DE3043976A1 - Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds. - Google Patents

Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds.

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Publication number
DE3043976A1
DE3043976A1 DE19803043976 DE3043976A DE3043976A1 DE 3043976 A1 DE3043976 A1 DE 3043976A1 DE 19803043976 DE19803043976 DE 19803043976 DE 3043976 A DE3043976 A DE 3043976A DE 3043976 A1 DE3043976 A1 DE 3043976A1
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Germany
Prior art keywords
chloro
fluoro
esters
substd
ethyl
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DE19803043976
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German (de)
Inventor
Hermann Dr. 5090 Leverkusen Hagemann
Reinhard Dr. Lantzsch
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Bayer AG
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Bayer AG
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Priority to DE19803043976 priority Critical patent/DE3043976A1/en
Priority to AT81108190T priority patent/ATE5312T1/en
Priority to DE8181108190T priority patent/DE3161438D1/en
Priority to EP81108190A priority patent/EP0050776B1/en
Priority to IL64071A priority patent/IL64071A0/en
Priority to CA000388520A priority patent/CA1164009A/en
Priority to DK467381A priority patent/DK467381A/en
Priority to BR8106820A priority patent/BR8106820A/en
Publication of DE3043976A1 publication Critical patent/DE3043976A1/en
Withdrawn legal-status Critical Current

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
    • C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • C07C69/747—Chrysanthemumic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Abstract

In the prodn. of 2,2-dimethyl-3- (fluoro-substd. 2-chloro- vinyl)- cyclopropanecarboxylic acid esters (I), HCl is eliminated from 2,2-dimethyl-3 -(fluoro-substd. 2,2-dichloroethyl)- cyclopropanecarboxylic acid esters (II) in a polar aprotic diluent in the presence of either (a) alkali carbonates and quat. ammonium or phosphonium salts or (b) potassium fluoride (where R1 is F, or CF3; and R2 is lower alkyl or the residue of an alcohol utilizable in pyrethroids). The starting esters (II) are new when R1 is CF3. The prods. are pesticides or intermediates for pesticides. High yields of (75-85%) can be obtd.

Description

Verfahren zur Herstellung von chlor-fluoralkenyl-Process for the production of chlorofluoroalkenyl

substituierten Cyclopropancarbonsäureestern Die Erfindung betrifft ein Verfahren zur Herstellung von chlor-fluoralkenyl-substituierten Cyclopropancarbonsäureestern durch Dehydrohalogenierung von chlorfluoralkyl-substituierten Cyclopropancarbonsäureestern.substituted cyclopropanecarboxylic acid esters The invention relates to a process for the preparation of chloro-fluoroalkenyl-substituted cyclopropanecarboxylic acid esters by dehydrohalogenation of chlorofluoroalkyl-substituted cyclopropanecarboxylic acid esters.

Es ist bereits bekannt, 3-(2',2'-dichloro-3',3',3'-trifluoropropyl)-2,2-dimethyl-cycloprpancarbonsäureester durch Dehydrochlorierung in die entsprechenden (2'-Chloro-3',3',3'-trifluoropropenyl)-ester zu überführen, indem man in Anwesenheit eines Alkalicarbonats in einem polaren aprotischen Lösungsmittel arbeitet.It is already known that 3- (2 ', 2'-dichloro-3', 3 ', 3'-trifluoropropyl) -2,2-dimethyl-cycloprpanecarboxylic acid ester by dehydrochlorination into the corresponding (2'-chloro-3 ', 3', 3'-trifluoropropenyl) esters to convert by standing in the presence of an alkali carbonate in a polar aprotic Solvent works.

Die dabei erreichbaren Ausbeuten von 55 - 63 % befriedigen jedoch für die technische Durchführung nicht (P-A 10 859).However, the achievable yields of 55-63% are satisfactory for the technical implementation not (P-A 10 859).

Es wurde nun gefunden, daß man Ester der Formel i in welcher R1 für Fluor oder Trifluormethyl steht, R2 für niederes Alkyl oder für den Rest eines bei Pyrethroiden verwendbaren Alkohols steht, erhält, indem man aus Estern der Formel II in welcher R1 und R2 die oben angegebene Bedeutung haben, Chlorwasserstoff in einem polaren aprotischen Verdünnungsmittel abspaltet, dadurch gekennzeichnet, daß man entweder in Gegenwart von Alkalicarbonaten und quartären Ammonium- oder Phosphoniumsalzen arbeitet oder in Geqenwart von Kaliumfluorid arbeitet.It has now been found that esters of the formula i in which R1 represents fluorine or trifluoromethyl, R2 represents lower alkyl or the radical of an alcohol which can be used in pyrethroids, is obtained by converting esters of the formula II in which R1 and R2 have the meaning given above, splitting off hydrogen chloride in a polar aprotic diluent, characterized in that one works either in the presence of alkali metal carbonates and quaternary ammonium or phosphonium salts or in the presence of potassium fluoride.

Diese Arbeitsweise führt zu Ausbeuten von 75 - 85 % was eine beträchtliche und überraschende Steigerung gegeniiber C m St-a-nd der Technik darstellt.This procedure leads to yields of 75-85% which is considerable and represents a surprising increase over C m St-a-nd the technology.

Die Verbindungen der Formel II sind zum Teil bekannt, bzw. lassen sich analog zu bekannten Verfahren herstellen (vgl. DE-OS 2 907 609). Verbindungen der Formel II, in welcher R1 für CF3 steht, sind neu.Some of the compounds of the formula II are known or are not known can be prepared analogously to known processes (cf. DE-OS 2 907 609). links of the formula II, in which R1 stands for CF3, are new.

An ihnen besteht besonderes Interesse, da sie zu hervorragenden Schädlingsbekämpfungsmitteln führen.They are of particular interest as they make excellent pesticides to lead.

Bevorzugt wird das erfindungsgemäße Verfahren zur Herstellung von Verbindungen der Formel I durchgeführt, in welcher R für Fluor oder Trifluormethyl steht und R2 für C1 4-Alkyl, Pentafluorbenzyl oder gegebenenfalls inrArStellung CN-substituiertes 3-Phenoxybenzyl, das sowohl im Phenoxyteil als auch im Benzylteil substituiert sein kann, steht.The process according to the invention is preferred for the production of Compounds of formula I carried out in which R is fluorine or trifluoromethyl and R2 is C1-4-alkyl, pentafluorobenzyl or optionally in the AR position CN-substituted 3-phenoxybenzyl, both in the phenoxy part and in the benzyl part may be substituted, stands.

Besonders bevorzugt werden Verbindungen hergestellt, in welchen R2 für Methyl, Ethyl, Pentafluorbenzyl oder 4-Fluor-3-phenoxybenzyl steht.Compounds are particularly preferably produced in which R2 represents methyl, ethyl, pentafluorobenzyl or 4-fluoro-3-phenoxybenzyl.

Verwendet man beispielsweise 2,2-Dimethyl-3-(2,2-dichlor-3, 3,4,4, 4-pentafluor-butyl) -cyclopropancarbonsäurepentafluorbenzylester als Ausgangsstoff, so kann der Reaktionsverlauf durch das folgende Formelschema wiedergegeben werden: Die Chlorwasserstoffabspaltung aus den Verbindungen der Formel II erfolgt mit Hilfe eines Alkalicarbonats in Gegenwart eines polaren aprotischen Verdünnungsmittels sowie in Gegenwart eines als Katalysator dienenden quartären Ammonium- oder Phosphoniumsalzes, oder in Gegenwart von Kaliumfluorid in einem polaren aprotischen Verdünnungsmittel.If, for example, 2,2-dimethyl-3- (2,2-dichloro-3, 3,4,4, 4-pentafluorobutyl) -cyclopropanecarboxylic acid pentafluorobenzyl ester is used as the starting material, the course of the reaction can be represented by the following equation: The hydrogen chloride is split off from the compounds of the formula II with the aid of an alkali metal carbonate in the presence of a polar aprotic diluent and in the presence of a quaternary ammonium or phosphonium salt serving as a catalyst, or in the presence of potassium fluoride in a polar aprotic diluent.

Als Verdünnungsmittel wird Dimethylformamid, Dimethylacetamid oder Acetonitril verwendet.The diluent used is dimethylformamide, dimethylacetamide or Acetonitrile used.

Als quartäre Ammoniumsalze werden bevorzugt eingesetzt.Preferred quaternary ammonium salts are used.

Tetrabutylammoniumbromid, Benzyltriethylammoniumchlorid oder Methyltrioctylammoniumchlorid.Tetrabutylammonium bromide, benzyltriethylammonium chloride or methyltrioctylammonium chloride.

Das Alkalicarbonat wird vorzugsweise äquimolar oder im überschuß (bis 5-Molar) eingesetzt.The alkali metal carbonate is preferably equimolar or in excess (up to 5 molar).

Besonders bevorzugt ist die Arbeitsweise in Acetonitril in Gegenwart von Kaliumcarbonat und einem quartären Ammoniumsalz.The procedure in acetonitrile in the presence is particularly preferred of potassium carbonate and a quaternary ammonium salt.

Besonders bevorzugt ist aber auch die Arbeitsweise in Dimethylformamidin-Gegenwart von Kaliumfluorid.However, the procedure in the presence of dimethylformamidine is also particularly preferred of potassium fluoride.

Beispiel 1 4 g cis/trans-2,2-Dimethyl-3-(2,2-dichlor-3 r 3,3-trifluorpropyl)-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-benzylester werden in 20 ml Acetonitril gelöst.example 1 4 g of cis / trans-2,2-dimethyl-3- (2,2-dichloro-3r 3,3-trifluoropropyl) -cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester are dissolved in 20 ml of acetonitrile.

Man gibt 4 g Kaliumcarbonat und 0,5 g Tetrabutylammoniumbromid zu und erhitzt im Autoklaven 4 Stunden auf 1800C.4 g of potassium carbonate and 0.5 g of tetrabutylammonium bromide are added and heated in the autoclave to 1800C for 4 hours.

Nach dem Abkühlen wird mit Wasser verdünnt und mit Salzsäure neutral gestellt. Man extrahiert mit Methylenchlorid, trocknet mit Natriumsulfat, engt am Rotationsdampfer ein und destilliert bei 60"C im Hochvakuum an Man erhält 3,4 g cis/trans-2,2-Dimethyl-3-(2-chlor-3,3,3-trifluorpropenyl)-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-benzylester, wobei die Z-tsomeren ganz stark überwiegen.After cooling, it is diluted with water and neutralized with hydrochloric acid posed. It is extracted with methylene chloride, dried with sodium sulfate, concentrated on Rotary evaporator and distilled at 60 ° C. in a high vacuum. 3.4 g are obtained cis / trans-2,2-dimethyl-3- (2-chloro-3,3,3-trifluoropropenyl) -cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester, whereby the Z-tsomers predominate very strongly.

20 Brechungsindex: nD = 1,519. 20 refractive index: nD = 1.519.

Beispiel 2 Analog Beispiel 1 wird aus 3,9 g cis/trans-2,2-Dimethyl-3-(2,2-dichlor-3,3,3-trifluorpropyl)-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-t'-cyanobenzylester 3,5 g cis/trans-2,2-Dimethyl-3-(2-chlor-3,3,3-trifluorpropenyl)-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-~l-cyano-benzylester erhalten.Example 2 Analogously to Example 1, 3.9 g of cis / trans-2,2-dimethyl-3- (2,2-dichloro-3,3,3-trifluoropropyl) -cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-t '-cyanobenzyl ester 3.5 g cis / trans-2,2-dimethyl-3- (2-chloro-3,3,3-trifluoropropenyl) -cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy- ~ l-cyano- Benzyl ester obtained.

Beispiel 3 1,02 g (2mMol) cis/trans-2,2-Dimethyl-3-(2,2-dichlor-3,3,4,4,4-pentafluor)-butyl-cyclopropancarbonsäurepentafluorbenzylester werden in 7 ml Dimethylacetamid gelöst und mit 0,6 g Kaliumfluorid versetzt und 4 Stunden auf 1400C erhitzt. Nach dem Abkühlen wird mit Wasser verdünnt, dann sofort dreimal mit Ether extrahiert und die vereinigten Etherauszüge mit konz. Kochsalzlösung neutral gewaschen. Die organische Phase wird mit Natriumsulfat getrocknet, abfiltriert, einrotiert und im Hochvakuum andestilliert. Der Rückstand besteht aus cis/trans-2,2-Dimethyl-3-(2-chlor-3,3,4,4,4-pentafluoro-but-1-enyl)-cyclopropancarbonsäurepentafluorbenzylester.Example 3 1.02 g (2 mmol) of cis / trans-2,2-dimethyl-3- (2,2-dichloro-3,3,4,4,4-pentafluoro) -butyl-cyclopropanecarboxylic acid pentafluorobenzyl ester are dissolved in 7 ml of dimethylacetamide and mixed with 0.6 g of potassium fluoride are added and the mixture is heated to 1400C for 4 hours. After cooling, it is diluted with water, then immediately extracted three times with ether and the combined ether extracts with conc. Washed saline solution neutral. The organic phase is dried with sodium sulfate, filtered off, concentrated in a rotary evaporator and distilled in a high vacuum. The residue consists of cis / trans-2,2-dimethyl-3- (2-chloro-3,3,4,4,4-pentafluoro-but-1-enyl) -cyclopropanecarboxylic acid pentafluorobenzyl ester.

Beispiel 4 2 g cis/trans-2,2-Dimethyl-3-(2,2-dichlor-3,3,4'4,4-pentafluor)-butyl-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-benzylester werden in 10 ml Acetonitril gelöst Man gibt 1,5 g Kaliumcarbonat (feingepulvert) und 0,3 g Tetrabutylammoniumchlorid zu und erhitzt im Autoklaven 12 Stunden auf 1700C. Die Aufarbeitung erfolgt analog Beispiel 1. Man erhält 1,6 g cis/trans-2,2-Dimethyl-3-(2-chlor-3,3t4,4,4-pentafluor-butenyl)-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-benzylester.Example 4 2 g of cis / trans-2,2-dimethyl-3- (2,2-dichloro-3,3,4'4,4-pentafluoro) -butyl-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester Dissolved in 10 ml of acetonitrile. 1.5 g of potassium carbonate (finely powdered) and 0.3 g of tetrabutylammonium chloride are added and the mixture is heated to 1700 ° C. in an autoclave for 12 hours. Working up is carried out as in Example 1. 1.6 g of cis / trans-2,2-dimethyl-3- (2-chloro-3,3t4,4,4-pentafluorobutenyl) -cyclopropanecarboxylic acid-4'-fluoro- 3'-phenoxy-benzyl ester.

Beispiel 5 2,9 g cis/trans-2,2-Dimethyl-3-(2,2-dichlor-3,3,4,4,4-pentafluor)-butyl-cyclopropancarbonsäure-4'-fluor-3'-phenoxy-,;-cyano-benzylester werden in 10 ml Dimethylformamid gelöst. Man gibt 0,7 g gut getrocknetes Kaliumfluorid hinzu und erhitzt eine Stunde auf 1500C. Nach dem Abkühlen wird mit Wasser verdünnt und neutral gestellt. Nach dreimaligem Extrahieren mit Ether werden die vereinigten Etherauszüge getrocknet und eingeengt.-Der entstandene 2,2-Dimethyl-3-(2-chlor-3,3,4,4,4-pentafluor) -butenyl-cyclopropancarbonsäure-4 -fluor-3 -phenoxy--' -cyano-benzylester wird chromatographisch (Kieselgel/n-Hexan/Chloroform 3:1) gereinigt.Example 5 2.9 g cis / trans-2,2-dimethyl-3- (2,2-dichloro-3,3,4,4,4-pentafluoro) -butyl-cyclopropanecarboxylic acid-4'-fluoro-3'-phenoxy- ,; - cyano-benzyl esters are dissolved in 10 ml of dimethylformamide. 0.7 g of well-dried potassium fluoride is added and the mixture is heated to 150.degree. C. for one hour. After cooling, it is diluted with water and made neutral. After extracting three times with ether, the combined ether extracts are dried and concentrated. The 2,2-dimethyl-3- (2-chloro-3,3,4,4,4-pentafluoro) -butenyl-cyclopropanecarboxylic acid-4-fluoro- 3-phenoxy- '-cyano-benzyl ester is purified by chromatography (silica gel / n-hexane / chloroform 3: 1).

Beispiel 6 307 g cis/trans-2,2-Dimethyl-3-(2,2-dichlor-3,3,3-trifluor-propyl)-cyclopropancarbonsäureethylester werden in 1000 ml Acetonitril gelöst. Man gibt 110 g Kaliumcarbonat und 20 g Methyltrioctylammoniunchlorid zu und erhitzt im Autoklaven 8 Stunden auf 1800C.Example 6 307 g of ethyl cis / trans-2,2-dimethyl-3- (2,2-dichloro-3,3,3-trifluoropropyl) cyclopropanecarboxylate are dissolved in 1000 ml of acetonitrile. 110 g of potassium carbonate and 20 g of methyltrioctylammonium chloride are added and heated in the autoclave to 1800C for 8 hours.

Nach dem Abkühlen wird mit Wasser verdünnt, mit Methylenchlorid extrahiert und mit verdünnter Salzsäure und dann mit Wasser neutral gewaschen. Nach Trocknen mit Natriumsulfat wird einrotiert. Durch fraktionierte Destillation erhält man 230,5 g (85 % d. Th.) 2,2-Dimethyl-3-(2-chlor-3,3,3-trifluorpropenyl)-cyclopropancarbonsäureester vom Siedepunkt Kp = 94-960/18 mbar.After cooling, it is diluted with water and extracted with methylene chloride and washed neutral with dilute hydrochloric acid and then with water. After drying with sodium sulfate is concentrated in a rotary evaporator. Fractional distillation gives 230.5 g (85% of theory) 2,2-dimethyl-3- (2-chloro-3,3,3-trifluoropropenyl) cyclopropanecarboxylic acid ester with a boiling point of Bp = 94-960 / 18 mbar.

Claims (3)

Patentansprüche: 1. Verfahren zur Herstellung von Estern der Formel I in welcher R1 für Fluor oder Trifluormethyl steht, R2 für niederes Alkyl oder für den Rest eines bei Pyrethroiden verwendbaren Alkohols steht, indem man aus Estern der Formel II in welcher R1 und R2 die oben angegebene Bedeutung haben, Chlorwasserstoff in einem polaren aprotischen Verdünnungsmittel abspaltet, dadurch gekennzeichnet, daß man entweder in Gegenwart von Alkalicarbonaten und quartären Ammonium- oder Phosphoniumsalzen arbeitet oder in Gegenwart von Kaliumfluorid arbeitet.Claims: 1. Process for the preparation of esters of the formula I. in which R1 represents fluorine or trifluoromethyl, R2 represents lower alkyl or the radical of an alcohol which can be used in pyrethroids, by converting from esters of the formula II in which R1 and R2 have the meaning given above, splitting off hydrogen chloride in a polar aprotic diluent, characterized in that one works either in the presence of alkali metal carbonates and quaternary ammonium or phosphonium salts or in the presence of potassium fluoride. 2. Ester der Formel II in welcher R2 für niederes Alkyl oder für den Rest eines bei Pyrethroiden verwendbaren Alkohols, steht.2. Esters of formula II in which R2 stands for lower alkyl or for the remainder of an alcohol which can be used in pyrethroids. 3. Ester der Formel II in welcher R2 für ethyl, Ethyl, Pentafluorbenzyl, gegebenenfalls in 4-Stellung CN-substituiertes 3-Phenoxy-4-fluor-benzyl, steht.3. Esters of formula II in which R2 stands for ethyl, ethyl, pentafluorobenzyl, optionally 3-phenoxy-4-fluoro-benzyl which is CN-substituted in the 4-position.
DE19803043976 1980-10-23 1980-11-21 Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds. Withdrawn DE3043976A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19803043976 DE3043976A1 (en) 1980-11-21 1980-11-21 Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds.
AT81108190T ATE5312T1 (en) 1980-10-23 1981-10-12 PROCESS FOR THE PREPARATION OF CHLORINE-FLUORALKENYL- SUBSTITUTED CYCLOPROPANECARBONIC ESTERS.
DE8181108190T DE3161438D1 (en) 1980-10-23 1981-10-12 Process for the preparation of chloro-fluoroalkenyl-substituted cyclopropane-carboxylic-acid esters
EP81108190A EP0050776B1 (en) 1980-10-23 1981-10-12 Process for the preparation of chloro-fluoroalkenyl-substituted cyclopropane-carboxylic-acid esters
IL64071A IL64071A0 (en) 1980-10-23 1981-10-19 Preparation of chloro-fluoro-alkenyl-substituted cyclopropane-carboxylic acid esters
CA000388520A CA1164009A (en) 1980-10-23 1981-10-22 Process for the preparation of chloro-fluoroalkenyl- substituted cyclopropanecarboxylic acid esters
DK467381A DK467381A (en) 1980-10-23 1981-10-22 METHOD OF PREPARING CHLOR-FLUORALKENYL-SUBSTITUTED CYCLOPROPANCARBOXYL ACID ESTERS
BR8106820A BR8106820A (en) 1980-10-23 1981-10-22 PROCESS FOR THE PREPARATION OF ESTHERES

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19803043976 DE3043976A1 (en) 1980-11-21 1980-11-21 Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds.

Publications (1)

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DE3043976A1 true DE3043976A1 (en) 1982-07-01

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DE19803043976 Withdrawn DE3043976A1 (en) 1980-10-23 1980-11-21 Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds.

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