CA1159085A - PROCESS FOR THE PRODUCTION OF .alpha.-CHLOROACETOACETIC ACID CHLORIDE - Google Patents
PROCESS FOR THE PRODUCTION OF .alpha.-CHLOROACETOACETIC ACID CHLORIDEInfo
- Publication number
- CA1159085A CA1159085A CA000363082A CA363082A CA1159085A CA 1159085 A CA1159085 A CA 1159085A CA 000363082 A CA000363082 A CA 000363082A CA 363082 A CA363082 A CA 363082A CA 1159085 A CA1159085 A CA 1159085A
- Authority
- CA
- Canada
- Prior art keywords
- diketene
- chlorine
- inert solvent
- percent
- solvent
- 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
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
PROCESS FOR THE PRODUCTION OF
? -CHLOROACETOACETIC ACID CHLORIDE
.
ABSTRACT OF THIS INVENTION
A process for the production of ?-chloroacetoacetic acid chloride by reaction of chlorine and diketene. A solution of chlorine dissolved in an inert solvent and a solution of diketene dissolved in an inert solvent are introduced simultaneously in a continuous current into a tube reactor in such a way that the two solvents immediately mix homogeneously and a turbulent flow develops. The mole ratio of chlorine to diketene is between 0.9 to 1 and 1.2 to 1. The same inert solvent can be used for both the chlorine and diketene. Preferably a chlorinated hydrocarbon is used as the inert solvent. Preferably both the diketene and chlorine are each used in the form of a 1 to 15 percent by weight solution. Preferably a temperature which lies belows the boiling point of the solvent is maintained in the reaction tube.
? -CHLOROACETOACETIC ACID CHLORIDE
.
ABSTRACT OF THIS INVENTION
A process for the production of ?-chloroacetoacetic acid chloride by reaction of chlorine and diketene. A solution of chlorine dissolved in an inert solvent and a solution of diketene dissolved in an inert solvent are introduced simultaneously in a continuous current into a tube reactor in such a way that the two solvents immediately mix homogeneously and a turbulent flow develops. The mole ratio of chlorine to diketene is between 0.9 to 1 and 1.2 to 1. The same inert solvent can be used for both the chlorine and diketene. Preferably a chlorinated hydrocarbon is used as the inert solvent. Preferably both the diketene and chlorine are each used in the form of a 1 to 15 percent by weight solution. Preferably a temperature which lies belows the boiling point of the solvent is maintained in the reaction tube.
Description
BACK&ROUND OF THIS INVENTION
1. Field Of This Invention This invention relates to the production of ~-chloroaceto-acetic acid chloride from chlorine and diketene.
1. Field Of This Invention This invention relates to the production of ~-chloroaceto-acetic acid chloride from chlorine and diketene.
2. Prior Art _.~
The production of ~-chloroacetoacetic acid chloride from chlorine gas and diketene is known. The reaction takes place exothermally and therefore requires a large amount of cooling.
Undesirable o~-chloroacetoacetic acid chloride develops, especial-ly when the reaction proceeds too slowly. According to the Japanese Patent Publication No. 113,824 (1976), such disadvantages are supposedly avoided when dissolved diketene is allowed to flow downwardly in a column reaction vessel at the same time diluted chlo~ine gas is fed into it in a continuous current or counter-current manner. However, the process merely leads to selectivities of less than 90 percent. In addition, the monetary expenditure for space and production for such column reaction vessels is undesirably high. Also the capacity of such column reaction v0ssels is very low because of the relatively small exchange surface and the small flow velocities.
BROAD DESCRIPTION OF THIS INVENTIO N
An object of this invention is to provide a process which avoids the above-mentioned disadvantages and problems. Ano-ther object of this invention is to provide a process which tends to avoid the formation o~ undesirable byproducts. A further object of this invention is to provide a process which has high reaction selectivity, allows high throughput of reaction and is highly quantitative in reaction. ~nothex object of -this invention is to provide a process which allows the use of a small ~0 reactor. Other objects and advantages of this invention are set out herein or are obvious herefrom to one ordinarily skilled in the art. The objects and advantages of this invention are achieved by the process of this invention.
This invention involves a process for the production of y-chloroacetoacetic acid chloride by reaction of chlorine and diketene. In the pxocess, a solution of chlorine dissolved in an inert solvent and a solution of diketene dissolved in an inert ; solyent are simultaneously introduced into a tube reactor in a continuous current in such a manner that the two solvents 20 immediately mix homogeneously and a turbulent flow develops. The molar ratio of chlorine to diketene is between 0.9 to 1 and 1.2 to 1. Preferably the same inert solvent is used for both of the chlorine and diketene solutions. Preferably a chlorinated hydro-carbon .is used as the inert solvent. ~ost preferably methylene chloride is used as the inert solvent. Preferably the chlorine is used in the form of a 1 to 15 percent by weight solution.
Pxeferably the diketene is used in the form of a 1 to 15 percent ' by weight solution. Also, pre~erably a temperature which lies below the boiling point of the insert solvent is maintained in the reaction tube.
The process is carried out by dissolving the diketene in an inert solvent, Preferably the solvent is a chlorinated hydro-carbon, such as, dichloroethane, dichlorop:ropane, l-chloro-2-fluoroethane, l,l-dichloroethane, 1,2-dichloroethane, methyl chloroform, l-chlorobutane, 2-chlorobutane, l-bromobutane t eth.yl bromide, l-bromo-2-chloroethane, ethyl chloride, l-bromo-2-fluoroethane, l-iodobutane, bromochloromethane, :~ibromomethane, l,l-dibromoethane, difluoroiodomethane, l-bromopropane, bromo-chlorofluoromethane, 2-bromopropane, bromodichloromethane, ;~
bromofluoromethane/ bromotrichloromethane, dibromodifluoromethane, pentachloromethane, l,1,1,2-tetrachloroethane, fluoroiodomethane, i~domethane,.diiodofluoromethane, 1,1,2,2-tetrachloromethane, 1,1,2~trichloroethane, l-chloropropane, 1~2-dibromopropane, 1,~,3-trichloropropane, 1,1,1,2-t~trachloropropane, carbon tetrachloride and chloroform. Most preferably the inert solvent is methylene chLori~e (dichloromethane). Preferably the concen-tration of diketene is 1 to 15 percent by weight in the solvent.
P.referably the chlorine is dissolved in an inert solvent to a concentration of 1 to 15 percent by weight. The inert solvent used to dissolve the chlorine is preferably a chlorinated hydro-carbon and is most preferably methylene chloride. ~lso r pre-Eerably the same solvent is used to ~separately) dissolve the chlorine~ and the diketene.
',''',' .
. , .
~ . ~ ,......... .
The two dissolved components are simultaneously inserted in a continuous and cocurrent manner into a reaction tube. The reaction starts spon~aneously. At the same time, a gas phase is not necessary nor does such a gas phase develop during the process. As compared to known processes, the required reaction space can be kept small since gas does not form and no gas phase is needed. Also, as a result, expensive processing of exhaust gas is avoided. The reaction tube is dimensioned, corresponding to the quantity (rate) of the produc~ that is to be produced, in SUC}l a manner that a turbulent flow develops in the reaction tube as a result of the (partial) streams of the educts. The turbulent flow achieved in the process of this invention is defined by a Reynolds number higher than 2,500 and preferably between 5,000 and 20,000. Within the scope of this invention a bundle oF tube reactors can be used, provided that they are also dimensioned so that formation of a turbulent flow is achieved.
The reaction tube is cooled from the outside, preferably by means of brine cooling. The cooling is dimensioned such that the reaction temperature is maintained below the boiling point , ~ of the solvent.
The dissolved educts for their part are introduced into the reactor at ambient temperature. In view o~ the cooling capacity of the apparatus, operation can also be done with precooled educts, for example, as low as ~30C.
The reaction which takes place in the reaction tube is almost quantitative - as a result, in relation to the reactor volume, high throughputs are achieved. In the process of this invention, selectivities of over 98 percent are achieved. It is obvious that as a result of such high selectivities, there is only trace ~0 formation of undesirable byproducts, such as ~, ~ -dichloroaceto-acetic acid chloride, The ~-chloroacetoacetic acid chloride is separated by distillative separation, especially from the solvent from the reaction mixture. But the ~-chloroacetoacetic acid chloride can be le~t in the inert solvent and then reacted as a reaction mixture, ~or example, by allowing an alcohol, phenol, amine or aniline to flow therein to form the corresponding ester, amide or anilide. By distillative separation o~ the solvent, the compounds are obtained in a pure ~orm. The distilled solvent, ~reed o~ accompanying substances, can be fed back to the 1~ reaction process ~or use again therein.
By way oE summary, ~-chloroacetoacetic acid chloride is produced ~rom chlorine and diketene. The two starting products are separately dissolved in an inert solvent and are continuously conducted into a tube reactor in a continuous cocurren-t manner.
The two starting components must immediately be homogeneously mixed and turbulent flow must immediately occur in the tube reactor. When a small reactor volume is used, high yield and selectivity o~ ~-chloroacetoacetic acid chloride results. The products can be reacted in a known manner into ~-chloroaceto-cetic acid ester ` ~, .`
~591t~
DETAILED DESCRIPTIO~ OF THIS INVENTION
~ s used herein, all percentages and ratios are on a welghtbasis unless otherwise stated herein or otherwise obvious herefrom to one ordinarily skilled in the art.
A reaction tube, having a 1 m length and a hydraulic-lnside diameter of 2 mm, was mounted horizontally. While the tube was cooled from the outside with brine of -20C., the two reactants (in solution form) were fed to the reaction tube in a contin-uou5 cocurrent manner. The requisite turbulant flow was ~ ~
achieved and maintained in the reaction tube. The diketene solu-tion consisted of 84 g of diketene (1 mole) and 1.5 liter o methylene chloriae; and the chlorine solution consisted of 76 g of chlorine (1.07 mole~ and 1.5 liter of methylene chloride. The two solutions were dosed`into the tube such that a flow velocity of 1 m/s developed in the tube.
21C. was the highest temperature measured in the reaction medium. U~on emergence from the reactor, the reaction solution had a temperature of 2C. The solution emer~ing to the reactor, was taken and cooled to -15C. The ~-chloroacetoacetic acid chloride product was reacted with an equimolar quantity of ethyl alcohol to form ~-chloroacetoacetic ethyl ester. Follow-ing such, the excess chlorine, as well as the methylene chloride, was removed by distilling it off. Gas chromatographic analysis of the crude ~-chloroacetoacetic ethyl ester showed a content of 9~.1 percent thereo (plus 0.~ percent oE acetoacetic ester, zero p~rcent of ~ -chloroacetoacetic ester and 0.3 percent of ~, ~ -dichIoroacetoacetic ester).
L5~
EX~PLE 2 Example 1 was repeated, however, ~2g of diketene~per 1.5 liter of methylene chloride and 38 g of chlorine per 1.5 liter of methylene chloride were used. A flow velocity of 1.66 m/s occurred in the tu~e reactor. Analysis oE the crude ~-chloroacetoaceticethyl ester showed a content of 96.8 percent thereof.
EXA~PLE 3 Example 1 was repeated, however~ 168 g of diketene per 1.5 liter of methylene chloride and 152 g of chlorine per l.5 liter of methylene chloride were used. A flow velocity of 0.5 m/s occurred in the tube reactor. The content of the crude -chloroacetoaceticethyl ester was 89.1 percent.
A tubç, having a 3 m length and a hydraulic-inside diameter of-4 mm, was used as the reactor. The tube was mounted vertically and was cooled with brine of -10C. The solutions were fed, in a continuous cocurrent manner, into the head of the reactor. The solutions had the same concentrations as those in Example 3.
The flow velocity however was 0.75 m/s. The highest temperature occurring in the reaction medium was 45~. Analysis of the ~ -chloroacetoaceticethyl ester showed a content of 9~.8 per-cent.
PX~MP~S
Example 4 was repeated, however, ~4 g o~ diketene per 1.5 liter of methylene chloride and 76 g of chlorine per 1.5 liter of methylene chloride were used. The flow velocity was 1 m/s.
The content of the crude ~ -chloroacetoaceticethyl ester was 95.3 percent (i.e , ester in the crude mixture).
The production of ~-chloroacetoacetic acid chloride from chlorine gas and diketene is known. The reaction takes place exothermally and therefore requires a large amount of cooling.
Undesirable o~-chloroacetoacetic acid chloride develops, especial-ly when the reaction proceeds too slowly. According to the Japanese Patent Publication No. 113,824 (1976), such disadvantages are supposedly avoided when dissolved diketene is allowed to flow downwardly in a column reaction vessel at the same time diluted chlo~ine gas is fed into it in a continuous current or counter-current manner. However, the process merely leads to selectivities of less than 90 percent. In addition, the monetary expenditure for space and production for such column reaction vessels is undesirably high. Also the capacity of such column reaction v0ssels is very low because of the relatively small exchange surface and the small flow velocities.
BROAD DESCRIPTION OF THIS INVENTIO N
An object of this invention is to provide a process which avoids the above-mentioned disadvantages and problems. Ano-ther object of this invention is to provide a process which tends to avoid the formation o~ undesirable byproducts. A further object of this invention is to provide a process which has high reaction selectivity, allows high throughput of reaction and is highly quantitative in reaction. ~nothex object of -this invention is to provide a process which allows the use of a small ~0 reactor. Other objects and advantages of this invention are set out herein or are obvious herefrom to one ordinarily skilled in the art. The objects and advantages of this invention are achieved by the process of this invention.
This invention involves a process for the production of y-chloroacetoacetic acid chloride by reaction of chlorine and diketene. In the pxocess, a solution of chlorine dissolved in an inert solvent and a solution of diketene dissolved in an inert ; solyent are simultaneously introduced into a tube reactor in a continuous current in such a manner that the two solvents 20 immediately mix homogeneously and a turbulent flow develops. The molar ratio of chlorine to diketene is between 0.9 to 1 and 1.2 to 1. Preferably the same inert solvent is used for both of the chlorine and diketene solutions. Preferably a chlorinated hydro-carbon .is used as the inert solvent. ~ost preferably methylene chloride is used as the inert solvent. Preferably the chlorine is used in the form of a 1 to 15 percent by weight solution.
Pxeferably the diketene is used in the form of a 1 to 15 percent ' by weight solution. Also, pre~erably a temperature which lies below the boiling point of the insert solvent is maintained in the reaction tube.
The process is carried out by dissolving the diketene in an inert solvent, Preferably the solvent is a chlorinated hydro-carbon, such as, dichloroethane, dichlorop:ropane, l-chloro-2-fluoroethane, l,l-dichloroethane, 1,2-dichloroethane, methyl chloroform, l-chlorobutane, 2-chlorobutane, l-bromobutane t eth.yl bromide, l-bromo-2-chloroethane, ethyl chloride, l-bromo-2-fluoroethane, l-iodobutane, bromochloromethane, :~ibromomethane, l,l-dibromoethane, difluoroiodomethane, l-bromopropane, bromo-chlorofluoromethane, 2-bromopropane, bromodichloromethane, ;~
bromofluoromethane/ bromotrichloromethane, dibromodifluoromethane, pentachloromethane, l,1,1,2-tetrachloroethane, fluoroiodomethane, i~domethane,.diiodofluoromethane, 1,1,2,2-tetrachloromethane, 1,1,2~trichloroethane, l-chloropropane, 1~2-dibromopropane, 1,~,3-trichloropropane, 1,1,1,2-t~trachloropropane, carbon tetrachloride and chloroform. Most preferably the inert solvent is methylene chLori~e (dichloromethane). Preferably the concen-tration of diketene is 1 to 15 percent by weight in the solvent.
P.referably the chlorine is dissolved in an inert solvent to a concentration of 1 to 15 percent by weight. The inert solvent used to dissolve the chlorine is preferably a chlorinated hydro-carbon and is most preferably methylene chloride. ~lso r pre-Eerably the same solvent is used to ~separately) dissolve the chlorine~ and the diketene.
',''',' .
. , .
~ . ~ ,......... .
The two dissolved components are simultaneously inserted in a continuous and cocurrent manner into a reaction tube. The reaction starts spon~aneously. At the same time, a gas phase is not necessary nor does such a gas phase develop during the process. As compared to known processes, the required reaction space can be kept small since gas does not form and no gas phase is needed. Also, as a result, expensive processing of exhaust gas is avoided. The reaction tube is dimensioned, corresponding to the quantity (rate) of the produc~ that is to be produced, in SUC}l a manner that a turbulent flow develops in the reaction tube as a result of the (partial) streams of the educts. The turbulent flow achieved in the process of this invention is defined by a Reynolds number higher than 2,500 and preferably between 5,000 and 20,000. Within the scope of this invention a bundle oF tube reactors can be used, provided that they are also dimensioned so that formation of a turbulent flow is achieved.
The reaction tube is cooled from the outside, preferably by means of brine cooling. The cooling is dimensioned such that the reaction temperature is maintained below the boiling point , ~ of the solvent.
The dissolved educts for their part are introduced into the reactor at ambient temperature. In view o~ the cooling capacity of the apparatus, operation can also be done with precooled educts, for example, as low as ~30C.
The reaction which takes place in the reaction tube is almost quantitative - as a result, in relation to the reactor volume, high throughputs are achieved. In the process of this invention, selectivities of over 98 percent are achieved. It is obvious that as a result of such high selectivities, there is only trace ~0 formation of undesirable byproducts, such as ~, ~ -dichloroaceto-acetic acid chloride, The ~-chloroacetoacetic acid chloride is separated by distillative separation, especially from the solvent from the reaction mixture. But the ~-chloroacetoacetic acid chloride can be le~t in the inert solvent and then reacted as a reaction mixture, ~or example, by allowing an alcohol, phenol, amine or aniline to flow therein to form the corresponding ester, amide or anilide. By distillative separation o~ the solvent, the compounds are obtained in a pure ~orm. The distilled solvent, ~reed o~ accompanying substances, can be fed back to the 1~ reaction process ~or use again therein.
By way oE summary, ~-chloroacetoacetic acid chloride is produced ~rom chlorine and diketene. The two starting products are separately dissolved in an inert solvent and are continuously conducted into a tube reactor in a continuous cocurren-t manner.
The two starting components must immediately be homogeneously mixed and turbulent flow must immediately occur in the tube reactor. When a small reactor volume is used, high yield and selectivity o~ ~-chloroacetoacetic acid chloride results. The products can be reacted in a known manner into ~-chloroaceto-cetic acid ester ` ~, .`
~591t~
DETAILED DESCRIPTIO~ OF THIS INVENTION
~ s used herein, all percentages and ratios are on a welghtbasis unless otherwise stated herein or otherwise obvious herefrom to one ordinarily skilled in the art.
A reaction tube, having a 1 m length and a hydraulic-lnside diameter of 2 mm, was mounted horizontally. While the tube was cooled from the outside with brine of -20C., the two reactants (in solution form) were fed to the reaction tube in a contin-uou5 cocurrent manner. The requisite turbulant flow was ~ ~
achieved and maintained in the reaction tube. The diketene solu-tion consisted of 84 g of diketene (1 mole) and 1.5 liter o methylene chloriae; and the chlorine solution consisted of 76 g of chlorine (1.07 mole~ and 1.5 liter of methylene chloride. The two solutions were dosed`into the tube such that a flow velocity of 1 m/s developed in the tube.
21C. was the highest temperature measured in the reaction medium. U~on emergence from the reactor, the reaction solution had a temperature of 2C. The solution emer~ing to the reactor, was taken and cooled to -15C. The ~-chloroacetoacetic acid chloride product was reacted with an equimolar quantity of ethyl alcohol to form ~-chloroacetoacetic ethyl ester. Follow-ing such, the excess chlorine, as well as the methylene chloride, was removed by distilling it off. Gas chromatographic analysis of the crude ~-chloroacetoacetic ethyl ester showed a content of 9~.1 percent thereo (plus 0.~ percent oE acetoacetic ester, zero p~rcent of ~ -chloroacetoacetic ester and 0.3 percent of ~, ~ -dichIoroacetoacetic ester).
L5~
EX~PLE 2 Example 1 was repeated, however, ~2g of diketene~per 1.5 liter of methylene chloride and 38 g of chlorine per 1.5 liter of methylene chloride were used. A flow velocity of 1.66 m/s occurred in the tu~e reactor. Analysis oE the crude ~-chloroacetoaceticethyl ester showed a content of 96.8 percent thereof.
EXA~PLE 3 Example 1 was repeated, however~ 168 g of diketene per 1.5 liter of methylene chloride and 152 g of chlorine per l.5 liter of methylene chloride were used. A flow velocity of 0.5 m/s occurred in the tube reactor. The content of the crude -chloroacetoaceticethyl ester was 89.1 percent.
A tubç, having a 3 m length and a hydraulic-inside diameter of-4 mm, was used as the reactor. The tube was mounted vertically and was cooled with brine of -10C. The solutions were fed, in a continuous cocurrent manner, into the head of the reactor. The solutions had the same concentrations as those in Example 3.
The flow velocity however was 0.75 m/s. The highest temperature occurring in the reaction medium was 45~. Analysis of the ~ -chloroacetoaceticethyl ester showed a content of 9~.8 per-cent.
PX~MP~S
Example 4 was repeated, however, ~4 g o~ diketene per 1.5 liter of methylene chloride and 76 g of chlorine per 1.5 liter of methylene chloride were used. The flow velocity was 1 m/s.
The content of the crude ~ -chloroacetoaceticethyl ester was 95.3 percent (i.e , ester in the crude mixture).
Claims (17)
1. Process for the production of ? -chloroacetoacetic acid chloride by reacting chlorine and diketene, characterized in that a solution of chlorine dissolved in an inert solvent and a solution of diketene dissolved in an inert solvent are simultaneously and continuously introduced in a continuous co-current manner into a tube reactor in such a way that the two solutions immediately mix homogeneously and a turbulent flow develops, the mole ratio of chlorine to diketene being between 0.9 to 1 and 1.2 to 1.
2. Process as claimed in Claim 1 wherein the same inert solvent is used to separately dissolve the chlorine and the diketene.
3. Process as claimed in Claim 2 wherein the inert solvent is a chlorinated hydrocarbon.
4. Process as claimed in Claim 3 wherein the inert solvent is methylene chloride.
5. Process as claimed in Claim 3 wherein the chlorine solution contains 1 to 15 percent by weight of chlorine.
6. Process as claimed in Claim 5 wherein the diketene solution contains 1 to 15 percent by weight of diketene.
7. Process as claimed in Claim 6 wherein a temperature, which lies below the boiling point of the solvent, is maintained in the reaction tube.
8. Process as claimed in Claim 7 wherein the turbulent flow in the tube reactor has a Reynolds number of at least 2,500.
9. Process as claimed in Claim 8 wherein the Reynolds number is between 5,000 and 20,000.
10. Process as claimed in Claim 1 wherein each of the inert solvents is a chlorinated hydrocarbon.
11. Process as claimed in Claim 1 wherein the chlorine solution contains 1 to 15 percent by weight of chlorine.
12. Process as claimed in Claim 1 wherein the diketene solution contains 1 to 15 percent by weight of diketene,
13. Process as claimed in Claim 1 wherein a tempera-ture, which lies below the boiling point of the solvent, is maintained in the reaction tube.
14. Process as claimed in Claim 1 wherein the turbulent flow in the tube reactor has a Reynolds number of at least 2,500.
15. Process as claimed in Claim 14 wherein the Reynolds number is between 5,000 and 20,000.
16. Process as claimed in Claim 1 where the chlorine solution contains 1 to 15 percent by weight of chlorine and the diketene solution contains 1 to 15 percent by weight of diketene.
17. Process as claimed in Claim 16 wherein methylene chloride is used as the inert solvent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH9803/79 | 1979-11-01 | ||
| CH980379A CH642611A5 (en) | 1979-11-01 | 1979-11-01 | METHOD FOR PRODUCING GAMMA-chloroacetoacetic. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1159085A true CA1159085A (en) | 1983-12-20 |
Family
ID=4355809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000363082A Expired CA1159085A (en) | 1979-11-01 | 1980-10-23 | PROCESS FOR THE PRODUCTION OF .alpha.-CHLOROACETOACETIC ACID CHLORIDE |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0028709B1 (en) |
| JP (1) | JPS5675454A (en) |
| AR (1) | AR223902A1 (en) |
| AT (1) | ATE17712T1 (en) |
| BR (1) | BR8006943A (en) |
| CA (1) | CA1159085A (en) |
| CH (1) | CH642611A5 (en) |
| CS (1) | CS215076B2 (en) |
| DD (1) | DD153825A5 (en) |
| DE (1) | DE3071396D1 (en) |
| ES (1) | ES8107144A1 (en) |
| HU (1) | HU185915B (en) |
| MX (1) | MX155608A (en) |
| PL (1) | PL126702B1 (en) |
| ZA (1) | ZA806349B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6025955A (en) * | 1983-07-22 | 1985-02-08 | Nippon Synthetic Chem Ind Co Ltd:The | Production of gamma-chloroacetoacetic acid ester |
| CH666483A5 (en) * | 1985-01-16 | 1988-07-29 | Lonza Ag | PROCESS FOR THE PREPARATION OF THIOTETRONIC ACID. |
| CH667655A5 (en) * | 1986-09-24 | 1988-10-31 | Lonza Ag | METHOD FOR PRODUCING 4-ALKOXY-2 (5H) THIOPHENONES. |
| US5258523A (en) * | 1991-06-28 | 1993-11-02 | Lonza Ltd. | Process for the production of 2-aryl-2H-1,2,3-triazoles |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3950412A (en) * | 1971-06-08 | 1976-04-13 | Lonza Ltd. | Method for the production of haloacetoacetic acids |
| US3769338A (en) * | 1971-11-09 | 1973-10-30 | Ethyl Corp | Process for synthesizing citric acid |
| JPS4936210A (en) * | 1972-08-04 | 1974-04-04 | ||
| JPS5823373B2 (en) * | 1975-03-27 | 1983-05-14 | 日本合成化学工業株式会社 | Gamma - Chloracetosaxane chloride |
-
1979
- 1979-11-01 CH CH980379A patent/CH642611A5/en not_active IP Right Cessation
-
1980
- 1980-10-08 AT AT80106117T patent/ATE17712T1/en not_active IP Right Cessation
- 1980-10-08 EP EP80106117A patent/EP0028709B1/en not_active Expired
- 1980-10-08 DE DE8080106117T patent/DE3071396D1/en not_active Expired
- 1980-10-15 ZA ZA00806349A patent/ZA806349B/en unknown
- 1980-10-23 CA CA000363082A patent/CA1159085A/en not_active Expired
- 1980-10-28 JP JP15024480A patent/JPS5675454A/en active Granted
- 1980-10-29 BR BR8006943A patent/BR8006943A/en not_active IP Right Cessation
- 1980-10-29 CS CS807319A patent/CS215076B2/en unknown
- 1980-10-30 DD DD80224838A patent/DD153825A5/en not_active IP Right Cessation
- 1980-10-30 MX MX184562A patent/MX155608A/en unknown
- 1980-10-31 HU HU802635A patent/HU185915B/en not_active IP Right Cessation
- 1980-10-31 AR AR283087A patent/AR223902A1/en active
- 1980-10-31 PL PL1980227594A patent/PL126702B1/en unknown
- 1980-10-31 ES ES496428A patent/ES8107144A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| EP0028709B1 (en) | 1986-01-29 |
| ES496428A0 (en) | 1981-10-01 |
| ZA806349B (en) | 1981-10-28 |
| BR8006943A (en) | 1981-05-05 |
| EP0028709A1 (en) | 1981-05-20 |
| DD153825A5 (en) | 1982-02-03 |
| ATE17712T1 (en) | 1986-02-15 |
| PL126702B1 (en) | 1983-08-31 |
| PL227594A1 (en) | 1981-06-19 |
| ES8107144A1 (en) | 1981-10-01 |
| JPS5675454A (en) | 1981-06-22 |
| CS215076B2 (en) | 1982-07-30 |
| DE3071396D1 (en) | 1986-03-13 |
| AR223902A1 (en) | 1981-09-30 |
| CH642611A5 (en) | 1984-04-30 |
| HU185915B (en) | 1985-04-28 |
| MX155608A (en) | 1988-04-06 |
| JPH0244825B2 (en) | 1990-10-05 |
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