Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
  • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
  • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
  • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
  • A61P33/00—Antiparasitic agents
  • A61P33/10—Anthelmintics
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems

Definitions

• the present invention relates to novel 4,5-dicyanoimidazolyl derivatives of formula I below, which have anthelmintic, acaricidal and insecticidal activity.
• the invention relates also to pharmaceutical compositions and pesticides based on the compounds of formula I. It relates also to the preparation of the active ingredients and compositions and to the use thereof for controlling helminths, especially nematodes, cestodes and trematodes in warm-blooded animals, especially in domestic animals and productive livestock, and to the use thereof for controlling pests of the order Arthropoda, especially for controlling insects and representatives of the order Acarina.
• the present invention relates likewise to valuable intermediates which can be used for the preparation of active ingredients, especially those of formula I below.
• X is oxygen, sulfur, SO or SO 2 ;
• R 1 is hydrogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 cyanoalkyl, or a C 1 -C 6 alkylene substituted by C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkyloxycarbonyl, C 1 -C 6 alkylcarbonyl, C 1 -C 6 alkylcarbonyloxy or by COOH;
• R 2 is hydrogen, halogen, CN, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 cyanoalkyl, C 1 -C 6 -hydroxyalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio or
• R 3 is hydrogen, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, cyano or nitro;
• R 4 is hydrogen, halogen, nitro, cyano, NCS, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; and R 5 is hydrogen, halogen, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; or
• R 4 and R 5 together form a -O-(CH 2 ) m -O- bridge, wherein m is an integer selected from the group consisting of 1, 2 and 3, with the proviso that R 4 and R 5 are located at adjacent carbon atoms;
• alkyl by itself or as part of another substituent is to be understood as meaning, for example, the following straight-chained and branched groups, depending on the number of carbon atoms indicated: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, etc..
• Haloalkyl by itself or as part of haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl is a mono- to per-halogenated alkyl substituent, for example CH 2 CI, CHCI 2 , CCI 3 , CH 2 F, CHF 2 , CF 3 , CH 2 Br, CHBr 2 , CBr 3 , CH 2 I, CI 3 , CHClF, CHBrCl, CFBrCl, C 2 F 5 , CH 2 CH 2 Cl,
• halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, but especially chlorine.
• NCS is N ⁇ C-S-; alkylthio is alkyl-S-; alkylsulfinyl is alkyl-S(O)-; alkylsulfonyl is alkyl-S(O) 2 -; alkylcarbonyl is alkyl-C(O)-; alkylcarbonyloxy is alkyl-C(O)-O-; alkyloxycarbonyl is alkyl-O-C(O)-;
• alkylene is a saturated aliphatic bridge member that is unbranched or branched, for example -CH 2 -; -CH 2 CH 2 -; -CH 2 CH(CH 3 )-; -CH 2 CH(CH 3 )CH 2 -; -CH 2 C(CH 3 ) 2 -; etc..
• Cycloalkyl by itself or as part of a substituent is, depending on the number of carbon atoms indicated, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc..
• Cyanoalkyl is an alkyl group in which from one to three hydrogen atoms have been substituted by CN, preferably an alkyl group in which a CN group is located at the terminal carbon atom.
• hydroxyalkyl is an alkyl group in which from one to three hydrogen atoms have been substituted by OH, preferably an alkyl group in which an OH group is located at the terminal carbon atom.
• physiologically tolerable addition compounds is to be understood as meaning complexes or salts of a compound of formula I with an inorganic or organic base, which are formed by the addition of an equivalent amount of a salt-forming base to the base molecule of formula I, or with solvents such as dimethylformamide (DMF) or dimethylacetamide (DMA).
• suitable inorganic bases are 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 ).
• suitable organic bases are tetrabutylammonium hydroxide; trialkylamines, such as triethylamine, or dialkylamines, such as diethyl- or dipropyl-amine.
• X is oxygen or sulfur
• R 1 is hydrogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 hydroxyalkyl, or a Ci ⁇ C4alkylene substituted by C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 1 -C 3 hydroxyalkyl, C 1 -C 3 alkyloxycarbonyl, C 1 -C 3 alkylcarbonyl or by COOH;
• R 2 is hydrogen, halogen, CN, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 cyanoalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio or C 3 -C 6 cycloalkyl;
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro;
• R 4 is hydrogen, halogen, nitro, cyano, NCS, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;
• R 5 is hydrogen, halogen, nitro, C 1 -C 3 alkyl, C 1 -C 3 - ⁇ aloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy; or
• R 4 and R 5 together form a -O-(CH 2 ) m -O- bridge, wherein m is an integer selected from the group consisting of 1, 2 and 3, with the proviso that R 4 and R 5 are located at adjacent carbon atoms;
• X is oxygen or sulfur
• R 1 is hydrogen, C 1 - C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 hydroxyalkyl, or a C 1 -C 4 alkylene substituted by C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 1 -C 3 hydroxyalkyl, C 1 -C 3 alkyloxycarbonyl, C 1 -C 3 alkylcarbonyl or by COOH;
• R 2 is hydrogen, halogen, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro
• R 4 is hydrogen, halogen, C 1 -C 2 alkyl or OCF 3 ;
• R 5 is hydrogen, halogen, nitro, C 1 -C 2 alkyl, OCF 3 or CF 3 ;
• X is oxygen or sulfur
• R 1 is hydrogen
• R 2 is hydrogen, fluorine, chlorine, bromine, CN, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy;
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro;
• R 4 is hydrogen, halogen, C 1 -C 2 alkyl or OCF 3 ;
• R 5 is hydrogen, halogen, nitro, C 1 -C 2 alkyl, OCF 3 or CF 3 ;
• X is oxygen or sulfur
• R 1 is C 1 -C 2 alkyl, preferably methyl
• R 2 is hydrogen, halogen, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy;
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro;
• R 4 is hydrogen, halogen, C 1 -C 2 alkyl or OCF 3 ;
• R 5 is hydrogen, halogen, nitro, C 1 -C 2 alkyl, OCF 3 or CF 3 ;
• X is oxygen
• R 1 is hydrogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, or a C 1 -C4alkylene substituted by C 1 -C 3 -alkoxy, Ci ⁇ haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio, C 1 -C 3 alkylsulf ⁇ nyl, C 1 -C 3 haloalkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 1 -C 3 hydroxyalkyl, C 1 -C 3 alkyloxycarbonyl, C 1 -C 3 alkylcarbonyl or by COOH;
• R 2 is hydrogen, halogen, C 1 -C 2 haloalkyl, C 1 -C 2 haloalkoxy or C 1 -C 2 alkoxy;
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro;
• R 4 is hydrogen, halogen, C 1 -C 2 alkyl or OCF 3 ;
• R 5 is hydrogen, halogen, nitro, C 1 -C 2 alkyl, OCF 3 or CF 3 ; including the physiologically tolerable addition compounds.
• X is oxygen or sulfur
• R 1 is hydrogen, C 1 -C 3 alkyl or C 1 -C 2 hydroxyalkyl
• R 2 is hydrogen, fluorine, chlorine, CF 3 , CN, C 1 -C 2 alkyl or C 1 -C 2 alkoxy;
• R 3 is hydrogen, fluorine or chlorine
• R 4 is hydrogen
• R 5 is hydrogen, fluorine, chlorine, nitro, C 1 -C 2 alkoxy, OCF 3 or CF 3 ;
• R 4 and R 5 together form a -O-CH 2 CH 2 -O- group which links the carbon atoms C-5 and
• X is oxygen or sulfur
• R 1 is C 1 -C 3 haloalkyl, or a C 1 -C 4 alkylene substituted by C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 hydroxyalkyl or by COOH;
• R 2 is hydrogen, halogen, CN, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 cyanoalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 haloalkylthio or C 3 -Cgcycloalkyl;
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro;
• R 4 is hydrogen, halogen, nitro, cyano, NCS, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;
• R 5 is hydrogen, halogen, nitro, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy; or
• R 4 and R 5 together form a -O-(CH 2 ) m -O- bridge, wherein m is an integer selected from the group consisting of 2 and 3, with the proviso that R 4 and R 5 are located at adjacent carbon atoms;
• X is oxygen or sulfur
• R 1 is C 1 -C 3 haloalkyl, or a C 1 -C 4 alkylene substituted by C 1 -C 3 alkoxy;
• R 2 is hydrogen, halogen, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy
• R 3 is hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyano or nitro
• R 4 is hydrogen, halogen, C 1 -C 2 alkyl or OCF 3 ;
• R 5 is hydrogen, halogen, nitro, C 1 -C 2 alkyl, OCF 3 or CF 3 ;
• R 1 , R 2 , R 3 , R 4 , R 5 and X are as defined under formula I, with a suitable oxidising agent and, in those cases in which R 1 in the compound of formula II is hydrogen, introducing an alkyl radical mentioned under Ri in formula I by subsequent alkylation, or
• R 4 and R 5 are as defined under formula I and Y is a customary leaving group.
• the cyclisation of variant (a) may be carried out using cyclising agents known per se.
• suitable cyclising agents are:
• Iodine in a polar organic solvent for example N-methyl-2-pyrrolidone
• an inorganic base such as sodium acetate
• Organic oxidising agents such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), in a polar inert solvent, such as acetonitrile, and at elevated temperature [cf. EP-283 173].
• DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
• Aqueous organic oxidising agents such as sodium hypochlorite [cf. Jpn. Kokai Tokhyo koko 79, 112, 861] or N-chlorosuccinimide in a polar organic solvent, such as N,N- dimethylformamide (DMF), with the addition of a soluble organic base, such as nicotinamide [cf. Synthesis 1058 (1984)].
• a polar organic solvent such as N,N- dimethylformamide (DMF)
• DMF N,N- dimethylformamide
• reaction temperatures are customarily from +20° to +100°C, preferably from +40° to +90°C.
• a compound of formula II wherein Ri is hydrogen is preferably used as starting material and one of the alkyl substituents mentioned under Ri from the group C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 cyanoalkyl, and a C 1 -C 5 -alkylene substituted by C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfmyl, C 1 -C 6 haloalkylsulfmyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 haloalkoxy, C 1 -C 6 hydroxyalkyl, C 1 -C 6 alkyl, C 1
• Variant (b) [reaction of III with IV] is preferably carried out in the presence of an inert polar organic solvent, such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAA) or DMF, the reaction advantageously being carried out in the presence of an inorganic base at temperatures of from 0° to +180°C, preferably from +20° to +160°C.
• an inorganic base is oxides, hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals (e.g.
• alkali metal alcoholates for example sodium ethanolate, sodium propanolate, potassium tert-butanolate and sodium methanolate.
• the base is advantageously added in an amount of from 10 to 100 % of the equimolar amount, based on the reactants.
• the water of reaction formed in this reaction may optionally be removed from the reaction mixture by means of a customary entrainer, for example methylene chloride, benzene or toluene.
• Customary leaving groups in connection with reaction (b) are to be understood as being, for example, halogen, especially chlorine, bromine or iodine, preferably chlorine, or sulfonyl radicals, such as benzoylsulfonyl, paratosyl or lower-alkylsulfonyl, especially mesyl.
• the compounds of formula II are novel and, on account of their structure, are especially suitable for the preparation of the active end products of formula I or of other active substances having that partial structure. They therefore form an important part of the present invention.
• R 2 , R 3 and X are as defined under formula I and R 1 is H, as described under reaction (a) in the case of formula II and, in those cases in which R 1 in the compound of formula V is hydrogen, introducing an alkyl radical mentioned under R 1 in formula I by subsequent alkylation.
• reaction it is especially advantageous to use iodine/N-methylpyrrolidone as cyclising agent.
• a compound of formula V wherein R 1 is hydrogen is preferably used as starting material and one of the alkyl substituents mentioned under R 1 from the group C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 cyanoalkyl, and a C 1 -C 6 alkylene substituted by C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 haloalkoxy, C 1 -C 6 hydroxyalky
• the compounds of formula III may also be prepared from compounds of formula VI ,
• R 1 , R 2 - R 3 and X may have all the meanings given under formula I, by demethylation at the CH 3 -X- group.
• demethylating agent for example, aluminium chloride in chlorobenzene, it being possible to proceed analogously to J.W. ApSimon et al., Can. J. Chem. 60, 308 (1982).
• the compounds of formula VI may in turn be prepared according to methods known in the literature.
• the compounds of formula II are prepared by reacting compounds of formula VII ,
• R 2 , R 3 , R 4 , R 5 and X are as defined under formula I, with 2,3-diamino-maleic acid dinitrile (DAMN) of formula IX ,
• R 1 is as defined under formula I, and, in those cases in which R 1 in the compound of formula IX is hydrogen, introducing an alkyl radical mentioned under R 1 in formula I by subsequent alkylation.
• the compounds of formula V are prepared in a completely analogous manner, namely by reacting a compound of formula VIII ,
• R 2 , R 3 and X are as defined under formula I, with DAMN (of formula IX).
• the reactions with DAMN may be carried out analogously to the reactions described in the literature, for example analogously to DE 3 726 044 or R.W. Begland et al., J. Org. Chem. 39, 2341 (1974).
• a compound of formula IX wherein R 1 is hydrogen is preferably used as starting material and one of the alkyl substituents mentioned under Ri from the group C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 6 cyanoalkyl, and a C 1 -C 6 alkylene substituted by C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 haloalkoxy, C 1 -C 6 hydroxyal
• the compounds of formula VII are novel, and the invention relates also to them. They are valuable precursors in the preparation of the active compounds of formula I. In them there is already a partial structure that is important for the activity of the end products.
• the compounds of formula VII are prepared by reacting compounds of formula VIII with compounds of formula IV, the reaction preferably being carried out in an inert polar solvent, such as DMSO or DMF, and advantageously in the presence of an inorganic base at temperatures of from 0° to +180°C, preferably from +20° to +160°C.
• suitable inorganic bases are 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 and Na 2 CO 3 ), and also acetates, for example CH 3 COONa and
• bases are alkali metal alcoholates, for example sodium ethanolate, sodium propanolate, potassium tert-butanolate and sodium methanolate.
• the base is advantageously added in an amount of from 10 to 100 % of the equimolar amount, based on the reactants.
• the water of reaction formed in this reaction may optionally be removed from the reaction mixture by means of a customary entrainer, for example methylene chloride, benzene or toluene.
• the compounds of formula I according to the invention are valuable active ingredients in pest control while being well tolerated by warm-blooded animals, fish and plants.
• they not only exhibit a broad activity spectrum against helminths, such as nematodes, cestodes and trematodes, that parasitise the animal organism, especially mammals, their action being directed especially against nematodes (roundworms), but they may also be used equally successfully against phytopathogenic insects and arachnids which occur on useful plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the protection of stored goods and material stocks, and in the hygiene sector, especially on domestic animals and productive livestock. They are effective against all or individual development stages of normally sensitive and also resistant species of insects and arachnids.
• novel compounds of formula I according to the invention are suitable, for example, for controlling parasitic nematodes of the orders (according to
• domestic animals and productive livestock such as cattle, sheep, goats, horses, pigs, red deer, cats, dogs and fowl. They may 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 on 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 activity of the compounds of formula I according to the invention may manifest itself in the death of the pests immediately or only at a later date, for example at moulting, or in reduced oviposition and/or a reduced hatching rate.
• the above-mentioned animal pests include: of the order Lepidoptera for example
• Euxoa spp. Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana,
• Lymantria spp. Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta,
• Operophtera spp. Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,
• Synanthedon spp. Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
• Agriotes spp. Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,
• 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.,
• 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,
• Fannia spp. Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp.,
• 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,
• the compounds of formula I according to the invention are therefore highly suitable inter alia for controlling pests from the group of the insects and arachnids in cotton, fruit, maize, soybean, citrus and vegetable crops.
• plant-eating insects such as Anthonomus grandis
• plant-eating insect larvae such as the larvae of Spodoptera littoralis or Heliothis virescens
• sucking insects such as Aphis craccivora or Bemisia tabaci
• soil insects such as Diabrotica balteata
• the compounds of formula I may also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against noxious insects as well as against phytopathogenic noxious insects that occur in the soil.
• the invention relates also to
• compositions comprising compounds of formula I as active ingredient, especially cropprotecting compositions, and to their use in the agricultural sector, including farming, horticulture and forestry, or related fields.
• the present invention relates also to the preparation of those compositions, which comprises homogeneously mixing and/or grinding the active ingredient with one or more substances or groups of substances described herein.
• the formulation stages can be supplemented by kneading, granulating (in the case of granules) and, optionally, compressing (in the case of pellets).
• a prophylactic and/or curative method of controlling plant pests and/or helminths in mammals which comprises applying the compounds of formula I according to the invention, or the compositions according to the invention, to the locus of the pest.
• Target subjects for the use as anthelmintics are all warm-blooded animals which may be infested with helminths, especially mammals and fowl, but most especially domestic animals, productive livestock and pet animals, such as cows, horses, donkeys, sheep, goats, llamas, camels, red deer, pigs, dogs, cats, rabbits, chickens, turkeys, ducks, geese, pheasants, partridges, etc., as well as all fur-producing breeding animals. Of course, infested zoo animals may also be treated successfully.
• 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 tapeworms, sucker worms and roundworms of the gastrointestinal tract and other organs (e.g. the liver, lungs, kidneys, lymph vessels, blood, etc.).
• novel compounds of formula I have a broad activity spectrum against helminths, such as nematodes, cestodes and trematodes, that parasitise the animal organism, especially warm-blooded animals, their action being directed especially against nematodes (roundworms).
• helminths such as nematodes, cestodes and trematodes
• Target crops to be protected against phytopathogenic pests within the scope of the present invention comprise e.g. the following species of plants:
• cereals wheat, barley, rye, oats, rice, maize, sorghum and related crops
• beet sucgar beet and fodder beet
• pomes drupes and soft fruit
• leguminous plants beans, lentils, peas, soybeans
• oil plants rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts
• cucumber plants cucumber, marrows, melons
• fibre plants cotton, flax, hemp, jute
• citrus fruit oranges, lemons, grapefruit, mandarins
• vegetables spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, banana
• the compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds.
• These further compounds can be fertilisers or micronutrient donors or other preparations that inf. ⁇ ence plant growth. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other
• the good pesticidal activity of the compounds of formula I according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.
• the activity of the compounds of the invention and of the compositions comprising them against animal pests can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides.
• suitable additives include representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis
• 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.
• a preferred method of applying a compound of formula I, or an agrochemical composition which comprises at least one of said compounds, is foliar application.
• the number of applications and the rate of application depend on the risk of infestation by the
• the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to 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 compounds of formula I may, however, also be applied to seeds (coating), either by impregnating the seeds with a liquid formulation comprising a compound of formula I, or by coating them with a solid formulation.
• compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or combinations of those compounds with other agrochemical active ingredients, and, where appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface- active compounds (surfactants).
• extenders e.g. solvents, solid carriers and, where appropriate, surface- active compounds (surfactants).
• Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols such as ethanol, propanol and butanol, and glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol mono-methyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetonol alcohol, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, or water, vegetable oils, such as rape oil, castor oil, coconut oil or soybean oil; and, where appropriate, also silicone
• the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
• Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent 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.
• surfactants will also be understood as comprising 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 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. Fatty acid methyltaurin salts may also be mentioned 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 which also includes the alkyl moiety of acyl radicals, 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.
• acyl radicals 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 2 sulfonic acid groups and one fatty acid radical containing approximately 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, or 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 nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, 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 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. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
• the pesticidal compositions for crop protection usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or of combinations of that compound with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
• a surfactant preferably 0.1 to 25 %, preferably 0.1 to 25 %, of a surfactant.
• Typical application concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm.
• the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, preferably from 10 to 1000 g/ha, especially from 20 to 600 g/ha.
• 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, boli, capsules and microencapsulations. Care must be taken to ensure that the formulation adjuvants are physiologically tolerable.
• Suitable binders for tablets and boli are chemically modified, water- or alcohol-soluble, polymeric natural substances, such as starch, cellulose or protein derivatives (e.g. methylcellulose, carboxymethylcellulose, ethylhydroxyethylcellulose, proteins such as zein, gelatine and the like) as well as synthetic polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, etc..
• Tablets also comprise fillers (e.g. starches, microcrystalline cellulose, sugars, lactose, etc.), lubricants and disintegrators.
• the anthelmintic compositions are in the form of feed concentrates, then there are used as carriers, for example, high-performance feed, fodder grain or protein concentrates.
• feed concentrates or compositions may comprise additives, vitamins, antibiotics, chemotherapeutics, or other pesticides, especially bacteriostats, fungistats, coccidiostats, or hormone preparations, substances having an anabolic action, or substances that promote growth, affect the meat quality of animals for slaughter, or that are otherwise beneficial to the organism.
• the finished feed or the finished drinking water preferably comprises the active ingredients in a concentration of approximately from 0.0005 to 0.02 % by weight (5-200 ppm).
• compositions according to the invention may 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, boli and capsules.
• the anthelmintic compositions according to the invention usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, Ia or mixtures thereof, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, including 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.
• compositions may also comprise further additives, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers, as well as other active ingredients for obtaining special effects.
• additives such as stabilisers, antifoams, viscosity regulators, binders, 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 may be used in all their spatial configurations, their mixtures, or in the form of their salts.
• the invention relates also to a method for the prophylactic protection of warm-blooded animals, especially domestic animals, productive livestock and pet animals, against parasitic helminths, which method comprises administering the compounds of formula I, or the active ingredient formulations prepared therefrom, to the animals in the form of an additive to their feed or their drinking water, or in solid or liquid form orally, by injection or parenterally.
• the invention relates also to the compounds of formula I according to the invention for use in one of the mentioned methods.
• Preferred formulations are composed especially of the following constituents (throughout, percentages are by weight):
• Emulsifiable concentrates are:
• 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 %
• 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 %
• surface-active agent 1 to 40 %, preferably 2 to 30 %
• 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 %
• active ingredient 0.5 to 30 %, preferably 3 to 15 %
• solid carrier 99.5 to 70 %, preferably 97 to 85 %
• compositions may also comprise further additives, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, as well as fertilisers or other active ingredients for obtaining special effects.
• stabilisers e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil)
• antifoams e.g. silicone oil
• preservatives e.g. silicone oil
• viscosity regulators binders
• tackifiers e.g. silicone oil
• a mixture of 20.3 g of 2-chloro-6-trifluoromethoxy-benzothiazole, 9.8 g of 4-hydroxybenzaldehyde, 22.1 g of anhydrous K 2 CO 3 and 100 ml of DMSO is stirred for 24 h at +60°C under a nitrogen atmosphere. Then the internal temperature is increased to +80°C and the mixture is stirred for a further 7 h. After cooling to room temperature, the mixture is filtered, and the filtrate is poured onto ice-water and extracted several times with ethyl acetate.
• the combined organic phases are washed in succession with 2N hydrochloric acid, 2N sodium hydroxide solution and saturated sodium chloride solution, dried over sodium sulfate and concentrated by evaporation.
• the crystalline crude product is dissolved in diethyl ether and the solution is purified with active carbon. Approximately half the solvent is evaporated off, n-hexane is added to the residue that remains, and the mixture is cooled in an ice-bath for the purpose of crystal formation.
• the crystalline product is isolated by filtration and dried, yielding 12.4 g of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde having a melting point of 67-68°C.
• the organic phase is washed several times with water and saturated sodium chloride solution and is dried over magnesium sulfate, and the solvent is removed in vacuo.
• the crystalline crude product is further dried in vacuo for 24 h at +80°C in order to remove final traces of DMF and is then dissolved in ethyl acetate, and the ester solution is purified with activated carbon. A portion of the ester is removed by concentration by evaporation and the solution that remains is made to crystallise by the addition of n-hexane.
• the crystalline phase is isolated by filtration and dried, yielding 10.4 g of 2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole having a melting point of 186-189°C.
• Emulsifiable concentrates a) b) c) a compound of Table 1 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether
• Emulsions of any desired concentration can be produced 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 produced from such concentrates by dilution with water.
• 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.
• 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.
• talcum 97 % - kaolin - 90 % 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, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
• Such granules can be mixed with the 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.
• polyethylene glycol (mol. wt. 200) 3 %
• 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. 2.9. Tablets or boli
• the methylcellulose is stirred into water.
• the silicic acid is stirred in and the mixture is suspended homogeneously.
• the active ingredient and the maize starch are mixed.
• the aqueous suspension is incorporated into that mixture, and the mixture is kneaded to form a dough.
• the mass so obtained is granulated through a 12 M sieve and dried.
• Preparation The active ingredient is dissolved in some of the solvent, with stirring; 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 the solvents and the surfactant, and the solution is made up to the desired volume with water. Sterile filtration through a suitable membrane filter having a pore diameter of 0.22 ⁇ m.
• the aqueous systems may also be used preferably for oral and/or intraruminal administration. 3.
• Biological Examples The anthelmintic activity is demonstrated by means of the following tests:
• the active ingredient is administered in the form of a suspension, by means of a stomach probe or by rumen injection, to sheep which have previously been artificially infested with nematodes such as Haemonchus contortus and Trichostrongylus colubriformis. From 1 to 3 animals are used per test or per dose. Each sheep is treated with only a single dose.
• a first evaluation is made by comparing the number of worm eggs excreted in the sheep's faeces before and after treatment.
• the active ingredient is administered in the form of a suspension, by means of a stomach probe or by rumen injection, to sheep which have previously been artificially infested with Fasciola hepatica. 3 animals are used per test or per dose. Each animal is treated with only a single dose.
• a first evaluation is made by comparing the number of worm eggs excreted in the sheep's faeces before and after treatment. Three to four weeks after the treatment, the sheep are sacrificed and dissected. Evaluation is made by counting the number of liver flukes remaining in the bile duct after the treatment. Untreated sheep infested at the same time and in the same manner are used as control or comparison. The difference in the number of liver flukes found in the two groups indicates the level of activity of the test compound.
• Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture comprising the test compound in a concentration of 400 ppm, 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.
• Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion comprising the test compound in a concentration of 400 ppm. 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.
• compound 1.4 from Table 1 is more than 80 % effective against Tetranychus urticae in this test.

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• 1993
  • 1993-06-30 EP EP93915749A patent/EP0603377A1/de not_active Withdrawn
  • 1993-06-30 WO PCT/EP1993/001682 patent/WO1994001432A1/en not_active Application Discontinuation
  • 1993-06-30 JP JP6502902A patent/JPH06511260A/ja active Pending
  • 1993-06-30 AU AU45619/93A patent/AU4561993A/en not_active Abandoned
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