CA1164009A - Process for the preparation of chloro-fluoroalkenyl- substituted cyclopropanecarboxylic acid esters - Google Patents
Process for the preparation of chloro-fluoroalkenyl- substituted cyclopropanecarboxylic acid estersInfo
- Publication number
- CA1164009A CA1164009A CA000388520A CA388520A CA1164009A CA 1164009 A CA1164009 A CA 1164009A CA 000388520 A CA000388520 A CA 000388520A CA 388520 A CA388520 A CA 388520A CA 1164009 A CA1164009 A CA 1164009A
- Authority
- CA
- Canada
- Prior art keywords
- radical
- process according
- ester
- formula
- diluent
- 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.)
- Expired
Links
Classifications
-
- 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
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional 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
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
Abstract
Process for the preparation of chloro-fluoroalkenyl-substituted cyclopropanecarboxylic acid esters ABSTRACT OF THE DISCLOSURE
A process for the production of an ester of the formula in which R1 is a fluorine atom or a trifluoromethyl group, and R2 is a C1-4 alkyl radical or a radical of an alcohol which can be used for pyrethroids, comprising splitting off hydrogen chloride from an ester of the formula in a polar aprotic diluent, in the presence of (a) an alkali metal carbonate and a quaternary ammonium or phosphonium salt or (b) potassium fluoride. Those starting esters where R1 is trifluoromethyl are new. The end products are insecticidally active when R2 is a radical of an alcohol usually used in pyrethoids.
*******************************
A process for the production of an ester of the formula in which R1 is a fluorine atom or a trifluoromethyl group, and R2 is a C1-4 alkyl radical or a radical of an alcohol which can be used for pyrethroids, comprising splitting off hydrogen chloride from an ester of the formula in a polar aprotic diluent, in the presence of (a) an alkali metal carbonate and a quaternary ammonium or phosphonium salt or (b) potassium fluoride. Those starting esters where R1 is trifluoromethyl are new. The end products are insecticidally active when R2 is a radical of an alcohol usually used in pyrethoids.
*******************************
Description
The invention relates to an unobvious process for the preparation of certain chloro-fluoroalkenyl-substituted cyclo-propanecarboxylic acid esters by dehydrohalogenation of chloro-fluoroalkyl-substituted cyclopropanecarboxylic acid esters.
It is already known that 3-(2',2'-dichloro-3',3',3'-trifluoropropyl)-2,2-dimethyl-cyclopropanecarboxylic acid esters can be converted into the corresponding (2'-chloro-3',3',3'-trifluoropropenyl)-esters by dehydrochlorination by carrying out the reaction in the presence of an alkali metal carbonate in a polar aprotic solvent. However, the yields of 55 - 63% which can thereby be achieved are not satisfactory for an industrial procedure (see European Published Patent Application 10,859).
According to the present invention we now provide a process for the production of an ester of the general formula RlCF CCl=C o R2
It is already known that 3-(2',2'-dichloro-3',3',3'-trifluoropropyl)-2,2-dimethyl-cyclopropanecarboxylic acid esters can be converted into the corresponding (2'-chloro-3',3',3'-trifluoropropenyl)-esters by dehydrochlorination by carrying out the reaction in the presence of an alkali metal carbonate in a polar aprotic solvent. However, the yields of 55 - 63% which can thereby be achieved are not satisfactory for an industrial procedure (see European Published Patent Application 10,859).
According to the present invention we now provide a process for the production of an ester of the general formula RlCF CCl=C o R2
2 ~ 2 tI) H C / \ CH
in which Rl represents a fluorine atom or a trifluoromethyl group and R2 represents a C1 4 alkyl group or a radical of an alcohol which can be used for pyrethroids, by splitting off hydrogen chloride from an ester of the general formula ~ ~ 6 ~
in which Rl represents a fluorine atom or a trifluoromethyl group and R2 represents a C1 4 alkyl group or a radical of an alcohol which can be used for pyrethroids, by splitting off hydrogen chloride from an ester of the general formula ~ ~ 6 ~
3 ~ CH3 (II) in which Rl and R2 have the abovementioned meaning, in a polar aprotic diluent, characterised in that either the reaction is carried out in the presence of alkali metal carbonates and quaternary ammonium or phosphonium salts or the reaction is carried out in the presence of potassium fluoride.
This procedure leads to yields of 75 - 85%, which is a considerable and surprising increase compared with the state of the art.
The compounds of the formula (II) are known in some cases, or they can be prepared by processes analogous to known processes (see DE-OS (German Published Specification) 2,907,609).
However certain compounds of the formula (II) are novel.
According to the present invention we therefore further provide, as new compounds, esters of the general formula (II') ~ 2 in which R2 represents a Cl 4 alkyl radical or a radical of an alcohol which can be used for pyrethroids.
Particularly preferred compounds of the invention are those in which _, _ ~_.. ., ~
~ ~ G ~
R2 represents a methyl, ethyl or penta-fluorooenzyl radical or a 3-phenoxy-4-fluor~-benzyl radical which is optionally substituted by CN in the ~-position.
The compounds of the present invention, are of particular interest, since they lead to outstanding agents for combating pests.
The process according to the invention is preferably carried out to prepare a compound of the formula (I) in û which R1 represents a fluorine atom or a trifluoromethyl group and R represents a C1_4 alkyl or pentafluorobenzyl group, or a 3-phenoxybenzyl group which is optionally substituted by CN in the ~-position and is optionally substituted both in the phenoxy part and in the benzyl part;
and is particularly preferably carried out to prepare a 0 compound in which R2 represents a methyl, ethyl, pentafluorobenzyl or 4-fluoro-3-phenoxybenzyl radical.
If, for example, 2,2-dimethyl-3-(2,2-dichloro-3,3,
This procedure leads to yields of 75 - 85%, which is a considerable and surprising increase compared with the state of the art.
The compounds of the formula (II) are known in some cases, or they can be prepared by processes analogous to known processes (see DE-OS (German Published Specification) 2,907,609).
However certain compounds of the formula (II) are novel.
According to the present invention we therefore further provide, as new compounds, esters of the general formula (II') ~ 2 in which R2 represents a Cl 4 alkyl radical or a radical of an alcohol which can be used for pyrethroids.
Particularly preferred compounds of the invention are those in which _, _ ~_.. ., ~
~ ~ G ~
R2 represents a methyl, ethyl or penta-fluorooenzyl radical or a 3-phenoxy-4-fluor~-benzyl radical which is optionally substituted by CN in the ~-position.
The compounds of the present invention, are of particular interest, since they lead to outstanding agents for combating pests.
The process according to the invention is preferably carried out to prepare a compound of the formula (I) in û which R1 represents a fluorine atom or a trifluoromethyl group and R represents a C1_4 alkyl or pentafluorobenzyl group, or a 3-phenoxybenzyl group which is optionally substituted by CN in the ~-position and is optionally substituted both in the phenoxy part and in the benzyl part;
and is particularly preferably carried out to prepare a 0 compound in which R2 represents a methyl, ethyl, pentafluorobenzyl or 4-fluoro-3-phenoxybenzyl radical.
If, for example, 2,2-dimethyl-3-(2,2-dichloro-3,3,
4,4,4-pentafluoro-butyl)-cyclopropanecarboxylic acid pentafluorobenzyl ester is used as the starting substance, the course of the reaction can be represented by the following equation:
CF3-CF2-Ccl2-c'i2 ~ C02-C~2 ~ 5 - HCl CF3 CF2 CCl C~ ~ o H C/ CH
Le A 20 705 û 9 Hydrogen chloride is split off from the compounds of 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, which serves as a catalyst, or in the presence of potassium fluoride in a polar aprotic diluent.
The polar aprotic diluent is preferably dimethyl-formamide, dimethylacetamide or acetonitrile.
Quaternary ammonium salts which are preferably employed are: tetrabutylammonium bromide, benzyltriethyl-ammonium chloride and methyltrioctylammonium chloride.
The alkali metal carbonate is preferably employed in an equimolar amount or in excess (up to 5 molar).
A process according to the invention carried out in acetonitrile, as diluent, in the presence of potassium carbonate and a quaternary ammonium salt is particularly preferred.
However, a process carried out in dimethylformamide, as diluent, in the presence of potassium fluoride is also particularly preferred.
The process according to the present ir,vention is further illustrated by the following Examples.
Example 1 Cl ~ C 02 C~ ~ F
4 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3,3_ trifluoropropyl~-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester were dissolved in 20 ml of acetonitrile.
4 9 of pO~assium carbonate and 0.5 9 of tetrabutylammonium bromide were added and the mixture was heated in 180C in Le A 20 705 an autoclave for 4 hours. After ccoling, the mixture was diluted with water and rendersd neutral with hvdrochloric acid. It was extracted with methylene chloride, dried with sodium sulphate and concentrated in a rotary evaporator, and the concentrate was subjected to incipient distillation at 60C under a high vacuum. 3.4 9 of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,3-trifluoropropenyl)-cyclopropane-carboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester, in which the Z-isomers were very predominant, were abtained.
Refractive index: nDU = 1.519 Example 2 ~3C CP:3 Cl ~ CC2rH~-l~
CF~ C~
3.5 9 of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,3-trifluoropropenyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-~'-c~ano-benzyl ester were obtained from 3.9 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3,3-trifluoro-propyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-~'-cyano-benzyl ester in a manner analogous to that in Example 1.
Example 3
CF3-CF2-Ccl2-c'i2 ~ C02-C~2 ~ 5 - HCl CF3 CF2 CCl C~ ~ o H C/ CH
Le A 20 705 û 9 Hydrogen chloride is split off from the compounds of 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, which serves as a catalyst, or in the presence of potassium fluoride in a polar aprotic diluent.
The polar aprotic diluent is preferably dimethyl-formamide, dimethylacetamide or acetonitrile.
Quaternary ammonium salts which are preferably employed are: tetrabutylammonium bromide, benzyltriethyl-ammonium chloride and methyltrioctylammonium chloride.
The alkali metal carbonate is preferably employed in an equimolar amount or in excess (up to 5 molar).
A process according to the invention carried out in acetonitrile, as diluent, in the presence of potassium carbonate and a quaternary ammonium salt is particularly preferred.
However, a process carried out in dimethylformamide, as diluent, in the presence of potassium fluoride is also particularly preferred.
The process according to the present ir,vention is further illustrated by the following Examples.
Example 1 Cl ~ C 02 C~ ~ F
4 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3,3_ trifluoropropyl~-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester were dissolved in 20 ml of acetonitrile.
4 9 of pO~assium carbonate and 0.5 9 of tetrabutylammonium bromide were added and the mixture was heated in 180C in Le A 20 705 an autoclave for 4 hours. After ccoling, the mixture was diluted with water and rendersd neutral with hvdrochloric acid. It was extracted with methylene chloride, dried with sodium sulphate and concentrated in a rotary evaporator, and the concentrate was subjected to incipient distillation at 60C under a high vacuum. 3.4 9 of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,3-trifluoropropenyl)-cyclopropane-carboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester, in which the Z-isomers were very predominant, were abtained.
Refractive index: nDU = 1.519 Example 2 ~3C CP:3 Cl ~ CC2rH~-l~
CF~ C~
3.5 9 of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,3-trifluoropropenyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-~'-c~ano-benzyl ester were obtained from 3.9 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3,3-trifluoro-propyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-~'-cyano-benzyl ester in a manner analogous to that in Example 1.
Example 3
5.C2 C02CH2 ~ F~
Le A 20 705 ~ ~` 6'~
1.02 9 (2mmols) of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3,4,4,4-pentafluoro)-butyl-cyclopropane carboxylic acid pentafluorobenzyl ester were dissolved in 7 ml of dimethylacetamide, 0.6 9 of potassium fluoride was added and the mixture was heated to 140C for 4 hours.
After cooling, the mixture was diluted with water and then immediately extracted three times with ether and the combined ether extracts were washed with concentrated sodium chloride solution until neutral. The organic 1û phase was dried with sodium sulphate and filtered, the filtrate was concentrated in a rotary evaporator and the concentrate was subjected to incipient distillation under a high vacuum. The residue consisted of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,4,4,4-pentafluoro-but-1-enyl)-cyclopropanecarboxylic acid pentafluorobenzyl ester.Example 4 F5 ~ CO2CH2 ~ -r 2 9 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 were dissolved in 10 ml of 2û acetonitrile. 1.5 9 of potassium carbonate (finely powdered) and 0.3 9 of tetrabutylammonium chloride were added and the mixture was heated to 170C in an autoclave for 12 hours. The mixture was worked up in a manner analogous to that in Example 1. 1.6 9 of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,4,4,4-pentafluoro-butenyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester were obtained.
Le A 20 705 ~6~&e9 Example 5 F5C, CN
2.9 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3, 4,4,4-pentafluoro-butyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-Kl-cyano-benzyl ester were dissolved in 10 ml of dimethylformamide. 0.7 9 of thoroughly dried potassium fluoride was added and the mixture was heated to 150C for one hour. After cooling, the mixture was diluted with water and rendered neutral. After extraction three times with ether, the combined ether extracts were dried and concentrated. The resulting 2,2-dimethyl-3-(2-chloro-3,3,4,4,4-pentafluoro-butenyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-~'-cyano-benzyl ester was purified by chromatography (silica gel/n-hexane/chloroform 3:1).
Example 6 307 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3, 3-trifluoro-propvl)-cyclopropanecarboxylic acid ethyl ester were dissolved in 1,000 ml of acetonitrile. 140 9 of potassium carbonate and 20 9 of methyltrioctylammonium chloride were added and the mixture was heated to 180C
in an autoclave for 8 hours. After cooling, the mixture was diluted with water and extracted with methylene chloride and the produc-t phase was washed with dilute hydrochloric acid, and then with water until neutral.
After drying with sodium sulphate, the product phase was evaporated in a rotary evaporator. Fractional distillation of the residue gave 230.5 9 (85o of theory) of 2,2-dimethyl-3-(2-chloro-3,3,3-trifluoropropenyl)-cyclo-propanecarboxylic acid ester of boiling point b.p. 94 to 96C/ 18 mbars.
Le A 20 705 -
Le A 20 705 ~ ~` 6'~
1.02 9 (2mmols) of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3,4,4,4-pentafluoro)-butyl-cyclopropane carboxylic acid pentafluorobenzyl ester were dissolved in 7 ml of dimethylacetamide, 0.6 9 of potassium fluoride was added and the mixture was heated to 140C for 4 hours.
After cooling, the mixture was diluted with water and then immediately extracted three times with ether and the combined ether extracts were washed with concentrated sodium chloride solution until neutral. The organic 1û phase was dried with sodium sulphate and filtered, the filtrate was concentrated in a rotary evaporator and the concentrate was subjected to incipient distillation under a high vacuum. The residue consisted of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,4,4,4-pentafluoro-but-1-enyl)-cyclopropanecarboxylic acid pentafluorobenzyl ester.Example 4 F5 ~ CO2CH2 ~ -r 2 9 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 were dissolved in 10 ml of 2û acetonitrile. 1.5 9 of potassium carbonate (finely powdered) and 0.3 9 of tetrabutylammonium chloride were added and the mixture was heated to 170C in an autoclave for 12 hours. The mixture was worked up in a manner analogous to that in Example 1. 1.6 9 of cis/trans-2,2-dimethyl-3-(2-chloro-3,3,4,4,4-pentafluoro-butenyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-benzyl ester were obtained.
Le A 20 705 ~6~&e9 Example 5 F5C, CN
2.9 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3, 4,4,4-pentafluoro-butyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-Kl-cyano-benzyl ester were dissolved in 10 ml of dimethylformamide. 0.7 9 of thoroughly dried potassium fluoride was added and the mixture was heated to 150C for one hour. After cooling, the mixture was diluted with water and rendered neutral. After extraction three times with ether, the combined ether extracts were dried and concentrated. The resulting 2,2-dimethyl-3-(2-chloro-3,3,4,4,4-pentafluoro-butenyl)-cyclopropanecarboxylic acid 4'-fluoro-3'-phenoxy-~'-cyano-benzyl ester was purified by chromatography (silica gel/n-hexane/chloroform 3:1).
Example 6 307 9 of cis/trans-2,2-dimethyl-3-(2,2-dichloro-3,3, 3-trifluoro-propvl)-cyclopropanecarboxylic acid ethyl ester were dissolved in 1,000 ml of acetonitrile. 140 9 of potassium carbonate and 20 9 of methyltrioctylammonium chloride were added and the mixture was heated to 180C
in an autoclave for 8 hours. After cooling, the mixture was diluted with water and extracted with methylene chloride and the produc-t phase was washed with dilute hydrochloric acid, and then with water until neutral.
After drying with sodium sulphate, the product phase was evaporated in a rotary evaporator. Fractional distillation of the residue gave 230.5 9 (85o of theory) of 2,2-dimethyl-3-(2-chloro-3,3,3-trifluoropropenyl)-cyclo-propanecarboxylic acid ester of boiling point b.p. 94 to 96C/ 18 mbars.
Le A 20 705 -
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a process for the production of pyrethroid esters of the general formula (I) in which R1 represents a fluorine atom or a trifluoromethyl group and R2 represents a C1-4 alkyl radical or a radical of an alcohol which can be used for pyrethroids, by splitting off hydrogen chloride from an ester of the general formula (II) in which R1 and R2 have the abovementioned meaning, in a polar aprotic diluent, the improvement which comprises carrying out the reaction in the pre-sence of an alkali metal carbonate and a quaternary ammonium or phosphonium salt, or in the presence of potassium fluoride.
2. A process according to claim 1, wherein an ester of formula (II) is used in which R2 represents a C1-4 alkyl or pentafluorobenzyl group, or a 3-phenoxybenzyl group which is optionally substituted by CN in the .alpha.-position and is optionally substituted in the benzyl part.
3. A process according to claim 2, wherein an ester of formula (II) is used in which R2 represents a methyl, ethyl, pentafluorobenzyl or 4-fluoro-3-phenoxybenzyl radical.
4. A process according to any of claims 1 to 3, wherein the polar aprotic diluent is dimethylformamide, dimethylacetamide or acetonitrile.
5. A process according to any of claims 1 to 3, wherein the quaternary ammonium salt is tetrabutylammonium bromide, benzyltriethylammonium chloride or methyltrioctylammonium chloride.
6. A process according to any of claims 1 to 3, in which the reaction is carried out in acetonitrile, as diluent, in the presence of potassium carbonate and a quaternary ammonium salt.
7. A process according to any of claims 1 to 3, in which the reaction is carried out in dimethylformamide, as diluent, in the presence of potassium fluoride.
8. Esters of the general formula (II') in which R2 represents a C1-4 alkyl radical or a radical of an alcohol which can be used for pyrethroids.
9. Compounds according to claim 8, wherein R2 represents a methyl, ethyl or pentafluorobenzyl radical or a 3-phenoxy-4-fluoro-benzyl radical which is optionally substituted by CN in the .alpha.-position.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803040001 DE3040001A1 (en) | 1980-10-23 | 1980-10-23 | Chloro-vinyl-cyclopropane-carboxylic acid ester(s) prodn. - by de-hydrochlorination of 3-fluoro-substd. 2,2-di:chloro-ethyl cpds. |
| DEP3040001.2 | 1980-10-23 | ||
| 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. |
| DEP3043976.0 | 1980-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1164009A true CA1164009A (en) | 1984-03-20 |
Family
ID=25788684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000388520A Expired CA1164009A (en) | 1980-10-23 | 1981-10-22 | Process for the preparation of chloro-fluoroalkenyl- substituted cyclopropanecarboxylic acid esters |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0050776B1 (en) |
| BR (1) | BR8106820A (en) |
| CA (1) | CA1164009A (en) |
| DE (1) | DE3161438D1 (en) |
| DK (1) | DK467381A (en) |
| IL (1) | IL64071A0 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8418331D0 (en) * | 1984-07-18 | 1984-08-22 | Ici Plc | Insecticidal ester |
| CN103232367B (en) * | 2013-05-15 | 2015-02-25 | 联保作物科技有限公司 | Pyrethroid compound as well as preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4183948A (en) * | 1977-01-24 | 1980-01-15 | Imperial Chemical Industries Limited | Halogenated esters |
| DE2831193A1 (en) * | 1978-07-15 | 1980-01-24 | Bayer Ag | FLUORALKENYL-SUBSTITUTED CYCLOPROPANCARBONIC ACID ESTERS AND THEIR USE AS INSECTICIDES |
-
1981
- 1981-10-12 DE DE8181108190T patent/DE3161438D1/en not_active Expired
- 1981-10-12 EP EP81108190A patent/EP0050776B1/en not_active Expired
- 1981-10-19 IL IL64071A patent/IL64071A0/en unknown
- 1981-10-22 BR BR8106820A patent/BR8106820A/en unknown
- 1981-10-22 CA CA000388520A patent/CA1164009A/en not_active Expired
- 1981-10-22 DK DK467381A patent/DK467381A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL64071A0 (en) | 1982-01-31 |
| EP0050776A1 (en) | 1982-05-05 |
| DE3161438D1 (en) | 1983-12-22 |
| DK467381A (en) | 1982-04-24 |
| EP0050776B1 (en) | 1983-11-16 |
| BR8106820A (en) | 1982-07-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4024163A (en) | Insecticides | |
| US5004822A (en) | Insecticides | |
| CA1146582A (en) | Halogenated esters | |
| HU184685B (en) | Isecticide and acaricide compositions containing halogenated esters of cyclopropane-carboxylic acid and process for producing the active agents | |
| JPH0127053B2 (en) | ||
| DE2034128C2 (en) | Cyclopentenolone esters, cyclopentenones and the use of the cyclopentenolone esters as insecticides | |
| DE2327660C3 (en) | Cyclopropanecarboxylic acid esters, process for their preparation and their use as insecticides | |
| US4056628A (en) | Insecticidal esters of alpha-phenoxy alkanoic acids with substituted benzyl alcohols | |
| US4137324A (en) | Optionally substituted phenyl-α-cyclopropyl acetic acid esters and use as insecticides | |
| CA1164009A (en) | Process for the preparation of chloro-fluoroalkenyl- substituted cyclopropanecarboxylic acid esters | |
| US4000181A (en) | α-Cyano-phenoxybenzyl cyclopropane carboxylate insecticides | |
| US4258202A (en) | Cyclopropanecarboxylic acids and esters | |
| DE2356702C2 (en) | Process for the preparation of trans-chrysanthemum monocarboxylic acid by hydrolysis of a cis / trans mixture of chrysanthemum monocarboxylic acid-C 1 -C 8 -alkyl esters | |
| US4551281A (en) | Process for the preparation of cyclopropane carboxylic acid esters | |
| US4464391A (en) | Pesticides | |
| PL123011B1 (en) | Method of manufacture of novel esters of phenylacetic acid and insecticidal and acaricidal agent | |
| US4482731A (en) | Process for the preparation of trans-3-(z-2-chloro-2-aryl-vinyl)-2,2-dimethyl-cyclopropane-1-carboxylic acid derivatives, and the use of intermediate products in agents for compating pests | |
| US4277490A (en) | Insecticidal 1-(2-naphthyl)-cyclobutane carboxylate | |
| JPS5812247B2 (en) | Insecticide | |
| JPS6347702B2 (en) | ||
| CA1141389A (en) | Fluoroalkenyl-substituted cyclopropane- carboxylic acid esters and their use as insecticides | |
| US4309555A (en) | Novel cyclopropane derivatives | |
| FR2431486A1 (en) | 1-Cyano-2,2-di:methyl-3-poly:halovinyl-cyclopropane(s) prepn. - for use as intermediates for pyrethroid insecticides, by decarboxylation of corresp. 1-cyano-1-carboxylic acid | |
| US5840958A (en) | 1S to 1R Epimerizations of pyrethroid intermediates | |
| CA1174689A (en) | Pyrethroids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |