WO1996018619A1 - Derives de m-diphenyloxazoline substitues - Google Patents

Derives de m-diphenyloxazoline substitues Download PDF

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Publication number
WO1996018619A1
WO1996018619A1 PCT/EP1995/004719 EP9504719W WO9618619A1 WO 1996018619 A1 WO1996018619 A1 WO 1996018619A1 EP 9504719 W EP9504719 W EP 9504719W WO 9618619 A1 WO9618619 A1 WO 9618619A1
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Prior art keywords
alkyl
fluorine
cycloalkyl
chlorine atoms
formula
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PCT/EP1995/004719
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German (de)
English (en)
Inventor
Wolfgang Krämer
Udo Kraatz
Reinhard Lantzsch
Albrecht Marhold
Christoph Erdelen
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Bayer Aktiengesellschaft
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Priority to AU43006/96A priority Critical patent/AU4300696A/en
Publication of WO1996018619A1 publication Critical patent/WO1996018619A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C233/67—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
    • C07C233/68—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • C07C233/73—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom of a carbon skeleton containing six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/10—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D263/14—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with radicals substituted by oxygen atoms

Definitions

  • the invention relates to new substituted m-biphenyloxazoline derivatives, several
  • R 1 represents hydrogen, halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy or any optionally substituted cycloalkyl or cycloalkylalkyl
  • R 2 represents hydrogen, alkyl, alkenyl, Alkynyl, haloalkyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl, cycloalkenyl or cycloalkenylalkyl, optionally substituted aralkyl or for the radical -COR 3 , where
  • R 3 represents alkyl, alkoxy, alkenyl, alkenyloxy, in each case optionally substituted cycloalkyl, cycloalkyloxy or cycloalkylalkyloxy, optionally substituted aryl or for the radical -NR 4 R 5 , where
  • R 4 represents hydrogen or alkyl
  • R 5 represents alkyl, haloalkyl, in each case optionally substituted cycloalkyl or cycloalkylalkyl or for in each case optionally substituted phenyl or phenylalkyl.
  • the compounds of the formula (I) are generally obtained as mixtures of stereoisomers. They can be used both in the form of their diastereomer mixtures and as pure diastereomers or enantiomers.
  • R 1 has the meaning given above and
  • R represents allyl or the radical -COR 3 , where
  • R 3 has the meaning given above, in a first stage in the presence of a base, optionally in the presence of a catalyst and optionally in the presence of a diluent, and optionally subsequently in a second stage the 4- (m-biphenyl) oxazolines of the formula (Ia) thus obtained
  • R 1 has the meaning given above and
  • R represents allyl or the radical -COR 3 , where
  • R 3 has the meaning given above, in the presence of a catalyst, optionally in the presence of an acid and a diluent, to give the 4- (4-hydroxy-3-biphenyl) oxazolines of the formula (Ib)
  • R 1 has the meaning given above; and optionally the 4- (4-hydroxy-3-biphenyl) oxyzolines of the formula (Ib) thus obtained
  • R 1 has the meaning given above, with compounds of the formula (III) MR 2 (III) in which
  • M stands for a leaving group
  • R 2 has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a base.
  • R 1 preferably represents hydrogen, fluorine, chlorine or bromine, C 1 -C 9 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkyl or C 1 -C 6 haloalkoxy with in each case one or more fluorine and / or chlorine atoms, for C 1 -C 12 alkenyl, C 3 -C 12 alkenyloxy or C 3 -C 6 haloalkenyl with one or more fluorine and / or chlorine atoms, for C 3 - C 12 -alkynyl, C 3 -C 12 -alkynyloxy or C 3 -C 6 -haloalkynyl with one or more fluorine and / or chlorine atoms, or for each optionally one or more times, identically or differently, by halogen or C 1 -C 4 -Alkyl substituted C 3
  • R 2 preferably represents hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl, C 3 -C 12 alkynyl, C 1 -C 6 haloalkyl with one or more fluorine and / or chlorine atoms , for C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl-C 1 -C 4 -alkyl, which are optionally mono- or polysubstituted in the cycloalkyl moiety, in each case mono- or polysubstituted, in each case halogen, C 1 -C 4 - as substituents Alkyl, optionally singly or multiply, identically or differently by C 2 -C 4 -alkenyl substituted by halogen and in each case optionally singly or multiply, identically or differently by
  • Halogen-substituted phenyl or styryl are suitable,
  • phenyl-C 1 -C 4 -alkyl or naphthylmethyl which is optionally mono- or polysubstituted in the aryl moiety, in each case mono- or polysubstituted, in each case as substituents halogen, C 1 -C 12 -alkyl, C 1 -C 12 -haloalkyl with one or more Fluorine and / or chlorine atoms, C 1 -C 12 alkoxy or C 1 - C 12 haloalkoxy with one or more fluorine and / or chlorine atoms are suitable,
  • R 3 preferably represents C 1 -C 12 -alkyl, C 1 -C 1 -alkoxy, C 3 -C 12 -alkenyl, C 3 -C 12 -alkenyloxy, for each in the cycloalkyl part optionally one or more times, identical or differently substituted C 3 -C 6 cycloalkyl, C 3 -C 10 cycloalkyloxy or C 3 -C 10 cycloalkyl-C 1 -C 6 alkoxy, where in each case as substituents C 1 -C 4 alkyl, halogen, C 1 -C 4 haloalkyl with one or more fluorine and / or chlorine atoms and C 2 -C 4 haloalkenyl with one or more fluorine and / or chlorine atoms come into question, for each optionally mono- or polysubstituted, identically or differently substituted Phenyl or naphthyl, where in each case as phenyl or naph
  • R 4 preferably represents hydrogen or C 1 -C 12 alkyl
  • R 5 preferably represents C 1 -C 12 alkyl, C 1 -C 12 haloalkyl with one or more fluorine and / or chlorine atoms, each in the cycloalkyl part optionally mono- or polysubstituted, identically or differently substituted, C 3 -C 6 - Cycloalkyl or C 3 -C 6 cycloalkyl-C 1 -C 4 alkyl, where in each case as substituents C 1 -C 4 alkyl, halogen, C 1 -C 4 haloalkyl with one or more fluorine and / or chlorine atoms and C 2 -C 4 haloalkenyl with one or more fluorine and / or chlorine atoms are suitable,
  • R 1 particularly preferably represents hydrogen, fluorine, chlorine or bromine, C 1 -C 6 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkyl or C 1 - C 4 haloalkoxy, each with two or more fluorine and / or chlorine atoms, C 3 - C 6 alkenyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyl or C 3 -C 6 alkynyloxy, or each optionally mono- to triple, identical or different, C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloal
  • R 2 particularly preferably represents hydrogen, represents C 1 -C 6 - alkyl, C 1 -C 12 - alkenyl, C 3 -C 6 -alkynyl, C 1 -C 4 haloalkyl having two or more fluorine and / or chlorine atoms, in each case in the cycloalkyl moiety is optionally mono- to trisubstituted by identical or different substituents, C 3 -C 6 - cycloalkyl or C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, in each case as substituents of fluorine, chlorine, bromine, C 1 -C 2 alkyl, optionally single or multiple, identical or different C 2 -C 4 substituted by fluorine or chlorine Alkenyl and, in each case, optionally single or double, identical or different, phenyl and styryl substituted by fluorine or chlorine,
  • phenyl-C 1 -C 4 -alkyl which is optionally monosubstituted to trisubstituted, identically or differently, in the phenyl part, where fluorine, chlorine, C 1 -C 4 -alkyl, halomethyl having one or more fluorine and / or chlorine atoms, C 1 -C 4 alkoxy or C 1 -C 4 haloalkoxy with one or more fluorine and / or chlorine atoms are suitable,
  • R particularly preferably represents C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 3 -C 6 - alkenyl, C 3 -C 6 alkenyloxy, in each case in the cycloalkyl moiety is optionally mono- to trisubstituted by identical or differently substituted C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyloxy or C 3 -C 6 cycloalkyl-C 1 -C 4 alkoxy, where in each case as substituents C 1 -C 2 alkyl, fluorine, chlorine C 1 -C 2 haloalkyl with 1 to 5 fluorine and / or chlorine atoms and C 2 -alkylene with 1 to 3 fluorine and / or chlorine atoms are suitable,
  • substituents for phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the substituents being halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 2 -haloalkyl having 1 to 5 fluorine and / or chlorine atoms as well as C 1 -C 4 haloalkoxy with one or more fluorine and / or chlorine atoms,
  • R 4 particularly preferably represents hydrogen or C 1 -C 2 alkyl
  • R 3 particularly preferably represents C 1 -C 4 -alkyl or optionally substituted once or twice, identically or differently in the phenyl moiety
  • R 1 very particularly preferably represents hydrogen, chlorine, bromine or trifluoromethoxy very particularly preferably represents hydrogen
  • R 4 very particularly preferably represents hydrogen.
  • R 5 very particularly preferably represents methyl, ethyl or phenyl which is optionally monosubstituted by chlorine.
  • hydrocarbon radicals mentioned above in the definition of the compounds according to the invention such as alkyl or alkenyl, can - also in conjunction with
  • Heteroatoms such as alkoxy - be straight-chain or branched as far as possible
  • Formula (II) provides a general definition of the m-biphenylchloroethylbenzamides required as starting materials for carrying out process (a) according to the invention.
  • R preferably or particularly preferably represents allyl or the radical -COR 3 , where R 3 has the meanings given above
  • R 1 and R have the meaning given above, in the presence of a catalyst, such as, for example, ferric chloride and in the presence of a diluent, for example halogenated hydrocarbons such as methylene chloride, at temperatures between 0 ° C and 80 ° C (see also
  • R 1 has the meaning given above, alkylated or acylated in a generally known manner (see, for example, J. of Chem Soc 1937, pp. 771-773).
  • N- (1-methoxy-2-chloroethyl) -2,6-difluorobenzamide of the formula (IV) is known (cf. EP-A 0 594 179).
  • Some of the biphenyl derivatives of the formula (Va) are known or are obtainable in a generally known manner, such as by alkylation or acylation of the corresponding OH derivatives of the formula (Vb) (see e.g. J. of Chem Soc
  • M stands for a customary leaving group.
  • R 2 stands for -COR 3 , preferably meanings for M are halogen, such as especially chlorine or bromine, anhydride and imidazolide. If R 2 stands for its other meanings, preferably meanings for M are halogen, such as in particular Chlorine or bromine, alkylsulfonyloxy, such as, in particular, methyl sulfonyloxy, and optionally substituted arylsulfonyloxy, such as, in particular, phenylsulfonyloxy, p-chlorophenylsulfonyloxy or tolylsulfonyloxy
  • the compounds of the formula (III) are generally known compounds of organic chemistry
  • Suitable diluents for carrying out the first stage of process (a) according to the invention are all inert organic solvents. They can optionally be used in a mixture with water. Hydrocarbons such as toluene, xylene, tetralin, hexane, cyclohexane, halogenated hydrocarbons such as methylene chloride, chloroform are preferably used , Chlorobenzene, o-dichlorobenzene, alcohols such as methanol, ethanol, glycol, the isomeric propanols, butanols, pentanols, ethers such as diethyl ether, diisopropyl ether, dimethoxyethane, tetrahydrofuran, dioxane, nitriles such as acetonitrile or butyronitrile, amides such as dimethylformamide, sulfoxides such as dimethyl sulfide, such as dimethyl S
  • Suitable bases for carrying out the first stage of process (a) according to the invention are all customary acid acceptors.
  • Tertiary amines such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), N, N-dimethylanin are preferably usable , furthermore alkaline earth metal oxides such as magnesium and calcium oxide, furthermore alkali and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, alkali metal hydroxides such as sodium and potassium hydroxide, furthermore alcoholates such as sodium ethanolate or potassium tert-butoxide when carrying out the first stage of the process (a) according to the invention is optionally carried out in the presence of a phase transfer catalyst
  • Phase transfer catalysts are, for example, tertiary ammonium compounds such as tetraoctylammonium bromide or benz
  • reaction temperatures can be varied within a substantial range when carrying out the first stage of process (a) according to the invention. In general, temperatures between -10 ° C and 150 ° C, preferably between -10 ° C and 80 ° C.
  • the first stage of process (a) according to the invention is generally carried out under normal pressure.
  • Suitable diluents for carrying out the second stage of process (a) according to the invention are preferably water / alcohol mixtures, such as water / methanol, water / ethanol or water / propanol, and
  • Water / amide mixtures such as water / dimethylformamide, water / dimethylacetamide and the water / toluene mixture are suitable.
  • the second stage of process (a) according to the invention is carried out in the presence of a catalyst.
  • a metallic palladium / carbon mixture or palladium complex compounds (palladium in the oxidation stage +0), such as, for example, tetrakis (triphenylphosphine) palladium (O), are preferably used. .
  • the second step of process (a) according to the invention is optionally carried out in the presence of an acid.
  • an acid inorganic or organic acids or Lewis acids are suitable.
  • sulfuric acid, methanesulfonic acid, benzene sulfonic acid, p-toluenesulfonic acid, aluminum chloride, phosphorus oxychloride or boron trifluoroetherate are preferred.
  • reaction temperatures can be varied within a substantial range generally one works at temperatures between 0 ° C and 150 ° C, preferably between 0 ° C and 80 ° C
  • the second stage of process (a) according to the invention is generally carried out under atmospheric pressure.
  • preferably 0.01 (mole) of 4- (m-biphenyl) oxazoline of the formula (Ia) is used up to 0.1 mol of catalyst and optionally 0.01 to 1 mol of acid.
  • Working up is carried out by customary methods
  • inert solvents can be used as diluents in carrying out process (b) according to the invention.
  • Hydrocarbons such as gasoline, benzene, toluene, xylene and tetrahedron, and furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, can also be used
  • Ketones such as acetone and methylsopropyl ketone
  • furthermore ethers such as diethyl ether, tetrahydrofuran and dioxane
  • carboxylic acid esters such as ethyl acetate
  • strongly polar solvents such as dimethyl sulfoxide and sulfolane
  • Suitable bases for carrying out process (b) according to the invention are all customary acid acceptors.
  • Tertiary amines such as triethylamine, pyndine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclonones (DBN), Hunig base and N, N are preferably usable -Dimethyl-anihn, also alkaline earth metal oxides, such as magnesium and calcium oxide, also alkah and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate and alkali or alkaline earth metal hydroxides such as sodium hydroxide or potassium hydroxide
  • Process (b) can be varied within a substantial range. In general, temperatures between -20 ° C and + 120 ° C, preferably between 0 ° C and 80 ° C.
  • Process (b) according to the invention is generally carried out under normal pressure
  • the reaction is generally carried out in approximately equivalent amounts.
  • Working up is carried out by customary methods.
  • the active compounds are suitable to combat animal pests, in particular insects, arachnids and nematodes, which protect in agriculture, in forests, in the supply and material and in the hygiene sector.You can preferably use them as plant protection products.You are against normally sensitive and resistant species and against all or individual stages of development effective
  • the pests mentioned above include
  • Aleurodes brassicae Bemisia tabaci
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pempheusumpp.
  • Ceuthorrhynchus assimihs, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Agrebri moht, Tenebrio moht Conoderus spp., Melolontha melolontha, Amphimallon solstitiahs Costelvtra zealandica
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp From the order of Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp, Gastrophilus spp., Hyppobosca , Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp, Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata,
  • Acarina for example Acarus siro, Argas spp., Ormthodoros spp., Dermanyssus galhnae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp,
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
  • the active compounds according to the invention are notable for high insecticides and acaricidal activity
  • the active compounds can be converted into the customary formulations, such as solutions or emulsions , Wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulation in polymeric substances.
  • formulations are prepared in a known manner, for example by mixing the active ingredients with Extenders, that is to say liquid solvents and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents are essentially suitable.
  • Aromatics such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol, and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils
  • alcohols such as but
  • Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g.
  • emulsifiers and / or foam-generating agents are: eg nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, eg alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations.
  • Other additives can be mineral and vegetable oils
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used
  • the formulations generally contain between 0J and 95% by weight of active compound, preferably between 0.5 and 90%
  • the active substance according to the invention can be used in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants,
  • Bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides are present.
  • the insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • the following are particularly advantageous mixed partners, for example
  • Dichlorophene diclobutrazole, diclofluanid, diclomezm, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditahmfos, dithianon, dodine, drazoxolone,
  • Mancopper Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,
  • Tebuconazole Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
  • Bacillus thuringiensis Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
  • Fenamiphos Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenothxinfox, Fufionophon, Fufionophon, Fufionophon, Fufionophon, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fufion, Fu
  • Imidacloprid Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin, Lambda-cyhalothrin, Lufenuron,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds by which the effect of the active ingredients is increased without the added synergist itself having to be active
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight
  • the application takes place in a customary manner adapted to the application forms
  • the active ingredient When used against hygiene and storage pests, the active ingredient is characterized by an excellent residual effect on wood and clay as well as a good stability to alkali on limed substrates
  • the compounds of the formula 1 according to the invention have a high insecticidal action against insects which destroy industrial materials.
  • the following are examples and preferably, but are not limited, are preferred
  • Lyctus pubescens Trogoxylon aequale, Minthes rugicolhs, Xyleborus spec Tryptodendron spec Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec Dinoderus minutus
  • Kalotermes flavicollis such as Cryptotermes brevis, Heterotermes indicola, Reticuhtermes flavipes, Reticuhtermes santonensis, Reticulitermes lucifugus Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus Bristle tail, such as Lepisma saccharina.
  • technical materials are understood to mean non-living materials, such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints.
  • the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
  • Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone masts, wooden cladding,
  • the active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, for example by mixing the active ingredients with at least one solution or. Diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and other processing aids
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
  • the amount of the compositions or concentrates used is of the type and Occurrence of the insects and depending on the medium. The optimal amount can be determined by using test series.
  • the organic chemical solvents used are preferably oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Suitable mineral oils or their aromatic fractions or solvent mixtures containing mineral oils are used as such difficultly volatile, water-insoluble, oily and oil-like solvents , preferably white spirit, petroleum and / or alkylbenzene
  • Mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C, turpentine oil and the like are advantageous for use
  • liquid aliphatic hydrocarbons with a boiling range from 180 to 210 ° C. or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range from 180 to 220 ° C. and / or spindeol and / or monochloronaphthalene, preferably ⁇ -monochloronaphthalene, are used
  • organic slightly volatile oily or oil-like solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number 35 and a flash point above
  • insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture
  • Aliphatic compounds containing hydroxyl and / or ester and / or ether groups are preferably used.
  • organic chemical solvents such as glycol ether, ester or the like for use
  • the known organic-chemical binders are water-thinnable and / or synthetic resins which are soluble or dispersible or emulsifiable in the organic-chemical solvents used and / or binding drying oils, in particular binders consisting of or containing an acrylate resin Vinyl resin, e.g. polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as inden coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / / or synthetic resin used
  • Vinyl resin e.g. polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as inden coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, dyes, pigments, water repellents, odor correctors and inhibitors or inhibitors known per se can be used Corrosion protection agents and the like are used
  • the organic-chemical binder is preferably at least one alkyd resin or modified alkyd resin and / or a drying vegetable O1 in the medium or in the concentrate.
  • binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture) .
  • a fixing agent mixture
  • a plasticizer mixture
  • these additives are intended to prevent volatilization of the active ingredients and crystallization or failure.Preferably they replace 0.01 to 30% of the binder (based on to 100% of the binder used)
  • the plasticizers are from the chemical classes of the phthalic esters such as dibutyl, dioctyl or benzyl butyl phthalate, Phosphorsaureester such as tributyl phosphate, Adipinsaureester such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, Glycerinester and p-toluenesulfonic acid ester Fixing agents are chemically based on polyvinyl alkyl ethers such as polyvinyl methyl ether or ketones such as benzophenone and ethylene benzophenone
  • Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants
  • a particularly effective wood preservation is achieved by industrial impregnation processes, e.g. vacuum, double vacuum or pressure processes
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides
  • the additional admixing partners are preferably the insecticides and fungicides mentioned in WO 94/29 268.
  • the compounds mentioned in this document are an express component of the present application
  • Insecticides such as chlorpyriphos, phoxime, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron and triflumuron can be used as very particularly preferred mixing partners.
  • fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole,
  • Emulsifier 1 part by weight of alkyl aryl polyglycol ether
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the Plutella maculipennis cockroach while the leaves are still moist
  • the kill is determined in%. 100% means that all the caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the compound according to Preparation Example 1 with an exemplary active compound concentration of 0J%, caused 100% destruction after 7 days
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration
  • Rice seedlings (Oryza sativa) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the green rice leafhopper (Nephotettix cincticeps) while the seedlings are still moist
  • the kill is determined in%. 100% means that all cicadas have been killed, 0% means that none of the cicadas have been killed.
  • the compound according to Preparation Example 3 caused a kill with an active compound concentration of 0J% from 100% after 6 days

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

Abstract

La présente invention concerne de nouveaux dérivés de m-diphényloxazoline ayant la formule (I) dans laquelle R1 et R2 ont la notation indiquée dans la description; l'invention concerne aussi des procédés et de nouveaux produits intermédiaires pour leur fabrication ainsi que leur utilisation pour la lutte contre les parasites animaux.
PCT/EP1995/004719 1994-12-12 1995-11-30 Derives de m-diphenyloxazoline substitues WO1996018619A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43006/96A AU4300696A (en) 1994-12-12 1995-11-30 Substituted m-biphenyloxazoline derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944444111 DE4444111A1 (de) 1994-12-12 1994-12-12 Substituierte m-Biphenyloxazolin-Derivate
DEP4444111.8 1994-12-12

Publications (1)

Publication Number Publication Date
WO1996018619A1 true WO1996018619A1 (fr) 1996-06-20

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PCT/EP1995/004719 WO1996018619A1 (fr) 1994-12-12 1995-11-30 Derives de m-diphenyloxazoline substitues

Country Status (3)

Country Link
AU (1) AU4300696A (fr)
DE (1) DE4444111A1 (fr)
WO (1) WO1996018619A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000058291A1 (fr) * 1999-03-26 2000-10-05 Novartis Ag Enantiomeres purs d'oxazoline 2,4-substituee, utiles comme pesticides
US6410581B1 (en) 1997-03-05 2002-06-25 Bayer Aktiengesellschaft Disubstituted biphenyloxazolines
US6413912B2 (en) 1997-11-04 2002-07-02 Syngenta Crop Protection, Inc. Azoline derivatives

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9709907D0 (en) 1997-05-15 1997-07-09 Ciba Geigy Ag Novel combinations
US6552039B2 (en) 1999-11-12 2003-04-22 Syngenta Crop Protection, Inc. Fungicidal combinations comprising a 4-phenoxyquinoline

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345775A1 (fr) * 1988-06-09 1989-12-13 Yashima Chemical Industrial Co., Ltd. Dérivé d'oxazoline ou de thiazoline
EP0432661A2 (fr) * 1989-12-09 1991-06-19 Yashima Chemical Industrial Co., Ltd. Dérivés de phenyl-2-oxazoline ou thiazoline substituée en 2 procédé, pour leur préparation et insecticides et acaricides les contenant
WO1993025079A1 (fr) * 1992-06-12 1993-12-23 Yashima Chemical Industrial Co., Ltd. Acaricide
EP0594179A1 (fr) * 1992-10-23 1994-04-27 Yashima Chemical Industry Co., Ltd. Dérivés de N-alkoxymethylbenzamide et procédé pour leur préparation, et leur utilisation pour la préparation de dérivés de benzamide
WO1995004726A1 (fr) * 1993-08-04 1995-02-16 E.I. Du Pont De Nemours And Company Oxazolines et thiazolines arthropodicides
EP0696584A1 (fr) * 1994-08-12 1996-02-14 Bayer Ag Biphenyloxazolines substitués et leur application comme pesticides

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345775A1 (fr) * 1988-06-09 1989-12-13 Yashima Chemical Industrial Co., Ltd. Dérivé d'oxazoline ou de thiazoline
EP0432661A2 (fr) * 1989-12-09 1991-06-19 Yashima Chemical Industrial Co., Ltd. Dérivés de phenyl-2-oxazoline ou thiazoline substituée en 2 procédé, pour leur préparation et insecticides et acaricides les contenant
WO1993025079A1 (fr) * 1992-06-12 1993-12-23 Yashima Chemical Industrial Co., Ltd. Acaricide
EP0645085A1 (fr) * 1992-06-12 1995-03-29 Yashima Chemical Industrial Co., Ltd. Acaricide
EP0594179A1 (fr) * 1992-10-23 1994-04-27 Yashima Chemical Industry Co., Ltd. Dérivés de N-alkoxymethylbenzamide et procédé pour leur préparation, et leur utilisation pour la préparation de dérivés de benzamide
WO1995004726A1 (fr) * 1993-08-04 1995-02-16 E.I. Du Pont De Nemours And Company Oxazolines et thiazolines arthropodicides
EP0696584A1 (fr) * 1994-08-12 1996-02-14 Bayer Ag Biphenyloxazolines substitués et leur application comme pesticides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6410581B1 (en) 1997-03-05 2002-06-25 Bayer Aktiengesellschaft Disubstituted biphenyloxazolines
US6413912B2 (en) 1997-11-04 2002-07-02 Syngenta Crop Protection, Inc. Azoline derivatives
WO2000058291A1 (fr) * 1999-03-26 2000-10-05 Novartis Ag Enantiomeres purs d'oxazoline 2,4-substituee, utiles comme pesticides

Also Published As

Publication number Publication date
DE4444111A1 (de) 1996-06-13
AU4300696A (en) 1996-07-03

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