WO2017025985A1 - Process of producing ethyl difluoroacetate - Google Patents
Process of producing ethyl difluoroacetate Download PDFInfo
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- WO2017025985A1 WO2017025985A1 PCT/IN2016/050264 IN2016050264W WO2017025985A1 WO 2017025985 A1 WO2017025985 A1 WO 2017025985A1 IN 2016050264 W IN2016050264 W IN 2016050264W WO 2017025985 A1 WO2017025985 A1 WO 2017025985A1
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- ethyl difluoroacetate
- producing ethyl
- difluoroacetate
- producing
- oxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
Definitions
- the present invention relates generally to a process of preparing a reagent used as an intermediate for producing pharmaceutical and agrochemical products. More particularly the present invention relates to an industrially viable process of producing ethyl difluoroacetate.
- Ethyl difluoroacetate is an important intermediate for the production of pharmaceutical and agrochemical products.
- Journal of Organic Chemistry, 28, P-1133-4, i963 reports the reaction of alpha, alpha- difluoro ethers with glass or silica gel and sulfuric acid at temperatures ranging between 70 to 160°C to give the corresponding ester and silicon tetrafluoride.
- Amer. Chem. Soc, 1950, 72, 1860 mentions the preparation of ethyl difluoroacetate with sulphuric acid in presence of siliceous material.
- JP 2013-147474A provides a method for the preparation of Ethyl difluoroacetate using 1,1,2,2-tetrafluoroethyl ether in the presence of ethanol, silica and sulphuric acid.
- the main drawback in all the above prior arts is the generation of toxic SiF 4 gas as a by-product; besides being toxic it has limited commercial value.
- JP 2008280305 provides a method for the preparation of Ethyl difluoroacetate using 1 , 1 ,2,2-tetrafluoroethyl ether in the presence of ethanol, sulphuric acid and alkali metal oxide or alkaline earth metal oxide or Group 13 metal oxide.
- the specification mentions use of AI2O 3 , Ga 2 0, Ga 2 (3 ⁇ 4, ⁇ 3 ⁇ 40 and !3 ⁇ 4(3 ⁇ 4, all of which are either amphoteric or basic metaloxides, which are easily soluble in mineral acids.
- the mostpreferred oxide is AI2O 3 , the drawback of which is lower yields and also generation of by-product which has no commercial value.
- US5, 710,317 describes the preparation of Ethyl difluoroacetate by reacting difluoroacetic acid fluoride with an alcohol of the formula ROH wherein R is an Ci-4 alkyl group.
- US20120190884 describes a method of producing Ethyl difluoroacetate that involves reacting difluoroacetyl fluoride with an aliphatic or cycloaliphatic alcohol in the presence of sodium carbonate.
- CN 102875379k describes a method of preparation of Ethyl difluoroacetate involving the reaction of difluoroacetamide with an alcohol in the presence of a strong acid.
- the present invention overcomes the problems in the prior art in the manufacture of Ethyl difluoroacetate and produces Ethyl difluoroacetate in high yield and purity and concomitantly generatesvaluable by-products namely BF 3 -etherate or high purity Phosphoric Acid which have ready commercial use.
- a basic object of the present invention is to overcome the disadvantages and drawbacks of the known art.
- Another object of the invention is to provide an industrially viable process of producing Ethyl difluoroacetateusing metalloid oxides such as Boron trioxide which forms acidic oxide, insoluble in mineral acids.
- Another object of the invention is to provide an industrially viable processof producing Ethyl difluoroacetate by using Group 15 poly atomic non-metal oxides like phosphorus pentoxide.
- Another object of the invention is to provide a process of producing Ethyl difluoroacetate that produces useful by-products, such as BF 3 -etherate or high purity Phosphoric acid.
- Another object of the invention is to provide an industrially viable process of producing Ethyl difluoroacetate in high yield and high purity.
- Another object of the invention is to provide an industrial viable process with significantly reduced reaction time.
- a process of producing ethyl difluoroacetate comprising the steps of reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE) with an oxide of elements selected from the groups 13or 15 in the presence of sulphuric acid followed by the addition of an alcohol to produce ethyl difluoroacetate and a useful by-product.
- the process of producing ethyl difluoroacetate comprising the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE), boron trioxide with sulphuric acid followed by addition of ethanol to produce ethyl difluoroacetate.
- BF 3 gas is generated.
- the generated BF 3 can be absorbed in an organic solvent like diethyl ether, tetrahydrofuran, hexane, heptane, acetic acid etc. with which it can form complex.
- the method of producing Ethyl difluoroacetate comprising the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- Ethoxy ethane (ETFEE), with sulphuric acid in presence of Phosphorus pentoxide followed by addition of ethanol. During the reaction, PF 5 is generated in gaseous form. The generated PF 5 is absorbed in water scrubber and further processed by methods well documented in prior art, to get high purity 85% phosphoric acid which has commercial value. A process of producing Ethyl difluoroacetate in high yield and high purity with reduced reaction times and a useful by-product.
- EMFEE 1,1,2,2 -tetrafluoro-1- Ethoxy ethane
- the present invention relates to a process of producing ethyl difluoroacetate in high yield and high purity with reduced reaction times and gives useful by- products.
- the by products can be recovered and used in the industry.
- the process of producing ethyl difluoroacetate comprises the steps of reacting the suspension of 1, 1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE) with an oxide of elements selected from the groups 13 or 15 in the presence of sulphuric acid followed by the addition of an alcohol to produce ethyl difluoroacetate and a useful by-product.
- the Group 13 oxide can be a metalloid oxide such as Boron trioxide which is an acidic oxide
- the Group 15 oxide is a poly atomic non-metal oxide like Phosphoruspentoxide.
- the alcohol can be any alcohol from the group, but preferably ethyl alcohol is used.
- C1-C4 Other alcohols (C1-C4) can also be used for the synthesis of acetate derivative.
- the sulphuric acid used is for obtaining high purity range of productbetween 98% to 100%.
- Sulphuric acid of 100% purity can be obtained by mixing 98% Sulphuric acid with 105% Oleum.
- the by-products obtained are non-toxic, useful byproducts can be recovered by using methods well known in the art.
- the process comprises the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE), boron trioxide with sulphuric acid followed by addition of ethanol to produce ethyl difluoroacetate. During the reaction, BF 3 gas is generated.
- the generated BF 3 can be absorbed in an organic solvent like diethyl ether, tetrahydrofuran, hexane, heptane, acetic acid etc. with which it can form complex.
- Ethyl difluoroacetate can be further purified by using methods such as fractional distillation.
- BF 3 gas can be regenerated from the complex and further used as intermediates of pharmaceutical and agrochemical products.
- the method of producing Ethyl difluoroacetate in high yield and high purity consists of the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- Ethoxy ethane (ETFEE), with sulphuric acid in presence of Phosphorus pentoxidefollowed by addition of ethanol. During the reaction, PF5 is generated in gaseous form. The generated PF5IS absorbed in water scrubber and further processed by methods well documented in prior art, to get high purity 85% phosphoric acid which has commercial value in pharmaceutical, agrochemical, rubber, cosmetic, speciality chemicalsand many more.
- ETFEE 1,1,2,2 -tetrafluoro-1- Ethoxy ethane
- B2O 3 or P2O5 reduces the reaction time considerably, thereby, making the process commercially advantageous. Further the use of B2O 3 or P2O5 in the reaction scheme, both being good dehydrating agents, also ensures that the reaction environment is always anhydrous and the loss of yield due to formation of hydrolysisby-product such as difluoroacetic acid is insignificant, and Ethyl difluoroacetate is produced in high yields and high purity.
- Hastelloy C -autoclave was made clean and dry with nitrogen.
- 1,1,2,2 - tetrafluoro-l-ethoxy ethane (ETFEE) 2550 gm (17.46 mol), Boron trioxide (B 2 0 3 ) having 80% purity 525 gm (6.03 mol on 100% basis), and99.5 % Ethanol 193 gm (4.19 mol) were added to the autoclave at room temperature.
- the temperature of the autoclave was slowly increased to about 50-55°C under continuous stirring at an RPM sufficient to keep the B2O 3 in complete suspension in the reaction mass.
- Purity of the product could be further increased to more than 99.5% EDFA by fractional distillation at atmospheric pressure with an overall yield of 84.5 %.
- Example 1 was repeated this time using 425 gm Boron trioxide (6.03 mol on 100% basis) and 856 gms (8.73 moles) 100% Sulfuric acid (prepared by mixing 611 gms 98% Sulphuric acid and 245 gms 105 % Oleum) all other things remaining the same as in Example l.
- the crude EDFA obtained in this example was 2040 gms having GC purity of 96.78%.
- the product yield obtained was about 91 %.
- use of 100% Sulphuric acid improved yield of EDFA due to less formation of Difluoroacetic acid.
- Example 2 was repeated with Phosphorous pentoxide (P2O5) instead of B2O 3 . 545 gmof P2O5 having 99.8% purity (3.84 mol on 100% basis) was used as reagent. All other parameters were same as in Example 2. After seventeen hours of reaction period, the ETFEE was found to be completely convertedandl990.4 gms of crude EDFA was recovered by distillation having a purity of 96.76%. The crude product yield obtained was about 88.8%and post- distillation yield of pure EDFA was 82%. PF 5 which is generated during the reaction was absorbed in water scrubber. The formation of difluoro acetic acid was less than 0.5%.
- P2O5 Phosphorous pentoxide
- the process provides ethyl difluoroacetate in high yield and high purity.
- the process does not generate toxic by-products that have no commercial value
- the process generates useful by -products of high purity that can be reused in the industry.
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Process of producing Ethyl difluoroacetateby reacting 1,1,2,2 –Tetrafluoro-1-Ethoxy Ethane with an oxide of elements selected from the groups 13 or 15 in the presence of sulphuric acid followed by the addition of an alcohol to produce ethyl difluoroacetate and a useful by-product.
Description
PROCESS OF PRODUCING ETHYL DIFLUOROACETATE
This application takes priority from two provisional applications: application number 3042/MUM/2015 titled "METHOD OF PRODUCING ETHYL DIFLUOROACETATE" dated 11th August 2015 and application number 4392/MUM/2015 titled "METHOD OF PRODUCING ETHYL DIFLUOROACETATE" dated 23rd November 2015.
Technical Field of the invention
The present invention relates generally to a process of preparing a reagent used as an intermediate for producing pharmaceutical and agrochemical products. More particularly the present invention relates to an industrially viable process of producing ethyl difluoroacetate.
Background of the invention
Ethyl difluoroacetate is an important intermediate for the production of pharmaceutical and agrochemical products. Several methods are known in the art. Journal of Organic Chemistry, 28, P-1133-4, i963reports the reaction of alpha, alpha- difluoro ethers with glass or silica gel and sulfuric acid at temperatures ranging between 70 to 160°C to give the corresponding ester and silicon tetrafluoride. /. Amer. Chem. Soc, 1950, 72, 1860 mentions the preparation of ethyl difluoroacetate with sulphuric acid in presence of siliceous material. The use of silica to scavenge HF and regenerate sulphuric acid hasbeen subsequently reported in JP 2013-147474A, which provides a method for the preparation of Ethyl difluoroacetate using 1,1,2,2-tetrafluoroethyl ether in the presence of ethanol, silica and sulphuric acid. The main drawback in all the above prior arts is the generation of toxic SiF4 gas as a by-product; besides being toxic it has limited commercial value.
JP 2008280305provides a method for the preparation of Ethyl difluoroacetate using 1 , 1 ,2,2-tetrafluoroethyl ether in the presence of ethanol, sulphuric acid and alkali metal oxide or alkaline earth metal oxide or Group 13 metal oxide. The specification mentions use of AI2O3, Ga20, Ga2(¾, Ι¾0 and !¾(¾, all of which are either amphoteric or basic metaloxides, which are easily soluble in mineral acids. The mostpreferred oxide is AI2O3, the drawback of which is lower yields and also generation of by-product which has no commercial value. US5, 710,317 describes the preparation of Ethyl difluoroacetate by reacting difluoroacetic acid fluoride with an alcohol of the formula ROH wherein R is an Ci-4 alkyl group. US20120190884 describes a method of producing Ethyl difluoroacetate that involves reacting difluoroacetyl fluoride with an aliphatic or cycloaliphatic alcohol in the presence of sodium carbonate.CN 102875379k describes a method of preparation of Ethyl difluoroacetate involving the reaction of difluoroacetamide with an alcohol in the presence of a strong acid.
All these methods known in the prior art suffer from the drawback of having to go through multiple synthesis steps, each contributing to loss of yield, rendering the process commercially unviable. Amine sulphate is generated as residue and it is also an additional cost for effluent treatment for amine recovery.
The present invention overcomes the problems in the prior art in the manufacture of Ethyl difluoroacetate and produces Ethyl difluoroacetate in high yield and purity and concomitantly generatesvaluable by-products namely BF3-etherate or high purity Phosphoric Acid which have ready commercial use.
Objects of the invention A basic object of the present invention is to overcome the disadvantages and drawbacks of the known art.
Another object of the invention is to provide an industrially viable process of producing Ethyl difluoroacetateusing metalloid oxides such as Boron trioxide which forms acidic oxide, insoluble in mineral acids. Another object of the invention is to provide an industrially viable processof producing Ethyl difluoroacetate by using Group 15 poly atomic non-metal oxides like phosphorus pentoxide.
Another object of the invention is to provide a process of producing Ethyl difluoroacetate that produces useful by-products, such as BF3-etherate or high purity Phosphoric acid.
Another object of the invention is to provide an industrially viable process of producing Ethyl difluoroacetate in high yield and high purity.
Another object of the invention is to provide an industrial viable process with significantly reduced reaction time.
These and other objects of the present invention are achieved in the preferred embodiments disclosed below.
Summary of the Invention
A process of producing ethyl difluoroacetate comprising the steps of reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE) with an oxide of elements selected from the groups 13or 15 in the presence of sulphuric acid followed by the addition of an alcohol to produce ethyl difluoroacetate and a useful by-product. According to an embodiment the process of producing ethyl difluoroacetate comprising the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy
ethane (ETFEE), boron trioxide with sulphuric acid followed by addition of ethanol to produce ethyl difluoroacetate. During the reaction, BF3 gas is generated. The generated BF3 can be absorbed in an organic solvent like diethyl ether, tetrahydrofuran, hexane, heptane, acetic acid etc. with which it can form complex.
In another embodiment the method of producing Ethyl difluoroacetate comprising the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- Ethoxy ethane (ETFEE), with sulphuric acid in presence of Phosphorus pentoxide followed by addition of ethanol. During the reaction, PF5 is generated in gaseous form. The generated PF5 is absorbed in water scrubber and further processed by methods well documented in prior art, to get high purity 85% phosphoric acid which has commercial value. A process of producing Ethyl difluoroacetate in high yield and high purity with reduced reaction times and a useful by-product.
Detailed Description of the Invention The present invention will be described with respect to preferred embodiments but the invention is not limited thereto but only by the claims.
The present invention relates to a process of producing ethyl difluoroacetate in high yield and high purity with reduced reaction times and gives useful by- products. The by products can be recovered and used in the industry.
The process of producing ethyl difluoroacetate comprises the steps of reacting the suspension of 1, 1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE) with an oxide of elements selected from the groups 13 or 15 in the presence of sulphuric acid followed by the addition of an alcohol to produce ethyl difluoroacetate and a useful by-product. The Group 13 oxide can be a metalloid oxide such as Boron
trioxide which is an acidic oxide, the Group 15 oxide is a poly atomic non-metal oxide like Phosphoruspentoxide.The alcohol can be any alcohol from the group, but preferably ethyl alcohol is used. Other alcohols (C1-C4) can also be used for the synthesis of acetate derivative. The sulphuric acid used is for obtaining high purity range of productbetween 98% to 100%. Sulphuric acid of 100% purity can be obtained by mixing 98% Sulphuric acid with 105% Oleum. The by-products obtained are non-toxic, useful byproducts can be recovered by using methods well known in the art. In one embodiment the process comprises the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy ethane (ETFEE), boron trioxide with sulphuric acid followed by addition of ethanol to produce ethyl difluoroacetate. During the reaction, BF3 gas is generated. The generated BF3 can be absorbed in an organic solvent like diethyl ether, tetrahydrofuran, hexane, heptane, acetic acid etc. with which it can form complex. Ethyl difluoroacetate can be further purified by using methods such as fractional distillation. BF3gas can be regenerated from the complex and further used as intermediates of pharmaceutical and agrochemical products. In another embodiment the method of producing Ethyl difluoroacetate in high yield and high purity consists of the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- Ethoxy ethane (ETFEE), with sulphuric acid in presence of Phosphorus pentoxidefollowed by addition of ethanol. During the reaction, PF5 is generated in gaseous form. The generated PF5IS absorbed in water scrubber and further processed by methods well documented in prior art, to get high purity 85% phosphoric acid which has commercial value in pharmaceutical, agrochemical, rubber, cosmetic, speciality chemicalsand many more.
The use of B2O3 or P2O5 reduces the reaction time considerably, thereby, making the process commercially advantageous. Further the use of B2O3 or P2O5 in the reaction scheme, both being good dehydrating agents, also ensures that the reaction environment is always anhydrous and the loss of yield due to formation
of hydrolysisby-product such as difluoroacetic acid is insignificant, and Ethyl difluoroacetate is produced in high yields and high purity.
Examples
The invention will now be illustrated with examples which are not construed to be viewed as limiting the scope of the invention.
Example-1:
5.0 lit Hastelloy C -autoclave was made clean and dry with nitrogen. 1,1,2,2 - tetrafluoro-l-ethoxy ethane (ETFEE) 2550 gm (17.46 mol), Boron trioxide (B203) having 80% purity 525 gm (6.03 mol on 100% basis), and99.5 % Ethanol 193 gm (4.19 mol) were added to the autoclave at room temperature. The temperature of the autoclave was slowly increased to about 50-55°C under continuous stirring at an RPM sufficient to keep the B2O3 in complete suspension in the reaction mass.
98% Sulphuric acid 856 gm (8.73mol) was added to the autoclave at a steady rate in about 2.0 hr by maintaining the reaction temperature at about 55°C by circulating water at -20° C through cooling coil to remove exothermic heat liberated. After completion of sulphuric acid addition the temperature of reaction mass was maintained at 55°C for further period of ten hours. Thereafter, 99.5% ethanol 290 gm(6.30 mol) was dropped in to the autoclave and the temperature was maintained at 55°C for a further period offive hours to complete the reaction.During sulphuric acid addition, BF3 gas was generated, which was absorbed in organic solvent, which was filled in another autoclave and temperature maintained at below 5°C. After completion of reaction, the residual BF3 from the reaction mass was swept out in to the absorber in to the same autoclave. The reaction mass was distilled to recover ethyl difluoroacetate (EDFA) at atmospheric pressure, andat a maximum oil bath temperature of about 130°Cand
fraction temperature of 100° C to 105° C. This was followed by vacuum distillation at 600 mm Hg absolute pressure to recover residual Ethyl difluoroacetate. 1907 gmsof crude EDFA having GC purity 98.2% was recovered. The EDFA product yield was86.43%.
Purity of the product could be further increased to more than 99.5% EDFA by fractional distillation at atmospheric pressure with an overall yield of 84.5 %.
Example-2:
Example 1 was repeated this time using 425 gm Boron trioxide (6.03 mol on 100% basis) and 856 gms (8.73 moles) 100% Sulfuric acid (prepared by mixing 611 gms 98% Sulphuric acid and 245 gms 105 % Oleum) all other things remaining the same as in Example l.The crude EDFA obtained in this example was 2040 gms having GC purity of 96.78%. The product yield obtainedwas about 91 %. In the second example use of 100% Sulphuric acid improved yield of EDFA due to less formation of Difluoroacetic acid.
Example-3:
Example 2 was repeated with Phosphorous pentoxide (P2O5) instead of B2O3. 545 gmof P2O5 having 99.8% purity (3.84 mol on 100% basis) was used as reagent. All other parameters were same as in Example 2. After seventeen hours of reaction period, the ETFEE was found to be completely convertedandl990.4 gms of crude EDFA was recovered by distillation having a purity of 96.76%. The crude product yield obtained was about 88.8%and post- distillation yield of pure EDFA was 82%. PF5 which is generated during the reaction was absorbed in water scrubber. The formation of difluoro acetic acid was less than 0.5%.
The main advantages associated with the present process are to synthesize the EDFA with low fluoride content, in higher yield, with thebyproduct generated of commercial value, mentionedas under:
The process provides ethyl difluoroacetate in high yield and high purity.
The process does not generate toxic by-products that have no commercial value
The process generates useful by -products of high purity that can be reused in the industry.
The process considerably reduces reaction times hence being increasing the economic and commercial viability of the process. The process is hence environmentally friendly The process of producing ethyl difluoroacetate as described above.The invention is capable of other embodiments and of being practiced and carried out in other ways without departing from its scope. The phrases and terminology used herein are for the purpose of description and may not be construed as being limiting. Furthermore, the foregoing description of the embodiments and the best mode of practicing are provided for the purpose of illustration only and not for the purpose of limitation, the invention being identified in the claims.
Claims
1. A process of producing ethyl difluoroacetate comprising the steps of: reacting the suspension of 1,1,2,2 -tetrafluoro-1- ethoxy ethane with an oxide of elements selected from the groups 13 or 15 in the presence of sulphuric acid followed by the addition of an alcohol to produce ethyl difluoroacetate and a useful by-product.
2. The process of producing ethyl difluoroacetate as claimed in claim 1 wherein the Group 13 oxide is Boron trioxide.
3. The process of producing ethyl difluoroacetate as claimed in claim 1 wherein the Group 15 oxide is Phosphoruspentoxide.
4. The process of producing ethyl difluoro acetate as claimed in claim 1 wherein the alcohol is ethanol or any other alcohol ROH wherein R is a Ci-4 alkyl group.
5. The process as claimed in claim 1 wherein the byproduct is a useful gas like boron triflouride or phosphorus pentaflouride.
6. The process of producing ethyl difluoroacetate as claimed in claim 5 wherein boron triflouride is recovered by absorption in an organic solvent like diethyl ether, tetrahydrofuran, hexane, heptane, acetic acid or any such solvent with which it can form a complex.
7. The process of producing ethyl difluoroacetate as claimed in claim 5 wherein phosphorus pentaflouride is absorbed in water scrubber and recovered as phosphoric acid.
8. The process of producing ethyl difluoroacetate as claimed in claim 1 wherein sulphuric acid is of purity ranging between 98% to 100%.
9. The process of producing ethyl difluoroacetate as claimed in claim 1 wherein ethyl difluoroacetate is produced in high yield and high purity.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN3042/MUM/2015 | 2015-08-11 | ||
| IN3042MU2015 | 2015-08-11 | ||
| IN4392/MUM/2015 | 2015-11-23 | ||
| IN4392MU2015 | 2015-11-23 |
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| Publication Number | Publication Date |
|---|---|
| WO2017025985A1 true WO2017025985A1 (en) | 2017-02-16 |
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| Application Number | Title | Priority Date | Filing Date |
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| PCT/IN2016/050264 WO2017025985A1 (en) | 2015-08-11 | 2016-08-08 | Process of producing ethyl difluoroacetate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008280305A (en) * | 2007-05-11 | 2008-11-20 | Daikin Ind Ltd | Method for producing fluorocarboxylic acid ester |
| WO2012011524A1 (en) * | 2010-07-23 | 2012-01-26 | ダイキン工業株式会社 | Process for producing difluoroacetic esters |
-
2016
- 2016-08-08 WO PCT/IN2016/050264 patent/WO2017025985A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008280305A (en) * | 2007-05-11 | 2008-11-20 | Daikin Ind Ltd | Method for producing fluorocarboxylic acid ester |
| WO2012011524A1 (en) * | 2010-07-23 | 2012-01-26 | ダイキン工業株式会社 | Process for producing difluoroacetic esters |
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