CA1123855A - Process to 3-phenoxybenzyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropane- carboxylate - Google Patents
Process to 3-phenoxybenzyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropane- carboxylateInfo
- Publication number
- CA1123855A CA1123855A CA310,777A CA310777A CA1123855A CA 1123855 A CA1123855 A CA 1123855A CA 310777 A CA310777 A CA 310777A CA 1123855 A CA1123855 A CA 1123855A
- Authority
- CA
- Canada
- Prior art keywords
- lower alkyl
- dichlorovinyl
- dimethylcyclopropanecarboxylate
- phenoxybenzyl
- alcohol
- 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
- 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
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT: PROCESS TO 3-PHENOXYBENZYL 3-(2,2-DIHALOVINYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLATE The insecticide, 3-phenoxybenzyl 3-(2,2-dihalo-vinyl)-2,2-dimethylcyclopropanecarboxylate, is produced in high yield by the alcoholysis of a lower alkyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylate with 3-phenoxybenzyl alcohol in the presence of a cata-lytic quantity of lower alkyl titanium alkoxide. r6lA52
Description
PROCESS TO 3-PHENOXYBENZY~ 3-(~,2-DI~ALOVINYL)-2,~-DIMETHYLCYCLOPROPANECARBOXYLATE
This invention relates to a novel process for pre-paring an insecticidal cyclopropanecarboxylate, a pyre-throid, by alcoholysis of a lower alkyl ester precursor.
U.S. Patent 4,024,163 discloses new insecticides, pyrethroids, which are esters containing a 3-(2,~-di-halovinyl)-2,2-dimethylcyclopropanecarboxylic acid unit;
3-phenoxybenzyl alcohol is one of the alcohol moieties disclosed. 3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate is one of the most active of the new pyrethroids and is expected to be commercial-ized throughout the world. Chemical processes capable of producing 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate efficiently from readilyavailable starting materials are being sought, and a number of synthesis routes have been disclosed.
The most economical processes ~or making 3-phenoxy-benzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane~
carboxylate involve the initial production of a lower alkyl 3-(~j2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate, followed by introduction of the 3-phenoxy-benzyl alcohol moiety as the last step, this for the reason that the lower alkyl precursors are ea~ier to handle and are less expensi~e as intermediates. Gen-erally, the 3-phenoxybenzyl alcohol unit is introduced by (1) hydrolyzing the lower alkyl ester, (2) making the acyl halide, and then (3) reacting the acyl hal-ide with 3-phenoxybenzyl alcohol, for example, U.S.
3~55 Patent 4,024,163. This 3-step process is time-consuming, proceeds in relatively low overall yield, wastes val-uable chemi~al compoundsl and is expensive.
Other techniques may be utilized to transform the lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate to the 3-phenoxybenzyl ester. For ex-ample, transesterification, wherein the lower alkyl cy-cylopropanecarboxylate is reacted with a second ester, a 3-phenoxybenzyl carboxylate, may be employed. Also, ~o it is known that an ester may be treated with an alco-hol in the presence of an acidic or basic catalyst, re-sulting in alcoholysis, wherein the alcohol moiety of the ester is switched. These processes do not go to completion, but approach equilibria. In order to affect the equilibria to yield more of the desired ester, a large excess of the reactant ester or alcohol is often employed, or the product ester or alcohol is removed.
The overall practical efficiency with which the desired ester is produced may be influenced by the choice of catalyst. Among the basic catalysts disclosed in the prior art are metal alkoxides; for example, the alco-holysis of methyl methacrylate with ~4 to C18 alcohols in the presence of titanium isopropylate has been dis-closed.
The present invention provides a process for pre-paring a 3-phenoxybenzyl 3-~2,2-dihalovinyl)-2,2-di-methylcyclopropanecarboxylate which comprises heating a mixture containing a lower alkyl 3-(2,2-dihalovinyl)-
This invention relates to a novel process for pre-paring an insecticidal cyclopropanecarboxylate, a pyre-throid, by alcoholysis of a lower alkyl ester precursor.
U.S. Patent 4,024,163 discloses new insecticides, pyrethroids, which are esters containing a 3-(2,~-di-halovinyl)-2,2-dimethylcyclopropanecarboxylic acid unit;
3-phenoxybenzyl alcohol is one of the alcohol moieties disclosed. 3-Phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate is one of the most active of the new pyrethroids and is expected to be commercial-ized throughout the world. Chemical processes capable of producing 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate efficiently from readilyavailable starting materials are being sought, and a number of synthesis routes have been disclosed.
The most economical processes ~or making 3-phenoxy-benzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane~
carboxylate involve the initial production of a lower alkyl 3-(~j2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate, followed by introduction of the 3-phenoxy-benzyl alcohol moiety as the last step, this for the reason that the lower alkyl precursors are ea~ier to handle and are less expensi~e as intermediates. Gen-erally, the 3-phenoxybenzyl alcohol unit is introduced by (1) hydrolyzing the lower alkyl ester, (2) making the acyl halide, and then (3) reacting the acyl hal-ide with 3-phenoxybenzyl alcohol, for example, U.S.
3~55 Patent 4,024,163. This 3-step process is time-consuming, proceeds in relatively low overall yield, wastes val-uable chemi~al compoundsl and is expensive.
Other techniques may be utilized to transform the lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate to the 3-phenoxybenzyl ester. For ex-ample, transesterification, wherein the lower alkyl cy-cylopropanecarboxylate is reacted with a second ester, a 3-phenoxybenzyl carboxylate, may be employed. Also, ~o it is known that an ester may be treated with an alco-hol in the presence of an acidic or basic catalyst, re-sulting in alcoholysis, wherein the alcohol moiety of the ester is switched. These processes do not go to completion, but approach equilibria. In order to affect the equilibria to yield more of the desired ester, a large excess of the reactant ester or alcohol is often employed, or the product ester or alcohol is removed.
The overall practical efficiency with which the desired ester is produced may be influenced by the choice of catalyst. Among the basic catalysts disclosed in the prior art are metal alkoxides; for example, the alco-holysis of methyl methacrylate with ~4 to C18 alcohols in the presence of titanium isopropylate has been dis-closed.
The present invention provides a process for pre-paring a 3-phenoxybenzyl 3-~2,2-dihalovinyl)-2,2-di-methylcyclopropanecarboxylate which comprises heating a mixture containing a lower alkyl 3-(2,2-dihalovinyl)-
2,2-dimethylcyclopropanecarboxylate, 3-phenoxybenzyl alcohol, and a lower alkyl titanium alkoxide in a sol-vent.
According to this invention, high yields of 3-phenoxybenzyl 3-(2,2-dichlorovinyl)~2,2-dimethylcyclo-propanecarboxylate are obtained from the corresponding lower alkyl ester by heating under reflux at a tempera-tur~ of at least 100 C a substantially anhydrous mix-ture containing (1) the lower alkyl ester, (2) an ap-~lZ3~355 proximately equimolar amount of 3-phenoxybenzyl alco-hol, and (3) a catalytic quantity of at least partially dissolved lower alkyl titanium alkoxide, all in an inert hydrocarbon solvent which forms an azeotropic 5 mixture with, or boils at a higher temperature than, the lower alkyl alcohol by-product,and removing said by-product from the mixture by distillation as it is produced.
An advantage of the present invention is that it lO provides a commercially acceptable process for converting a lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate to the insecticidal 3-phenoxybenzyl ester. Yields of at least 90% are obtained.
For purposes of this invention, the term "lower alkyl" means a straight or branched chain of 1-4 carbon atoms.
The use of approximately equimolar amounts of the ester and alcohol contemplates that one or the other may be in slight excess, 2-3~ for example.
A number of inert hydrocarbon solvents which form-azeotropic mixtures with, or boil at temperatures higher than, a given aliphatic alcohol are readily available and well known to those skilled in the art. If the lower alkyl alcohol is methanol or ethanol, n-octane, benzene, toluene, xylene, or mesitylene may be employed, for ex-ample.
Preferably, the lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate is either a methyl ~; or ethyl ester.
The lower alkyl titanium alkoxide is preferably selected from titanium methylate or titanium isopropyl-ate. A catalytic quantity of lower alkyl titanium alk-oxide, in the range 0.001-0.01 mole per mole of lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethyl~yclopropane-carboxylate, should be employed.
Although the reaction may proceed at lower tempera-tures, to achieve a reasonable reaction rate it is es-~lZ3~55 sential that the alcoholysis be conducted at a tempera-ture of 100-C or higher. The upper temperature limit is set by the decomposition temperature of reactants or products, at least 200 C.
In the following examples all temperatu~es are in degrees centigrade and pressures are in millimeters of mercury.
EXAMPLE I
Preparation_of 3-Phenoxybenzyl 3-(2,2-Dichloro-vinyl)-2l2-dimethylcyclopropanecarboxylate from Ethyl
According to this invention, high yields of 3-phenoxybenzyl 3-(2,2-dichlorovinyl)~2,2-dimethylcyclo-propanecarboxylate are obtained from the corresponding lower alkyl ester by heating under reflux at a tempera-tur~ of at least 100 C a substantially anhydrous mix-ture containing (1) the lower alkyl ester, (2) an ap-~lZ3~355 proximately equimolar amount of 3-phenoxybenzyl alco-hol, and (3) a catalytic quantity of at least partially dissolved lower alkyl titanium alkoxide, all in an inert hydrocarbon solvent which forms an azeotropic 5 mixture with, or boils at a higher temperature than, the lower alkyl alcohol by-product,and removing said by-product from the mixture by distillation as it is produced.
An advantage of the present invention is that it lO provides a commercially acceptable process for converting a lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate to the insecticidal 3-phenoxybenzyl ester. Yields of at least 90% are obtained.
For purposes of this invention, the term "lower alkyl" means a straight or branched chain of 1-4 carbon atoms.
The use of approximately equimolar amounts of the ester and alcohol contemplates that one or the other may be in slight excess, 2-3~ for example.
A number of inert hydrocarbon solvents which form-azeotropic mixtures with, or boil at temperatures higher than, a given aliphatic alcohol are readily available and well known to those skilled in the art. If the lower alkyl alcohol is methanol or ethanol, n-octane, benzene, toluene, xylene, or mesitylene may be employed, for ex-ample.
Preferably, the lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate is either a methyl ~; or ethyl ester.
The lower alkyl titanium alkoxide is preferably selected from titanium methylate or titanium isopropyl-ate. A catalytic quantity of lower alkyl titanium alk-oxide, in the range 0.001-0.01 mole per mole of lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethyl~yclopropane-carboxylate, should be employed.
Although the reaction may proceed at lower tempera-tures, to achieve a reasonable reaction rate it is es-~lZ3~55 sential that the alcoholysis be conducted at a tempera-ture of 100-C or higher. The upper temperature limit is set by the decomposition temperature of reactants or products, at least 200 C.
In the following examples all temperatu~es are in degrees centigrade and pressures are in millimeters of mercury.
EXAMPLE I
Preparation_of 3-Phenoxybenzyl 3-(2,2-Dichloro-vinyl)-2l2-dimethylcyclopropanecarboxylate from Ethyl
3-(2,2-Dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate Ethyl 3-(2,2-dichlorovinyl)-2,~-dimethylcyclopro-panecarboxylate (36,300 g, 150 moles) and 3-phenoxy-benzyl alcohol (30,400 g, t50 moles), together with 58,100 g of n-octane, in a vessel equipped with a con-denser topped with an automatic liquid dividing dis-tillation head, was stirred and heated under relux while 4500 g of distillate containing residual water and octane was removed, rendering the mixture substan-tially anhydrous. The mixture was then cooled, andtitanium isopropylate (227 g, 0.80 mole) was added~
ThP mixture was then stirred and heated under reflux for 13 hours, during which time 43,400 g of distillate containing n-octan~ and ethanol was collected. After removing the remaining solvent by distillation, crude 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcy-clopropanecarboxylate (60,800 g, 94.8~ yield, 91.4 purity) remained, the product being identified and as sayed by quantitative vapor phase chromatographic (VPC) analysis column against an authentic sample.
Similarly, heating under reflux for 5.5 hours a substantially anhydrous mixture containing 0.1 mole ethyl ester, 0.1 mole alcohol, and 0.14 ml titanium isopropylate in about 150 ml of xylene, removing ethanol as it was ormed, produced a solution whose solute con-tained 95.4% 3-phenoxybenzyl 3-~2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate according to VPC
I
1~23~35S
analysis.
EXAMPLE II
Pre~aration_of 3-Phenoxybenzyl 3-(2,2-Dichloro-vinyl)-2,2-dimethylcycloPropanecarboxylate from Methyl 3--(2,2-Dichlorovinyl)-2,2-dimethylcyclopropanecarbOXylate Methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate (22.74 g, 0.1 mole), and 3-phenoxybenzyl alcohol (20.68 g, 0.1 mole) in 150 ml of mesitylene was heated under reflux while 20 ml of distillate was re-moved, drying the mixture, making it substantially an-hydrous. The mixture was then cooled and 0.086 g of titanium methylate was added. The mixture was then heated under reflux for 4.25 hours, as the by-product methanol was removed from the reaction mixture by dis-tillation. VPC analysis indicated the solute was 93%3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate.
Similarly, after a substantially anhydrous mixture of 0.1 mole methyl ester and 0.1 mole alcohol in about 150 ml mesitylene containing 0.142 g titanium isopropyl-ate was heated under reflux for 1.5 hours, removing methanol continuously by distillation, VPC indicated the solute contained 94.7% 3-phenoxyben2yl 3-(2,?-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate.
~5 Similarly, after a substantially anhydrous mixture of 0.1 mole methyl ester, 0.1 mole alcohol, and 0.15 ml of titanium isopropylate in about 150 ml of n-octane was heated under reflux for 2.5 hours, removing methanol as it was produced, VPC analysis of the solute indicated it contained 93.5~ 3-phenoxybenzyl 3-(2,2-dichlorovinyl) 2,2-dimethylcyclopropanecarboxylate.
ThP mixture was then stirred and heated under reflux for 13 hours, during which time 43,400 g of distillate containing n-octan~ and ethanol was collected. After removing the remaining solvent by distillation, crude 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcy-clopropanecarboxylate (60,800 g, 94.8~ yield, 91.4 purity) remained, the product being identified and as sayed by quantitative vapor phase chromatographic (VPC) analysis column against an authentic sample.
Similarly, heating under reflux for 5.5 hours a substantially anhydrous mixture containing 0.1 mole ethyl ester, 0.1 mole alcohol, and 0.14 ml titanium isopropylate in about 150 ml of xylene, removing ethanol as it was ormed, produced a solution whose solute con-tained 95.4% 3-phenoxybenzyl 3-~2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate according to VPC
I
1~23~35S
analysis.
EXAMPLE II
Pre~aration_of 3-Phenoxybenzyl 3-(2,2-Dichloro-vinyl)-2,2-dimethylcycloPropanecarboxylate from Methyl 3--(2,2-Dichlorovinyl)-2,2-dimethylcyclopropanecarbOXylate Methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate (22.74 g, 0.1 mole), and 3-phenoxybenzyl alcohol (20.68 g, 0.1 mole) in 150 ml of mesitylene was heated under reflux while 20 ml of distillate was re-moved, drying the mixture, making it substantially an-hydrous. The mixture was then cooled and 0.086 g of titanium methylate was added. The mixture was then heated under reflux for 4.25 hours, as the by-product methanol was removed from the reaction mixture by dis-tillation. VPC analysis indicated the solute was 93%3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate.
Similarly, after a substantially anhydrous mixture of 0.1 mole methyl ester and 0.1 mole alcohol in about 150 ml mesitylene containing 0.142 g titanium isopropyl-ate was heated under reflux for 1.5 hours, removing methanol continuously by distillation, VPC indicated the solute contained 94.7% 3-phenoxyben2yl 3-(2,?-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate.
~5 Similarly, after a substantially anhydrous mixture of 0.1 mole methyl ester, 0.1 mole alcohol, and 0.15 ml of titanium isopropylate in about 150 ml of n-octane was heated under reflux for 2.5 hours, removing methanol as it was produced, VPC analysis of the solute indicated it contained 93.5~ 3-phenoxybenzyl 3-(2,2-dichlorovinyl) 2,2-dimethylcyclopropanecarboxylate.
Claims (11)
1. A process for preparing a 3-phenoxybenzyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylate which comprises heating a mixture containing a lower alkyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecar-boxylate, 3-phenoxybenzyl alcohol, and a lower alkyl titanium alkoxide in a solvent.
2. The process of claim 1 for preparing 3-phenoxy-benzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate characterized by heating under reflux at a temperature of at least 100°C a substantially anhydrous mixture containing (1) a lower alkyl 3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate, (2) an approximately equimolar amount of 3-phenoxybenzyl alco-hol, and (3) a catalytic quantity of at least partially dissolved lower alkyl titanium alkoxide, all in an inert hydrocarbon solvent which forms an azeotropic mixture with, or boils at a higher temperature than, the lower alkyl alcohol by-product, and removing said by-product from the mixture by distillation as it is produced.
3. A process according to claim 2 characterized in that the lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate is selected from methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and ethyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane-carboxylate.
4. A process according to claim 3 characterized in that the lower alkyl titanium alkoxide is selected from titanium methylate and titanium isopropylate.
5. A process according to claim 4 characterized in that ethyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate, an approximately equimolar amount of 3-phenoxybenzyl alcohol, and a catalytic quantity of titanium isopropylate in n-octane are heated under reflux, remov-ing ethanol as it is produced.
6. A process for preparing a 3-phenoxybenzyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylate which comprises heating a mixture containing a lower alkyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylate, 3-phenoxybenzyl alcohol, and a catalytic quantity of a lower alkyl titanium alkoxide in a solvent, the catalytic quantity of lower alkyl titanium alk-oxide being in the range 0.001 to 0.01 mole per mole of lower alkyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropanecarboxylate.
7. The process of claim 6 for preparing 3-phenoxy-benzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate characterized by heating under reflux at a temperature of at least 100°C a substantially anhydrous mixture containing (1) a lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecar-boxylate, (2) an approximately equimolar amount of 3-phenoxy-benzyl alcohol, and (3) the said catalytic quantity of at least partially dissolved lower alkyl titanium alkoxide, all in an inert hydrocarbon solvent which forms an azeotropic mixture with, or boils at a higher temperature than, the lower alkyl alcohol by-product, and removing said by-product from the mix-ture by distillation as it is produced.
8. A process according to claim 7 characterized in that the lower alkyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclo-propanecarboxylate is selected from methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate and ethyl 3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate.
9. A process according to claim 8 characterized in that the lower alkyl titanium alkoxide is selected from titanium methylate and titanium isopropylate.
10. A process according to claim 9 characterized in that ethyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecar-boxylate, an approximately equimolar amount of 3-phenoxybenzyl alcohol, and a catalytic quantity of titanium isopropylate in n-octane are heated under reflux, removing ethanol as it is produced.
11. A process for preparing 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate which com-prises heating under reflux at a temperature of at least 100°C
a substantially anhydrous mixture containlng (1) a lower alkyl 3-(2,2-dichlorovlnyl)-2,2-dimethylcyclopropanecarboxylate se-lected from methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate or ethyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, (2) an approximately equimolar amount of 3-phenoxybenzyl alcohol, and (3) 0.001 to 0.01 mole of ti-tanium isopropylate per mole of lower alkyl 3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate, all in an inert aliphatic hydrocarbon solvent which forms an azeo-tropic mixture with, or boils at a higher temperature than, the lower alkyl alcohol by-product, removing said by-product from the mixture by distillation as it is produced, stripping said solvent, leav-ing as a residue said 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate.
a substantially anhydrous mixture containlng (1) a lower alkyl 3-(2,2-dichlorovlnyl)-2,2-dimethylcyclopropanecarboxylate se-lected from methyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopro-panecarboxylate or ethyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate, (2) an approximately equimolar amount of 3-phenoxybenzyl alcohol, and (3) 0.001 to 0.01 mole of ti-tanium isopropylate per mole of lower alkyl 3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate, all in an inert aliphatic hydrocarbon solvent which forms an azeo-tropic mixture with, or boils at a higher temperature than, the lower alkyl alcohol by-product, removing said by-product from the mixture by distillation as it is produced, stripping said solvent, leav-ing as a residue said 3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US83905177A | 1977-10-03 | 1977-10-03 | |
| US839,051 | 1977-10-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1123855A true CA1123855A (en) | 1982-05-18 |
Family
ID=25278739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA310,777A Expired CA1123855A (en) | 1977-10-03 | 1978-09-06 | Process to 3-phenoxybenzyl 3-(2,2-dihalovinyl)-2,2-dimethylcyclopropane- carboxylate |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5459265A (en) |
| BR (1) | BR7806542A (en) |
| CA (1) | CA1123855A (en) |
| GB (1) | GB2005269B (en) |
| GT (1) | GT197854452A (en) |
| MX (1) | MX5105E (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5154841A (en) * | 1988-12-21 | 1992-10-13 | The Procter & Gamble Company | Process for preparing substituted imidazoline fabric conditioning compounds |
| CN1144778C (en) * | 1998-10-08 | 2004-04-07 | 住友化学工业株式会社 | Method for preparing cyclopropane carboxylic ester |
| CN1183095C (en) * | 1999-06-16 | 2005-01-05 | 住友化学工业株式会社 | Preparation method of cyclopropane carboxylic acid ester |
| WO2006080475A1 (en) | 2005-01-28 | 2006-08-03 | Sumitomo Chemical Company, Limited | Transition metal complex, method for producing such transition metal complex, substituted fluorene compound, method for producing such substituted fluorene compound, catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer |
-
1978
- 1978-09-06 CA CA310,777A patent/CA1123855A/en not_active Expired
- 1978-09-29 JP JP11941178A patent/JPS5459265A/en active Granted
- 1978-09-29 GB GB7838708A patent/GB2005269B/en not_active Expired
- 1978-10-02 MX MX787438U patent/MX5105E/en unknown
- 1978-10-02 BR BR7806542A patent/BR7806542A/en unknown
- 1978-10-02 GT GT197854452A patent/GT197854452A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GT197854452A (en) | 1980-03-25 |
| GB2005269A (en) | 1979-04-19 |
| JPS5549065B2 (en) | 1980-12-10 |
| JPS5459265A (en) | 1979-05-12 |
| MX5105E (en) | 1983-03-16 |
| GB2005269B (en) | 1982-03-10 |
| BR7806542A (en) | 1979-05-02 |
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