Classifications

• • 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
  • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

• the present invention relates to new substituted phenoxybenzyloxycarbonyl derivatives, several processes for their preparation and their use as insecticides and acaricides.
• phenoxybenzyl acetates or carboxylates e.g. 3'-phenoxybenzyl- ⁇ -isopropyl- (3,4-dimethoxy-phenyl) -acetate, (6-chloro-piperonyl) -2,2-dimethyl-3- (2,2-dimethyl-vinyl) -cyclopropanecarboxylate and 3 '-Phenoxy-benryl-2,2-dimethyl-3-indenyl-cyclopropane-carboxylate have insecticidal and acaricidal properties (see German Offenlegungsschriften2335347 and 2605828 and US patent 2,857,309).
• the general formula (1) includes the various possible steroisomers, the optical isomers and mixtures of these components.
• the substituted phenoxybenzyloxycarbonyl derivatives according to the invention show a better insecticidal and acaricidal action than the corresponding previously known products of analogous constitution and the same direction of action.
• the products according to the present invention thus represent a real enrichment of the technology.
• process variant a) 3- (4-fluorophenoxy) benzyl alcohol and 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylic acid chloride are used and process variant b) the sodium salt of 2,2-dimethyl-3- (2-phenylthiovinyl) cyclopropanecarboxylic acid and 3-phenoxy-a-cyano-benzylbromide as starting materials, the course of the reaction can be represented by the following formula schemes:
• the cyclopropanecarboxylic acid derivatives (V) which are also to be used as starting compounds can be prepared by acidic or alkaline saponification using processes known from the literature from the partially known ethyl cyclopropanecarboxylates (cf. Tetrahedron Letters 1976, 48, pp. 4359-4362).
• the free acids are converted into the corresponding salts or acid halides (111) and (V) by known processes.
• the partially known ethyl esters can in turn be prepared by processes known from the literature, for example from ethyl 2,2-dimethyl-3-formylcyclopropanecarboxylate and diester derivatives of 0,0-diethylmethanephosphonic acid, using the following formula:
• Examples of the cyclopropanecarboxylic acid derivatives (111) and (V) are: 3- [2-phenylvinyl] -, 3- [2- (2-chlorophenyl) vinyl] -, 3- [2- (4 -Chlorphenyl) vinyl] -, 3- [2- (3,4-dichlorophenyl) vinyl] -, 3- [2- (4-fluorophenyl) vinyl] -, 3- [2-pentachlorophenyl vinyl] - , 3- [2-pentafluorophenyl vinyl] -, 3- [2-phenylthio-vinyl] -, 3- [2- (2-chlorophenylthio) vinyl] -, 3-
• All customary acid binders can be used as acid acceptors.
• Alkali carbonates and alcoholates such as sodium and potassium carbonate, sodium and potassium methylate or ethylate, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proven particularly useful.
• the reaction temperature can be varied within a wide range. In general, the process is carried out between 0 and 150 ° C., preferably in process variant a) at 10 to 40 ° C. and in process variant b) at 100 to 130 ° C.
• the reaction is generally allowed to proceed at normal pressure.
• the processes for the preparation of the compounds according to the invention are preferably carried out using suitable solvents or diluents.
• suitable solvents or diluents Practically all inert organic solvents can be considered as such. These include in particular aliphatic and aromatic, optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, gasoline, methylene chloride, chloroform, carbon tetrachloride, chlorobenzene, or ether, e.g.
• ketones for example acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone
• nitriles such as aceto- and propionitrile
• formamides e.g. Dimethylformamide.
• the starting materials are preferably used in an equimolar ratio.
• An excess of one or the other reaction component has no significant advantages.
• the reaction components are usually combined in one of the specified solvents and, in the presence of an acid acceptor, are usually stirred for one to several hours at elevated temperature.
• the reaction mixture is then worked up in such a way that it is poured into water, the organic phase is separated off and then worked up as usual by washing, drying and distilling off the solvent.
• the procedure is customary in such a way that the methyl or ethyl ester of cyclopropanecarboxylic acid is optionally introduced in a suitable solvent together with a 10-30% excess of the alcohol of the formula (11) and with the addition of alkali metal methylate or ethylate heated.
• the resulting lower boiling alcohol is continuously distilled off.
• the cyclopropanecarboxylic acid derivative is preferably used in the form of an alkali metal salt. This is heated together with the benzyl halide derivative to 80 ° -140 ° C in one of the specified solvents. An excess of one or the other reaction component has no advantages. When the reaction has ended, the solvent is distilled off, the residue is taken up in methylene chloride and the organic phase is worked up as described above.
• the new compounds are obtained in the form of oils, which can usually not be distilled without decomposing, but through so-called «distillation», i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way.
• «distillation i.e. can be freed from the last volatile constituents by prolonged heating under reduced pressure to moderately elevated temperatures and can be cleaned in this way.
• the refractive index or the boiling point is used to characterize them.
• the substituted phenoxybenzyloxycarbonyl derivatives according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medical sector against animal parasites (ectoparasites) such as parasitic fly larvae and ticks.
• animal parasites ectoparasites
• the active ingredients are suitable for controlling animal pests, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
• the pests mentioned above include:
• Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
• Thysanura e.g. Lepisma saccharina.
• Orthoptera for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesti cus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.
• Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
• Homptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis, pad.
• Homptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Rhoralosobusumumisis,
• Nephotettix cincticeps Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
• Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
• Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.
• Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp.
• the active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as ULV cold and warm fog formulations.
• customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspension emulsion concentrates, seed powders, active ingredient-impregnated natural and synthetic substances, very fine encapsulations in polymeric substances and in coating compositions for seeds, also in formulations with fuel sets, such as smoking cartridges, cans, spirals, etc. as well as
• formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally 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.
• extenders that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• surface-active agents that is to say emulsifiers and / or dispersants and / or foam-generating agents.
• organic solvents can, for example, also be used as auxiliary solvents.
• liquid solvents aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, 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;
• Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; as solid carriers: natural rock flour, such as kaolin, clay,
• Adhesives such as carboxymethyl cellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
• Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo 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 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
• the active compounds according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.
• 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 100% by weight of active substance, preferably between 0.01 and 10% by weight.
• the application takes place in a customary manner adapted to the application forms.
• the active ingredients When used against hygiene pests and pests of stored products, the active ingredients are distinguished by an excellent residual action on wood and clay and by a good stability to alkali on limed substrates.
• the active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, diving (dipping), spraying (spraying), pouring-on and spot-on) and powdering and by parenteral use in the form of, for example, injection.
• 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.
• cabbage leaves (Brassica oleracea) are sprayed to runoff point and populated with horseradish leaf beetle larvae (Phaedon Cochleariae).
• the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.
• 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.
• Cabbage plants (Brassica oleracea) which are heavily infested with peach aphids (Myzus persicae) are sprayed to runoff point with the preparation of active compound.
• the kill is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
• 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.
• Bean plants Phaseolus vulgaris
• Triticae Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of development of the common spider mite or bean spider mite (Tetranychus urticae), are sprayed to runoff point with the preparation of active compound.
• the kill is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
• the active compound in question is mixed with the stated solvent in a ratio of 1: 2 and the concentrate thus obtained is diluted with water to the desired concentration.
• Emulsifier 80 parts by weight of alkylaryl glycol ether
• the toluene phase is then dried over sodium sulfate and the solvent is distilled off in a water jet vacuum.
• the last solvent residues are removed by briefly distilling at 60 ° C / 1 Torr bath temperature.
• 12.0 g (84% of theory) of 3 '- (4-fluorophenoxy) a-cyanobenzyl-2,2-dimethyl- (2-phenyl-2-chlorovinyl) cyclopropanecarboxylate are obtained as a yellow oil with the refractive index .
• cyclopropanecarboxylic acids (V) or their salts and acid chlorides (111) required as starting compounds can be prepared as described below: 26.3 g (0.1 mol) of ethyl 4-chlorobenzylphosphonate are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) are added dropwise in a countercurrent of nitrogen and with thorough stirring, and the reaction mixture is then stirred at -70 ° C. for a further 15 minutes.
• the cyclopropanecarboxylic acid ethyl esters depicted according to example a) or b) are saponified acid or alkaline to the corresponding acids by known methods. These are also converted into the corresponding salts (for example alkali or ammonium salts) or acid chlorides by processes which are also known.

Applications Claiming Priority (2)

Publications (2)

Family

ID=6013281

Family Applications (2)

Family Applications Before (1)

Country Status (22)

Families Citing this family (34)

Family Cites Families (24)

• 1977
  • 1977-07-06 DE DE19772730515 patent/DE2730515A1/de not_active Withdrawn
• 1978
  • 1978-06-16 US US05/916,163 patent/US4276306A/en not_active Expired - Lifetime
  • 1978-06-28 EP EP79103787A patent/EP0011695B1/de not_active Expired
  • 1978-06-28 EP EP78100252A patent/EP0000345B1/de not_active Expired
  • 1978-06-28 DE DE7979103787T patent/DE2861686D1/de not_active Expired
  • 1978-06-28 DE DE7878100252T patent/DE2860574D1/de not_active Expired
  • 1978-07-03 CS CS784410A patent/CS199214B2/cs unknown
  • 1978-07-03 IL IL55061A patent/IL55061A/xx unknown
  • 1978-07-04 PT PT68252A patent/PT68252A/pt unknown
  • 1978-07-04 AT AT484278A patent/AT361251B/de not_active IP Right Cessation
  • 1978-07-04 IT IT25315/78A patent/IT1097465B/it active Protection Beyond IP Right Term
  • 1978-07-04 CA CA 306758 patent/CA1254227C/en not_active Expired
  • 1978-07-04 DD DD78206509A patent/DD139991A5/de not_active IP Right Cessation
  • 1978-07-04 DD DD78215933A patent/DD146286A5/de unknown
  • 1978-07-05 EG EG420/78A patent/EG13788A/xx active
  • 1978-07-05 GR GR56693A patent/GR71682B/el unknown
  • 1978-07-05 ES ES471461A patent/ES471461A1/es not_active Expired
  • 1978-07-05 AR AR272845A patent/AR227617A1/es active
  • 1978-07-05 BR BR7804334A patent/BR7804334A/pt unknown
  • 1978-07-05 JP JP8106878A patent/JPS5414946A/ja active Granted
  • 1978-07-05 ZA ZA00783869A patent/ZA783869B/xx unknown
  • 1978-07-05 DK DK304178A patent/DK160300C/da not_active IP Right Cessation
  • 1978-07-05 HU HU78BA3674A patent/HU176473B/hu not_active IP Right Cessation
  • 1978-07-05 AU AU37787/78A patent/AU520095B2/en not_active Expired
  • 1978-07-06 TR TR20790A patent/TR20790A/xx unknown
  • 1978-07-06 PH PH21337A patent/PH16779A/en unknown
• 1979
  • 1979-03-28 ES ES479021A patent/ES479021A1/es not_active Expired
• 1982
  • 1982-06-24 US US06/391,732 patent/US4611009A/en not_active Expired - Lifetime
• 1986
  • 1986-06-26 JP JP61148365A patent/JPS6248646A/ja active Granted

Also Published As

Similar Documents

Legal Events