EP0000345A1 - Dérivés phénoxybenzyloxycarbonyles substitués, leur procédé de préparation et leur utilisation comme insecticides et acaricides - Google Patents
Dérivés phénoxybenzyloxycarbonyles substitués, leur procédé de préparation et leur utilisation comme insecticides et acaricides Download PDFInfo
- Publication number
- EP0000345A1 EP0000345A1 EP78100252A EP78100252A EP0000345A1 EP 0000345 A1 EP0000345 A1 EP 0000345A1 EP 78100252 A EP78100252 A EP 78100252A EP 78100252 A EP78100252 A EP 78100252A EP 0000345 A1 EP0000345 A1 EP 0000345A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- spp
- vinyl
- formula
- halogen
- derivatives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 [*-]C(c1cc(Oc2ccccc2)ccc1)C#N Chemical compound [*-]C(c1cc(Oc2ccccc2)ccc1)C#N 0.000 description 4
- AOCIKXYBLVXIKP-UHFFFAOYSA-N [IH]=CSc1ccccc1 Chemical compound [IH]=CSc1ccccc1 AOCIKXYBLVXIKP-UHFFFAOYSA-N 0.000 description 1
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 acetate or carboxylates e.g. 3'-phenoxy-benzyl- ⁇ -isopropyl (3,4-dimethoxy-phenyl) acetate.
- (6-Chloro-piperonyl) -2,2-dimethyl-3- (2,2-dimethyl'-vinyl) -cyclopropanecarboxyate and 3'-phenoxybenzyl-2,2-dimethyl-3-indenyl-cyclopropanecarboxylate have insecticidal and acaricidal properties (See German Laid-Open Patent Nos. 2,335,347 and 2,605,828 and U.S. Patent 2,857,329).
- the general formula (I) includes the various possible stereoisomers, 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 technology.
- process variant a) uses 3- (4-fluorophenoxy) benzyl alcohol and 2,2-dimethyl-3- (2-phenylvinyl) cyclopropanecarboxylic acid chloride and process variant b) uses the sodium salt of 2,2-dimethyl-3- (2 -phenylthio-vinyl) -cyclopropanecarboxylic acid and 3-phenoxy- ⁇ -cyano-benzyl bromide 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, 43, 5. 435? -4362). The free acids are converted into the corresponding salts or acid halides (III) 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:
- 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, have proven particularly useful Triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine.
- 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 4 ° 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 in the usual way 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, if appropriate in a suitable solvent, is initially introduced together with a 10-30% excess of the alcohol of the formula (II) 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 by so-called “distillation”. can be freed from the last volatile components 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 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 paraf fine, 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 ka
- 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, for example 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 death rate is ventilated 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 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 substance 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.
- reaction mixture is poured into 150 ml of water, the organic phase is separated off and washed again with 100 ml of water.
- the toluene phase is then dried over sodium sulfate and the solvent is distilled off in a water jet vacuum.
- Last solvent residues are removed by briefly distilling at 60 ° C./1 torr bath temperature.
- 12-, og (34% of theory) 3 '- (4-fluorophenoxy) - ⁇ -cyanobenzyl-2,2-dimethyl- (2-phenyl-2-chlorovinyl) -cyclopropanecarboxylate are obtained as a yellow oil with the refractive index : 1.5670.
- cyclopropanecarboxylic acids (V) or their salts and acid chlorides (III) required as starting compounds can be prepared as described below: 26.3 g (0.1 mol) of 4-chlorobenzylphosphonate diethyl ester are dissolved in 400 ml of absolute tetrahydrofuran and cooled to -70.degree. 0.11 mol of n-butyllithium (15% solution in hexane) is 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.
- cyclopropanecarboxylic acid ethyl esters shown in Example a) or b) are saponified by known or acidic or alkaline means to give the corresponding acids. These are also converted into the corresponding salts (e.g. alkali or ammonium salts) or acid chlorides by known processes.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2730515 | 1977-07-06 | ||
DE19772730515 DE2730515A1 (de) | 1977-07-06 | 1977-07-06 | Substituierte phenoxybenzyloxycarbonylderivate, verfahren zu ihrer herstellung und ihre verwendung als insektizide und akarizide |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000345A1 true EP0000345A1 (fr) | 1979-01-24 |
EP0000345B1 EP0000345B1 (fr) | 1981-04-01 |
Family
ID=6013281
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP79103787A Expired EP0011695B1 (fr) | 1977-07-06 | 1978-06-28 | Acides cyclopropanes carboxyliques substitués et leurs dérivés; procédé pour leur préparation et utilisation pour la préparation d'insecticides et d'acaricides |
EP78100252A Expired EP0000345B1 (fr) | 1977-07-06 | 1978-06-28 | Dérivés phénoxybenzyloxycarbonyles substitués, leur procédé de préparation et leur utilisation comme insecticides et acaricides |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP79103787A Expired EP0011695B1 (fr) | 1977-07-06 | 1978-06-28 | Acides cyclopropanes carboxyliques substitués et leurs dérivés; procédé pour leur préparation et utilisation pour la préparation d'insecticides et d'acaricides |
Country Status (22)
Country | Link |
---|---|
US (2) | US4276306A (fr) |
EP (2) | EP0011695B1 (fr) |
JP (2) | JPS5414946A (fr) |
AR (1) | AR227617A1 (fr) |
AT (1) | AT361251B (fr) |
AU (1) | AU520095B2 (fr) |
BR (1) | BR7804334A (fr) |
CA (1) | CA1254227C (fr) |
CS (1) | CS199214B2 (fr) |
DD (2) | DD146286A5 (fr) |
DE (3) | DE2730515A1 (fr) |
DK (1) | DK160300C (fr) |
EG (1) | EG13788A (fr) |
ES (2) | ES471461A1 (fr) |
GR (1) | GR71682B (fr) |
HU (1) | HU176473B (fr) |
IL (1) | IL55061A (fr) |
IT (1) | IT1097465B (fr) |
PH (1) | PH16779A (fr) |
PT (1) | PT68252A (fr) |
TR (1) | TR20790A (fr) |
ZA (1) | ZA783869B (fr) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0009792A1 (fr) * | 1978-10-11 | 1980-04-16 | Bayer Ag | Esters 4-fluoro-3-phénoxy-alpha cyanobenzyliques de l'acide 3-chlorostyryl-2,2-diméthyl-cyclopropanoique, procédé de préparation et utilisation comme ectoparasiticides |
FR2453140A1 (fr) * | 1979-04-03 | 1980-10-31 | American Cyanamid Co | Procede de preparation de pesticides de type ester a l'aide de catalyseurs de transfert de phase |
EP0022971A1 (fr) * | 1979-07-21 | 1981-01-28 | Bayer Ag | Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique |
EP0023598A1 (fr) * | 1979-07-21 | 1981-02-11 | Bayer Ag | Procédé de préparation de 1,1-dichloroalcènes |
EP0025542A2 (fr) * | 1979-09-12 | 1981-03-25 | Bayer Ag | Esters (+/-)-(alpha-cyano-3-phénoxy-4-fluoro-benzyliques) de l'acide (+/-)-trans-3-(E,Z-2-chloro-2-(4-chloro-phényl)-vinyl)-2,2-diméthyl-cyclopropane carboxylique, leurs isomères E- et Z-, procédé pour la préparation de ces composés, leur utilisation comme ectoparasiticides et leurs intermédiaires |
EP0043492A2 (fr) * | 1980-07-03 | 1982-01-13 | Bayer Ag | Esters d'acides 1-aryl-cyclopropan-1-carboxyliques, leur préparation et leur application comme insecticides |
EP0045424A1 (fr) * | 1980-08-02 | 1982-02-10 | Bayer Ag | Formulations "pour-on" actives contre les tiques |
EP0046950A1 (fr) * | 1980-09-03 | 1982-03-10 | Bayer Ag | Isomères optiquement actifs d'esters (alpha-cyano-4-fluoro-3-phénoxy)benzyliques d'acide trans-3-(2-chloro-2-(4-chlorophényl)-vinyl)-2,2-diméthylcyclopropionique, procédé pour leur préparation et utilisation comme ectoparasiticides |
EP0135853A2 (fr) * | 1983-09-17 | 1985-04-03 | Bayer Ag | Corps moulés contenant des pyréthroides pour la lutte contre les ectoparasites |
EP0088919B1 (fr) * | 1982-03-09 | 1987-01-14 | Bayer Ag | Formulations "pour-on" pesticides |
EP0224697A1 (fr) * | 1985-10-31 | 1987-06-10 | Bayer Ag | Utilisation des pyrethroids synthétiques pour l,obtentions d,un médicament destiné à la lutte contre des parasitoses chez les abeilles |
US5286749A (en) * | 1980-11-21 | 1994-02-15 | Pitman-Moore Inc. | Control of sheep ectoparasites |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4200644A (en) * | 1978-01-26 | 1980-04-29 | Fmc Corporation | Arylthiovinylcyclopropanecarboxylate insecticides |
DE2842542A1 (de) * | 1978-09-29 | 1980-04-17 | Bayer Ag | Substituierte bromostyryl-cyclopropancarbonsaeurephenoxybenzylester, verfahren zu ihrer herstellunnd ihre verwendung als insektizide und akarizide |
DE2852028A1 (de) * | 1978-12-01 | 1980-06-12 | Bayer Ag | Mittel gegen keratinschaedlinge und verfahren zur behandlung von wolle mit diesen mitteln |
IT1166681B (it) * | 1979-03-09 | 1987-05-06 | Montedison Spa | Piretroidi |
DE2920947A1 (de) * | 1979-05-23 | 1980-12-04 | Bayer Ag | 2-phenyl-alken-1-yl-cyclopropan- carbonsaeureester, verfahren zu ihrer herstellung sowie ihre verwendung als insektizide und akarizide und zwischenprodukte zu ihrer herstellung |
DE2922481A1 (de) * | 1979-06-01 | 1980-12-11 | Bayer Ag | Elektroparasitizide mittel enthaltend substituierte phenoxybenzyloxycarbonylderivate, (ihio)phosphorsaeureester, verfahren zu ihrer herstellung und ihre verwendung als ektoparasitizide |
FR2484256B1 (fr) * | 1979-06-29 | 1986-10-24 | Roussel Uclaf | Procede de lutte contre les parasites des animaux a sang chaud |
FR2471187A1 (fr) * | 1979-12-10 | 1981-06-19 | Roussel Uclaf | Nouvelles compositions destinees a la lutte contre les parasites des animaux a sang chaud |
JPS5786014A (en) * | 1980-11-18 | 1982-05-28 | Ishida Scales Mfg Co Ltd | Measuring or counting method by combination |
DE3048021A1 (de) * | 1980-12-19 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | Insektizide und akarizide mittel und ihre verwendung |
JPS57169627A (en) * | 1981-04-13 | 1982-10-19 | Yamato Scale Co Ltd | Combination balance |
JPS57175923A (en) * | 1981-04-24 | 1982-10-29 | Yamato Scale Co Ltd | Combined balance |
DE3127752A1 (de) * | 1981-07-14 | 1983-02-03 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von permethrinsaeurementhylester |
JPS5819516A (ja) * | 1981-07-28 | 1983-02-04 | Ishida Scales Mfg Co Ltd | 複数の種類の品物の混合組合せ計量方法 |
JPS5892914A (ja) * | 1981-11-30 | 1983-06-02 | Ishida Scales Mfg Co Ltd | 組合せ演算装置 |
JPS59622A (ja) * | 1982-06-26 | 1984-01-05 | Anritsu Corp | 組合せ計量装置 |
NZ221534A (en) * | 1986-08-27 | 1990-10-26 | Montedison Spa | Derivatives of 2,2-dimethyl-cyclopropane carboxylic acid; insecticides and acaricides |
DE3629387A1 (de) * | 1986-08-29 | 1988-03-03 | Bayer Ag | Verfahren zur diastereomerentrennung von cyclopropancarbonsaeureestern |
JPH02100028U (fr) * | 1989-01-25 | 1990-08-09 | ||
DE3906556A1 (de) * | 1989-03-02 | 1990-09-06 | Desowag Materialschutz Gmbh | Mittel oder konzentrat zum konservieren von holz oder holzwerkstoffen |
DE3907069A1 (de) * | 1989-03-04 | 1990-09-06 | Basf Ag | Substituierte 2-phenyl-alk(en)yl-1-yl-cyclopropancarbonsaeurebenzylester, verfahren zu ihrer herstellung und ihre verwendung zur bekaempfung von schaedlingen |
CN107365252A (zh) * | 2016-05-11 | 2017-11-21 | 江苏优士化学有限公司 | 3-(2-氯-2-(4-氯苯基)乙烯基)-2,2-二甲基环丙烷羧酸的合成方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1207371A (en) * | 1966-08-26 | 1970-09-30 | Roussel Uclaf | Cyclopropane carboxylic acids and derivatives thereof having insecticidal properties |
FR2067854A5 (en) * | 1969-11-19 | 1971-08-20 | Roussel Uclaf | Subst vinyl cyclo-propane-1-carboxylic acids insecticidal prepn |
NL7701321A (nl) * | 1976-02-17 | 1977-08-19 | Ciba Geigy | Werkwijze voor de bereiding van een ester. |
JPS52116440A (en) * | 1976-03-26 | 1977-09-29 | Sagami Chem Res Center | Preparation of vinylcyclopropane carboxylic acid ester |
FR2362588A1 (fr) * | 1976-08-27 | 1978-03-24 | Fmc Corp | Insecticides cyclopropane carboxyliques |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
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US3786052A (en) * | 1966-08-26 | 1974-01-15 | J Martel | Novel cyclopropanecarboxylic acids and esters |
NL133054C (fr) * | 1967-11-10 | |||
SE386669B (sv) * | 1968-07-12 | 1976-08-16 | Roussel Uclaf | Sett att framstella inre hemiacylalen av cis-3,3-dimetyl-2-formylcyklopropan-1-karbonsyra |
US3666789A (en) * | 1969-05-21 | 1972-05-30 | Sumitomo Chemical Co | Cyclopropanecarboxylic acid esters |
JPS5220473B1 (fr) * | 1970-06-29 | 1977-06-03 | ||
JPS515450B1 (fr) * | 1971-06-29 | 1976-02-20 | ||
US4024163A (en) * | 1972-05-25 | 1977-05-17 | National Research Development Corporation | Insecticides |
FR2248264B1 (fr) * | 1973-10-22 | 1977-05-27 | Roussel Uclaf | |
IN142702B (fr) * | 1974-09-10 | 1977-08-20 | Sagami Chem Res | |
JPS5813522B2 (ja) * | 1974-10-24 | 1983-03-14 | 住友化学工業株式会社 | 新しいシクロプロパンカルボン酸エステルを含有する殺虫、殺ダニ剤 |
US3966959A (en) * | 1975-02-13 | 1976-06-29 | American Cyanamid Company | Insecticidal and acaricidal, pyrethroid compounds |
CH602005A5 (en) | 1976-02-17 | 1978-07-14 | Ciba Geigy Ag | (3)-Phenoxy-benzyl styryl-cyclopropane carboxylates |
US4157397A (en) * | 1976-08-27 | 1979-06-05 | Fmc Corporation | Insecticidal (β-phenylvinyl)cyclopropanecarboxylates |
ZA775160B (en) * | 1976-08-27 | 1978-07-26 | Fmc Corp | Insecticidal styryl- and substituted-styrylcyclopropanecarboxylates |
DE2848495A1 (de) * | 1977-11-11 | 1979-05-17 | Ciba Geigy Ag | Cyclopropankarbonsaeureester, verfahren zu ihrer herstellung und ihre verwendung in der schaedlingsbekaempfung |
DE2800922A1 (de) * | 1978-01-10 | 1979-07-19 | Bayer Ag | Verfahren zur trennung stereoisomerer vinylcyclopropancarbonsaeuren |
US4200644A (en) * | 1978-01-26 | 1980-04-29 | Fmc Corporation | Arylthiovinylcyclopropanecarboxylate insecticides |
DE2810634A1 (de) * | 1978-03-11 | 1979-09-20 | Bayer Ag | Pentafluorbenzyloxycarbonylderivate, verfahren zu ihrer herstellung und ihre verwendung als insektizide und akarizide |
US4358409A (en) * | 1979-05-02 | 1982-11-09 | Bayer Aktiengesellschaft | Preparation of styryl cyclopropane insecticide intermediates |
-
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 DE DE7979103787T patent/DE2861686D1/de not_active Expired
- 1978-06-28 DE DE7878100252T patent/DE2860574D1/de not_active Expired
- 1978-06-28 EP EP79103787A patent/EP0011695B1/fr not_active Expired
- 1978-06-28 EP EP78100252A patent/EP0000345B1/fr not_active Expired
- 1978-07-03 CS CS784410A patent/CS199214B2/cs unknown
- 1978-07-03 IL IL55061A patent/IL55061A/xx unknown
- 1978-07-04 CA CA 306758 patent/CA1254227C/fr not_active Expired
- 1978-07-04 DD DD78215933A patent/DD146286A5/de 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 DD DD78206509A patent/DD139991A5/de not_active IP Right Cessation
- 1978-07-04 IT IT25315/78A patent/IT1097465B/it active Protection Beyond IP Right Term
- 1978-07-05 EG EG420/78A patent/EG13788A/xx active
- 1978-07-05 DK DK304178A patent/DK160300C/da not_active IP Right Cessation
- 1978-07-05 BR BR7804334A patent/BR7804334A/pt unknown
- 1978-07-05 JP JP8106878A patent/JPS5414946A/ja active Granted
- 1978-07-05 AU AU37787/78A patent/AU520095B2/en not_active Expired
- 1978-07-05 ZA ZA00783869A patent/ZA783869B/xx unknown
- 1978-07-05 AR AR272845A patent/AR227617A1/es active
- 1978-07-05 GR GR56693A patent/GR71682B/el unknown
- 1978-07-05 HU HU78BA3674A patent/HU176473B/hu not_active IP Right Cessation
- 1978-07-05 ES ES471461A patent/ES471461A1/es not_active Expired
- 1978-07-06 PH PH21337A patent/PH16779A/en unknown
- 1978-07-06 TR TR20790A patent/TR20790A/xx 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
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1207371A (en) * | 1966-08-26 | 1970-09-30 | Roussel Uclaf | Cyclopropane carboxylic acids and derivatives thereof having insecticidal properties |
FR2067854A5 (en) * | 1969-11-19 | 1971-08-20 | Roussel Uclaf | Subst vinyl cyclo-propane-1-carboxylic acids insecticidal prepn |
NL7701321A (nl) * | 1976-02-17 | 1977-08-19 | Ciba Geigy | Werkwijze voor de bereiding van een ester. |
JPS52116440A (en) * | 1976-03-26 | 1977-09-29 | Sagami Chem Res Center | Preparation of vinylcyclopropane carboxylic acid ester |
FR2362588A1 (fr) * | 1976-08-27 | 1978-03-24 | Fmc Corp | Insecticides cyclopropane carboxyliques |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, 1978, Vol. 88, p74106c, Colombus, Ohio, & JP-A-52 116 440 "Cyclopropanecarboxylate esters", 29 September '77 * |
INTERNATIONAL JOURNAL OF METHODS IN SYNTHETIC ORGANIC CHEMISTRY, 1975, p283, Nr. 4363, Stuttgart, Vinylcyclopropanes. * |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0009792A1 (fr) * | 1978-10-11 | 1980-04-16 | Bayer Ag | Esters 4-fluoro-3-phénoxy-alpha cyanobenzyliques de l'acide 3-chlorostyryl-2,2-diméthyl-cyclopropanoique, procédé de préparation et utilisation comme ectoparasiticides |
FR2453140A1 (fr) * | 1979-04-03 | 1980-10-31 | American Cyanamid Co | Procede de preparation de pesticides de type ester a l'aide de catalyseurs de transfert de phase |
EP0022971A1 (fr) * | 1979-07-21 | 1981-01-28 | Bayer Ag | Procédé pour la préparation de dérivés de l'acide 3-(2,2-dichlorovinyl)-2,2-diméthyl-cyclopropane-1-carboxylique |
EP0023598A1 (fr) * | 1979-07-21 | 1981-02-11 | Bayer Ag | Procédé de préparation de 1,1-dichloroalcènes |
EP0025542A2 (fr) * | 1979-09-12 | 1981-03-25 | Bayer Ag | Esters (+/-)-(alpha-cyano-3-phénoxy-4-fluoro-benzyliques) de l'acide (+/-)-trans-3-(E,Z-2-chloro-2-(4-chloro-phényl)-vinyl)-2,2-diméthyl-cyclopropane carboxylique, leurs isomères E- et Z-, procédé pour la préparation de ces composés, leur utilisation comme ectoparasiticides et leurs intermédiaires |
EP0025542A3 (en) * | 1979-09-12 | 1981-05-20 | Bayer Ag | (+/-)-(alpha-cyano-3-phenoxy-4-fluoro-benzylic)esters of (+/-)-trans-3-(e,z-2-chloro-2-(4-chloro-phenyl)-vinyl)-2,2-dimethyl-cyclopropane carboxylic acid, their e and z isomers, a process for their preparation and their application as ectoparasiticides |
EP0043492A2 (fr) * | 1980-07-03 | 1982-01-13 | Bayer Ag | Esters d'acides 1-aryl-cyclopropan-1-carboxyliques, leur préparation et leur application comme insecticides |
EP0043492B1 (fr) * | 1980-07-03 | 1983-10-05 | Bayer Ag | Esters d'acides 1-aryl-cyclopropan-1-carboxyliques, leur préparation et leur application comme insecticides |
EP0045424A1 (fr) * | 1980-08-02 | 1982-02-10 | Bayer Ag | Formulations "pour-on" actives contre les tiques |
EP0046950A1 (fr) * | 1980-09-03 | 1982-03-10 | Bayer Ag | Isomères optiquement actifs d'esters (alpha-cyano-4-fluoro-3-phénoxy)benzyliques d'acide trans-3-(2-chloro-2-(4-chlorophényl)-vinyl)-2,2-diméthylcyclopropionique, procédé pour leur préparation et utilisation comme ectoparasiticides |
US5286749A (en) * | 1980-11-21 | 1994-02-15 | Pitman-Moore Inc. | Control of sheep ectoparasites |
EP0088919B1 (fr) * | 1982-03-09 | 1987-01-14 | Bayer Ag | Formulations "pour-on" pesticides |
EP0135853A2 (fr) * | 1983-09-17 | 1985-04-03 | Bayer Ag | Corps moulés contenant des pyréthroides pour la lutte contre les ectoparasites |
EP0135853A3 (en) * | 1983-09-17 | 1987-05-20 | Bayer Ag | Shaped bodies containing pyrethroids for the control of ectoparasites |
EP0224697A1 (fr) * | 1985-10-31 | 1987-06-10 | Bayer Ag | Utilisation des pyrethroids synthétiques pour l,obtentions d,un médicament destiné à la lutte contre des parasitoses chez les abeilles |
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