 to 95 % by weight, of the compound of formula I, from 99.9 to 1 % by weight, preferably from 99.8 to 5 % by weight, of a solid or liquid adjuvant, including from 0 to 25 % by weight, preferably from 0 1 to 25 % by weight, of a surfactant.
  • compositions may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers, as well as other active ingredients for obtaining special effects
  • the present invention relates also to such anthelmintic compositions employed by the end user
  • the compounds of formula I can be used in any of their spatial configurations, as mixtures thereof or in the form of their salts
  • the invention also includes a method for the prophylactic protection of warm-blooded animals, especially productive livestock, domestic animals and game, against parasitic helminths, which method comprises administering the compounds of formula I or the active ingredient formulations prepared therefrom to the animals as an additive to feed or to drinks or in solid or liquid form orally, by injection or parenterally.
  • the invention also includes the compounds of formula I according to the invention for use in one of the said methods.
  • Emulsifiable concentrates active ingredient: 1 to 90 %, preferably 5 to 20 % surface-active agent: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Iniection solution active ingredient: 0.1 to 10 %, preferably 0.5 to 5 % non-ionic surfactant: 0.1 to 30 %, preferably 0.5 to 10 % mixture of ethanol and propylene glycol: 60 to 99 %, preferably 85 to 90 %
  • Iniection suspension (a ⁇ ueous or oily): active ingredient: 0.1 to 20 %, preferably 1 to 10 % non-ionic surfactant: 0.1 to 20 %, preferably 1 to 10 % water or vegetable oil: 60 to 99 %, preferably 85 to 95 %
  • compositions may also comprise further auxiliaries, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
  • auxiliaries such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
  • Example P1 R-(2-Acetamido-2-carboxyethyl) N-(2-tert-butyl-5-methylbenzothiazol-6-yl)- dithiocarbamate
  • a mixture of 13.9 g of 2-tert-butyl-6-isothiocyanato-5-methoxybenzothiazole and 9.0 g of N- acetyl-L-cysteine is stirred in 50 ml of dimethylformamide at room temperature under an argon atmosphere for 3 days. After cooling to 4°C, 500 ml of water are added dropwise with stirring. The resulting crystals are filtered, stirred twice in 500 ml of water and dried under a high vacuum at room temperature for 15 hours.
  • Example P3 1 ,4-Diazabicyclo[2.2.2]octanium N-(2-tert-butyl-5-methoxybenzothiazol-6-yl)- dithiocarbamate
  • Example P4 RS-(2-Acetamido-2-methoxycarbonylethyl) N-(2-tert-butyl-5-methoxybenzo- thiazol-6-yl)dithiocarbamate
  • the residue is chromatographed on 300 g of silica gel using 1500 ml of a 1 :2 mixture of ethyl acetoacetate/hexane, 2000 ml of a 1 :1 mixture of ethyl acetoacetate/hexane, 1500 ml of a 2:1 mixture of ethyl acetoacetate/hexane and 1000 ml of ethyl acetoacetate.
  • 1.4 g of a crude product are obtained which is recrystallised from diethyl ether.
  • the melting point of the pure product is 143-145°C.
  • Emulsifiable concentrates a) b) c) a compound of Table 1 25 % 40 % 50 % calcium dodecyl benzenesulfonate 5 % 8 % 6 % castor oil polyethylene glycol ether
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • Emulsifiable concentrates a) b) c) a compound of Table 1 10 % 8 % 60 % octylphenol polyethylene glycol ether
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • 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.
  • Powder mixtures dispersible in water a) b) c) a compound of Table 1 25% 50% 75% sodium lignosulfonate 5% 5% - oleic acid 3% - 5% sodium diisobutylnaphthalenesulfonate - 6% 10% octylphenol polyethylene glycol ether
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration
  • Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient and grinding the mixture
  • the active ingredient is dissolved in methylene chloride and the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
  • Such granules can be mixed with animal feed.
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water The mixture is extruded and then dried in a stream of air 2.8.
  • Granules a compound of Table 1 3 % polyethylene glycol (MW 200) 3 % kaolin 94 %
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • the methylcellulose is stirred into water. Once the materal has swelled, the silicic acid is stirred in and the mixture is made into a homogeneous suspension.
  • the active ingredient and corn starch are mixed together and the aqueous suspension is incorporated into the mixture which is then kneaded to a paste. The mass so obtained is granulated through a 12M sieve and dried.
  • Oily vehicle (slow release) a compound of Table 1 0.1-1.0 g groundnut oil ad 100 ml
  • Preparation The active ingredient is dissolved in a portion of the oil with stirring and optionally with gentle heating, and after cooling the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 ⁇ m membrane filter.
  • Preparation The active ingredient is dissolved in a portion of the solvent with stirring, and the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 ⁇ m membrane filter.
  • Aqueous solubilisate (rapid release) a compound of Table 1 0.1-1.0 g polyethoxylated castor oil (40 ethylene oxide units) 10 g
  • Preparation The active ingredient is dissolved in the solvents and the surfactant, and the solution is made up to the desired volume with water. Sterile-filtration is then carried out through a suitable membrane filter of 0.22 ⁇ m pore diameter.
  • aqueous systems can be used in a preferred manner also for oral and/or intraruminal administration.
  • the anthelmintic activity is demonstrated by means of the following trials:
  • a first evaluation is made by comparing the number of worm eggs excreted in the faeces of the sheep before and after treatment.
  • the sheep Seven to ten days after treatment the sheep are sacrificed and dissected. The evaluation is carried out by counting the worms remaining in the intestine after the treatment. Sheep simultaneously and similarly infested but untreated are used as a control or comparison.
  • a marked reduction in nematode infestation is achieved with compounds of formula I of Table 1.
  • a reduction in nematode infestation of approximately 90-100 % is achieved using 20 mg of active ingredient per kg of body weight with compounds 1.3 and 1 .7.
  • that result is obtained even with a further reduced dosage, for example with 10 mg of active ingredient per kg of body weight or even smaller amounts of active ingredient.
  • the active ingredient is administered in the form of a suspension using a stomach probe or by intraruminal injection to sheep that have previously been artificially infested with Fasciola hepatica. 3 animals are used for each dose and each trial. Each sheep is treated with only a single dose.
  • a first evaluation is made by comparing the number of worm eggs excreted in the faeces of the sheep before and after treatment.

Abstract

Composés de la formule (I) dans laquelle n, X, R1, R2, R3, R4, R5 et R6 sont tels que définis dans la revendication 1, et, le cas échéant, leurs tautomères, dans tous les cas sous une forme libre ou sous forme d'un sel acceptable sur le plan agrochimique, pouvant être utilisés comme ingrédients à activité agrochimique et pouvant être préparés selon une technique connue en soi.
PCT/EP1997/002731 1996-06-07 1997-05-27 Derives de benzazole WO1997047610A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU29623/97A AU2962397A (en) 1996-06-07 1997-05-27 Benzazole derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1434/96 1996-06-07
CH143496 1996-06-07

Publications (1)

Publication Number Publication Date
WO1997047610A1 true WO1997047610A1 (fr) 1997-12-18

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WO (1) WO1997047610A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1464326A (en) * 1974-06-19 1977-02-09 Smithkline Corp Benzimidazole carbamates
EP0041046A1 (fr) * 1980-05-22 1981-12-02 Ciba-Geigy Ag Dérivés de benzazoles, procédés pour leur préparation, leurs compositions pharmaceutiques et leur application
EP0175650A2 (fr) * 1984-09-19 1986-03-26 Ciba-Geigy Ag Benzazoles, procédé pour leur préparation compositions pharmaceutiques les contenant et leur utilisation
WO1988000183A1 (fr) * 1986-06-30 1988-01-14 Fmc Corporation Derives de s-trifluorobutenyle et leur utilisation comme pesticides
EP0356385A2 (fr) * 1988-08-17 1990-02-28 Ciba-Geigy Ag Benzazoles, procédé de préparation, compositions pharmaceutiques les contenant et leur utilisation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1464326A (en) * 1974-06-19 1977-02-09 Smithkline Corp Benzimidazole carbamates
EP0041046A1 (fr) * 1980-05-22 1981-12-02 Ciba-Geigy Ag Dérivés de benzazoles, procédés pour leur préparation, leurs compositions pharmaceutiques et leur application
EP0175650A2 (fr) * 1984-09-19 1986-03-26 Ciba-Geigy Ag Benzazoles, procédé pour leur préparation compositions pharmaceutiques les contenant et leur utilisation
WO1988000183A1 (fr) * 1986-06-30 1988-01-14 Fmc Corporation Derives de s-trifluorobutenyle et leur utilisation comme pesticides
EP0356385A2 (fr) * 1988-08-17 1990-02-28 Ciba-Geigy Ag Benzazoles, procédé de préparation, compositions pharmaceutiques les contenant et leur utilisation

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