CA1231347A - Process for the preparation of 2-chloropropionic acid - Google Patents
Process for the preparation of 2-chloropropionic acidInfo
- Publication number
- CA1231347A CA1231347A CA000484369A CA484369A CA1231347A CA 1231347 A CA1231347 A CA 1231347A CA 000484369 A CA000484369 A CA 000484369A CA 484369 A CA484369 A CA 484369A CA 1231347 A CA1231347 A CA 1231347A
- Authority
- CA
- Canada
- Prior art keywords
- acid
- prop ionic
- prop
- chlorination
- light
- 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
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Abstract of the disclosure:
2-Chloropropionic acid is prepared in a high yield and purity by chlorinating propionic acid in the presence of propionic anhydride as the sole additive and with the exclusion of free radical-formers and light, at tempera-tures between about 115 and 140°C. The reaction product is a valuable intermediate in a variety of fields.
2-Chloropropionic acid is prepared in a high yield and purity by chlorinating propionic acid in the presence of propionic anhydride as the sole additive and with the exclusion of free radical-formers and light, at tempera-tures between about 115 and 140°C. The reaction product is a valuable intermediate in a variety of fields.
Description
lo
- 2 -2-Chloropropionic acid, CH3cHclcooH~ is a valuable intermediate, in particular or the preparation of plant protection agents, pharmaceuticals and distaffs.
It is known to prepare 2-chloropropionic acid by 5 chlorinating prop ionic acid at 110 to 120C in the pro-since of catalysts; the catalysts used are in the main, P-containing and S-containing compounds (PCl3, Scholl Claus, etc.) and others but also propionyl chloride tcf. Ullmanns Encyclopedia don technician Chemise Columns Encyclopedia of Industrial Chemistry Thea Edition, Volume 19 t1980), pages 457/458).
If desired, it is also possible to add prop ionic android to the propionyl chloride catalyst British Patent No. 892~58~). Temperatures between 100 and 110C
are indicated in the British patent for the monochlorina-lion ox prop ionic acid. D;chlor;nat;on to give 2~2~
dichloropropionic acid is stated to take place at a higher temperature (15û to 160C).
The British patent mentioned above also contains a suggested mechanism for the chlorination of prop ionic acid in the piston. According to thus the reaction is stated to take place via tauto0eric propionyl chloride in accordance with the following scheme of reactions for the monochlorinat;on):
~3~3 Of CH3-CH2-COCl CH3-CH=C
I
l~C12 Jo CH3~CH-C\
C 1 OH Of 1 -Hal CH3_CHCl-COCl 1 CH3-cH2-cooH
CH3_CHCl_COoH CH3-CH2-COCl If it is intended to chlorinate prop;on;c acid in the Z~posit;onO free radical former and light should be excluded as far as possible, since chlorination under radical-form;ng conditions takes place mainly in the 3-position with the formation of 3-chLoroprop10nic acid, CH2Cl-CH2 KIWI
According to the investigations of Y. Ogata and K. Matsuyama on the effect of catalysts on the chlorine-lion of prop ionic acid of Tetrahedron, VoLulne 26 ~1970 pages 5~29-5937), the tautomeric form of prop ionic acid itself can be a possible intermediate product for the chlorination of prop ionic acid in the 2-position:
OH
CH3-CH2 COO = CH3-CH=C
OH
The authors also describe exponents on the moo-chlorination of prop ionic acid at 110C inter aria using Jo prop;on;c android as the sole catalyst for a reaction time of 3 hours (see Table 2 on page 5931)~ In the presence of 4 Sol X of prop ionic android relative to the starting prop ionic acid), the reaction product is stated to have contained 2-chloropropionic acid ted") in a ratio of 0.38 to ~-chloropropion;c acid to sheller prop ionic acid ("I
In the presence of 17 mow X of prop ionic ashy-drive, the ratio ~/~ + is stated to have been 0.71.
In our own experiments on the monochlorination of prop ionic acid at about 110C on the presence of 8 mow X of prop ionic android at a reaction time of 15 hours, an ~/~ Jo ratio of 0.76 was obtained without exclusion of light and an ~/~ ratio of 0.92 was obtained with the exclusion of light.
The feasibility of chlorinating prop ionic acid in the presence of prop ionic android us also mentioned in the earlier British Patent No. 621,531; the patent -which relates primarily to the chlorination of acetic 20 acid - does not, however, contain more precise details on this matter. The temperature range indicated for the chlorination of acetic acid (in the presence of acetic android or acutely chloride) is 100 to 110C~
The known processes for the preparation of 2-25 chloropropionic acid are not entirely satisfactory inverse respects If, for instance, phosphorus and sulfur compounds are used as catalysts sparingly soluble P-containing or Containing resinous products are wormed in some cases and make relatively frequent and expensive cleaning of the chlorination apparatus necessary; in the continuous process this can result in frequent plant interruptions. In addition, the P-contain;ng and S-containing residues must also be worked up in a manner which does not pollute the environment. Finally small quantities of P-compounds or S-compounds also frequently get into the 2-chloropropionic acid prepared by these processes, and these impair the quality of the 2-chloropropionic acid It is a disadvantage in the use of propionyl ~3~3~
chloride (boiling point 80C) as a catalyst that this come pound us, at least partially, readily stropped out at the chlorination temperature by the hydrogen chloride which us formed, and thus us lacking during the reaction, or S contaminates the hydrogen chloride and makes the reuse of the latter more difficult.
If prop;on;c android is used as the catalyst, particularly as evidenced by the experiments of Y. Ogata and K. Matsuyama, the ~/~ ~13 ratio at 110C us on any case not adequate for fairly high industrial requirements;
according to the same literature reference, higher tempera-lures promote the free radical mechanism and hence the formation of 3-chloroprop;on;c acid, which makes a fur-then reduction on the I 3 ratio likely.
it was therefore required to find an improved process for the preparation of 2-chloropropion;c acid.
It has been possible to achieve this object in accordance with the invention by chlorinating prop;onic acid on the presence of prop;onic android as the sole catalyst or adoptive Lowe avoiding free rad;cal-forming conditions at temperatures which are above the tempera-lures (about 110C~ hitherto used for the chlorination of prop ionic acid to give 2-chloropropionic acid in the presence of prop ionic android.
The invention relates, therefore, to a process for the preparation of 2-chloropropionic acid by chlorinate in prop ionic acid in the presence of propion;c android at an elevated temperature, Chile excluding free radical former and light, which comprises carrying out the chlorination without 3 further additive at temperatures between about 115 and about 140C~ Temperatures between about 120 and about 135C, on particular between about 125 and 135C, are preferred.
At these higher temperatures yields of over 90%
of theory of 2-chloroprop;onic acid are obtained at high to quantitative conversions and at an I I ratio which is consistently between about 0.99 and I
Thus result was extremely surprising, since, at higher temperatures, as a result of the formation of free ~3~3~
o radicals being promoted by an increase in the temperature, it would rather have been necessary to expect an increase in the proportion of 3-chloropropionic acid which is undesirable on this case and Shea is formed prefer en-tidally when prop ionic acid is chlorinated under con-doughtiness which form free radicals) and hence a lower I ratio.
The amount of prop ionic android added in accord-ante with the process according to the invention is generally between about 3 and about 30 mow %, preferably between about S and about 20 mow X, relative to the start-ivy prop ionic acid. It is possible to add higher amounts, but this affords no advantage. Other catalysts and/or additives should not be used concomitantly in the process.
In addition, care should also be taken that free radical-former and light remain excluded.
In other respects the process is carried out on the customary manner with the exclusion of light in equipment suitable for chlorination reactions Either a discontinuous procedure or a continuous procedure us possible The process can also be carried out either under normal pressure or under an excess pressure, the procedure under normal pressure being preferred.
The chlorine used for the chlorination can be diluted with gases which are inert towards the starting substances and final products of the reaction, such as for example, nitrogen or hydrogen chloride.
It is also possible to use inert solvents, such as, for example chlorinated hydrocarbons (chlorobenzene etch The invention represents a considerable advance because of the high yield achieved in the process accord-in to the invention, and the purity of the sheller-prop ionic acid, and also because of the avoidance of catalysts Shea are difficult to remove and also because, owing to its relatively high boiling point, the catalyst used in this case cannot be stripped out for instance as readily as, for example, propionyl chloride by the hydra gun chloride which is formed.
I
The Examples which follow serve to illustrate the invention in greater detail. The Examples of the oven lion (A) are followed by two comparison examples (B), Shea were carried out at about 110C, with and without the exclusion of light analogously to the tests of Y. gut and K. Matsuyama (foe. cit.).
A) Examples of the invention:
370 g (= 5 moles) of prop ionic acid and 104 g t- 0.8 mole - 16 mow X, relative to the prop ionic acid) of prop ionic android were heated to about 130C on a alter reactor, equipped with a reflex condenser, a stirrer, a thermometer and a gas inlet tube. 470 g of chlorine (= 6.62 moles) were then passed in with the exclusion of light in the course of 20 hours. A yield of 691 g was obtained after the hydrogen chloride had been blown out with nitrogen.
Analysis by gas chromatography gave the fulling result (after saponification with water, in order to con-vent residual chlorinated prop ionic android unto sheller prop ionic acid):
Prop ionic acid: 1.3X
2-Chloropropion;c acid ~"~"): 97O5X
It is known to prepare 2-chloropropionic acid by 5 chlorinating prop ionic acid at 110 to 120C in the pro-since of catalysts; the catalysts used are in the main, P-containing and S-containing compounds (PCl3, Scholl Claus, etc.) and others but also propionyl chloride tcf. Ullmanns Encyclopedia don technician Chemise Columns Encyclopedia of Industrial Chemistry Thea Edition, Volume 19 t1980), pages 457/458).
If desired, it is also possible to add prop ionic android to the propionyl chloride catalyst British Patent No. 892~58~). Temperatures between 100 and 110C
are indicated in the British patent for the monochlorina-lion ox prop ionic acid. D;chlor;nat;on to give 2~2~
dichloropropionic acid is stated to take place at a higher temperature (15û to 160C).
The British patent mentioned above also contains a suggested mechanism for the chlorination of prop ionic acid in the piston. According to thus the reaction is stated to take place via tauto0eric propionyl chloride in accordance with the following scheme of reactions for the monochlorinat;on):
~3~3 Of CH3-CH2-COCl CH3-CH=C
I
l~C12 Jo CH3~CH-C\
C 1 OH Of 1 -Hal CH3_CHCl-COCl 1 CH3-cH2-cooH
CH3_CHCl_COoH CH3-CH2-COCl If it is intended to chlorinate prop;on;c acid in the Z~posit;onO free radical former and light should be excluded as far as possible, since chlorination under radical-form;ng conditions takes place mainly in the 3-position with the formation of 3-chLoroprop10nic acid, CH2Cl-CH2 KIWI
According to the investigations of Y. Ogata and K. Matsuyama on the effect of catalysts on the chlorine-lion of prop ionic acid of Tetrahedron, VoLulne 26 ~1970 pages 5~29-5937), the tautomeric form of prop ionic acid itself can be a possible intermediate product for the chlorination of prop ionic acid in the 2-position:
OH
CH3-CH2 COO = CH3-CH=C
OH
The authors also describe exponents on the moo-chlorination of prop ionic acid at 110C inter aria using Jo prop;on;c android as the sole catalyst for a reaction time of 3 hours (see Table 2 on page 5931)~ In the presence of 4 Sol X of prop ionic android relative to the starting prop ionic acid), the reaction product is stated to have contained 2-chloropropionic acid ted") in a ratio of 0.38 to ~-chloropropion;c acid to sheller prop ionic acid ("I
In the presence of 17 mow X of prop ionic ashy-drive, the ratio ~/~ + is stated to have been 0.71.
In our own experiments on the monochlorination of prop ionic acid at about 110C on the presence of 8 mow X of prop ionic android at a reaction time of 15 hours, an ~/~ Jo ratio of 0.76 was obtained without exclusion of light and an ~/~ ratio of 0.92 was obtained with the exclusion of light.
The feasibility of chlorinating prop ionic acid in the presence of prop ionic android us also mentioned in the earlier British Patent No. 621,531; the patent -which relates primarily to the chlorination of acetic 20 acid - does not, however, contain more precise details on this matter. The temperature range indicated for the chlorination of acetic acid (in the presence of acetic android or acutely chloride) is 100 to 110C~
The known processes for the preparation of 2-25 chloropropionic acid are not entirely satisfactory inverse respects If, for instance, phosphorus and sulfur compounds are used as catalysts sparingly soluble P-containing or Containing resinous products are wormed in some cases and make relatively frequent and expensive cleaning of the chlorination apparatus necessary; in the continuous process this can result in frequent plant interruptions. In addition, the P-contain;ng and S-containing residues must also be worked up in a manner which does not pollute the environment. Finally small quantities of P-compounds or S-compounds also frequently get into the 2-chloropropionic acid prepared by these processes, and these impair the quality of the 2-chloropropionic acid It is a disadvantage in the use of propionyl ~3~3~
chloride (boiling point 80C) as a catalyst that this come pound us, at least partially, readily stropped out at the chlorination temperature by the hydrogen chloride which us formed, and thus us lacking during the reaction, or S contaminates the hydrogen chloride and makes the reuse of the latter more difficult.
If prop;on;c android is used as the catalyst, particularly as evidenced by the experiments of Y. Ogata and K. Matsuyama, the ~/~ ~13 ratio at 110C us on any case not adequate for fairly high industrial requirements;
according to the same literature reference, higher tempera-lures promote the free radical mechanism and hence the formation of 3-chloroprop;on;c acid, which makes a fur-then reduction on the I 3 ratio likely.
it was therefore required to find an improved process for the preparation of 2-chloropropion;c acid.
It has been possible to achieve this object in accordance with the invention by chlorinating prop;onic acid on the presence of prop;onic android as the sole catalyst or adoptive Lowe avoiding free rad;cal-forming conditions at temperatures which are above the tempera-lures (about 110C~ hitherto used for the chlorination of prop ionic acid to give 2-chloropropionic acid in the presence of prop ionic android.
The invention relates, therefore, to a process for the preparation of 2-chloropropionic acid by chlorinate in prop ionic acid in the presence of propion;c android at an elevated temperature, Chile excluding free radical former and light, which comprises carrying out the chlorination without 3 further additive at temperatures between about 115 and about 140C~ Temperatures between about 120 and about 135C, on particular between about 125 and 135C, are preferred.
At these higher temperatures yields of over 90%
of theory of 2-chloroprop;onic acid are obtained at high to quantitative conversions and at an I I ratio which is consistently between about 0.99 and I
Thus result was extremely surprising, since, at higher temperatures, as a result of the formation of free ~3~3~
o radicals being promoted by an increase in the temperature, it would rather have been necessary to expect an increase in the proportion of 3-chloropropionic acid which is undesirable on this case and Shea is formed prefer en-tidally when prop ionic acid is chlorinated under con-doughtiness which form free radicals) and hence a lower I ratio.
The amount of prop ionic android added in accord-ante with the process according to the invention is generally between about 3 and about 30 mow %, preferably between about S and about 20 mow X, relative to the start-ivy prop ionic acid. It is possible to add higher amounts, but this affords no advantage. Other catalysts and/or additives should not be used concomitantly in the process.
In addition, care should also be taken that free radical-former and light remain excluded.
In other respects the process is carried out on the customary manner with the exclusion of light in equipment suitable for chlorination reactions Either a discontinuous procedure or a continuous procedure us possible The process can also be carried out either under normal pressure or under an excess pressure, the procedure under normal pressure being preferred.
The chlorine used for the chlorination can be diluted with gases which are inert towards the starting substances and final products of the reaction, such as for example, nitrogen or hydrogen chloride.
It is also possible to use inert solvents, such as, for example chlorinated hydrocarbons (chlorobenzene etch The invention represents a considerable advance because of the high yield achieved in the process accord-in to the invention, and the purity of the sheller-prop ionic acid, and also because of the avoidance of catalysts Shea are difficult to remove and also because, owing to its relatively high boiling point, the catalyst used in this case cannot be stripped out for instance as readily as, for example, propionyl chloride by the hydra gun chloride which is formed.
I
The Examples which follow serve to illustrate the invention in greater detail. The Examples of the oven lion (A) are followed by two comparison examples (B), Shea were carried out at about 110C, with and without the exclusion of light analogously to the tests of Y. gut and K. Matsuyama (foe. cit.).
A) Examples of the invention:
370 g (= 5 moles) of prop ionic acid and 104 g t- 0.8 mole - 16 mow X, relative to the prop ionic acid) of prop ionic android were heated to about 130C on a alter reactor, equipped with a reflex condenser, a stirrer, a thermometer and a gas inlet tube. 470 g of chlorine (= 6.62 moles) were then passed in with the exclusion of light in the course of 20 hours. A yield of 691 g was obtained after the hydrogen chloride had been blown out with nitrogen.
Analysis by gas chromatography gave the fulling result (after saponification with water, in order to con-vent residual chlorinated prop ionic android unto sheller prop ionic acid):
Prop ionic acid: 1.3X
2-Chloropropion;c acid ~"~"): 97O5X
3-Chloropropionic acid to 0.1%
2,2DDichloropropionic Acadia%
I = 0.998 Example 2:
370 9 of prop ionic acid (5 moles) and 52 g of prop ionic android t- 0~4 mole = 8 mow Z9 relative to the prop ionic acid) were chlorinated at about 120C by the procedure of Example 1, 412 g of chlorine (= 5.8 moles) being passed in in the course of 15 hours. A sample gave the following result (as before after saponification with water):
Prop ionic acid: 5.7X
2-Chloropropionic acid ("~92.0%
3-Chloropropionic acid no 2,2 Dichloroprop;onic acid:1.6X
= 0.993 ~3~3~
B) Comparison examples Comparison Example 1 370 9 of prop ionic acid ($ moles and 52 9 of prop ionic android (0.4 mole = 8 mow I, relative to the prop ionic acid) were chlorinated at about 110C iota the exclusion of light in a lottery four-necked flask equipped with a reflex condenser, a stirrer, a thermometer and a gas inlet tube, 391 g of chlorine to 5.5 moles) being passed in in the course of 15 hours.
10 Analysis of a sample by gas chromatography gave the following result (as before after saponification with water):
Prop ionic acid: 11.5X
2-Chloropropionic acid ("~63.4X
3-Chloropropionic acid ~20.0X
2,2-Dichloropropionic Acadia ~/~ + = 0.76 Comparison Example 2 Comparison Example 1 was repeated with the exile-soon of light (under otherwise identical conditions The following gas chromatography figures were obtained:
Prop ionic acid: 5.2X
2-Chloropropion;c acid:82~8X
3-Chloropropionic acid 7.2%
2~2-Dichloropropionic Acadia%
~/~ + = 0.~2
2,2DDichloropropionic Acadia%
I = 0.998 Example 2:
370 9 of prop ionic acid (5 moles) and 52 g of prop ionic android t- 0~4 mole = 8 mow Z9 relative to the prop ionic acid) were chlorinated at about 120C by the procedure of Example 1, 412 g of chlorine (= 5.8 moles) being passed in in the course of 15 hours. A sample gave the following result (as before after saponification with water):
Prop ionic acid: 5.7X
2-Chloropropionic acid ("~92.0%
3-Chloropropionic acid no 2,2 Dichloroprop;onic acid:1.6X
= 0.993 ~3~3~
B) Comparison examples Comparison Example 1 370 9 of prop ionic acid ($ moles and 52 9 of prop ionic android (0.4 mole = 8 mow I, relative to the prop ionic acid) were chlorinated at about 110C iota the exclusion of light in a lottery four-necked flask equipped with a reflex condenser, a stirrer, a thermometer and a gas inlet tube, 391 g of chlorine to 5.5 moles) being passed in in the course of 15 hours.
10 Analysis of a sample by gas chromatography gave the following result (as before after saponification with water):
Prop ionic acid: 11.5X
2-Chloropropionic acid ("~63.4X
3-Chloropropionic acid ~20.0X
2,2-Dichloropropionic Acadia ~/~ + = 0.76 Comparison Example 2 Comparison Example 1 was repeated with the exile-soon of light (under otherwise identical conditions The following gas chromatography figures were obtained:
Prop ionic acid: 5.2X
2-Chloropropion;c acid:82~8X
3-Chloropropionic acid 7.2%
2~2-Dichloropropionic Acadia%
~/~ + = 0.~2
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of 2-chloropropionic acid by chlorinating propionic acid in the presence of propionic anhydride at an elevated temperature with the exclusion of free radical-formers and light, which comprises carrying out the chlorination without a further additive at temperatures between about 115 and about 140°C.
2. A process for the preparation of 2-chloropropionic acid by chlorinating propionic acid in the presence of propionic anhydride at an elevated temperature with the exclusion of free radical-formers and light, which comprises carrying out the chlorination without a further additive at temperatures between about 120 and about 135°C.
3. A process for the preparation of 2-chloropropionic acid by chlorinating propionic acid in the presence of propionic anhydride at an elevated temperature with the exclusion of free radical-formers and light, which comprises carrying out the chlorination without a further additive at temperatures between about 125 and about 135°C.
4. The process as claimed in claim 1, 2 or 3, wherein the amount of propionic anhydride added is between about 3 and about 30 mol % relative to the starting propionic acid.
5. The process as claimed in claim 1, 2 or 3, wherein the amount of propionic anhydride added is between about 5 and about 20 mol % relative to the starting propionic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3422672.9 | 1984-06-19 | ||
| DE19843422672 DE3422672A1 (en) | 1984-06-19 | 1984-06-19 | METHOD FOR PRODUCING 2-CHLORINE PROPIONIC ACID |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231347A true CA1231347A (en) | 1988-01-12 |
Family
ID=6238684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000484369A Expired CA1231347A (en) | 1984-06-19 | 1985-06-18 | Process for the preparation of 2-chloropropionic acid |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0165540B1 (en) |
| AU (1) | AU574473B2 (en) |
| CA (1) | CA1231347A (en) |
| DE (2) | DE3422672A1 (en) |
| HU (1) | HU197869B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2014221198A1 (en) * | 2013-09-16 | 2015-04-02 | Armstrong World Industries, Inc. | Methods for preparing methacrylic acid from biobased starting materials |
| AU2014221199A1 (en) * | 2013-09-16 | 2015-04-02 | Armstrong World Industries, Inc. | Methods for preparing acrylic acid from biobased starting materials |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2009170A1 (en) * | 2007-06-25 | 2008-12-31 | Electrolux Home Products Corporation N.V. | Coated detergent drawer |
| CN113292413A (en) * | 2021-06-08 | 2021-08-24 | 安徽星宇化工有限公司 | Preparation method of 3-chloropropionic acid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB621531A (en) * | 1947-01-13 | 1949-04-11 | Alan Roger Hammond | Manufacture of chlorinated aliphatic acids |
| DE936443C (en) * | 1951-01-12 | 1955-12-15 | Monsanto Chemicals | Process for the production of monochloroacetic acid |
| GB793912A (en) * | 1955-09-12 | 1958-04-23 | Dow Chemical Co | Manufacture of monochloroacetic acid |
| GB892584A (en) * | 1958-06-09 | 1962-03-28 | British Celanese | Improvements in and relating to the production of alpha.alpha-dichloropropionic acid |
-
1984
- 1984-06-19 DE DE19843422672 patent/DE3422672A1/en not_active Withdrawn
-
1985
- 1985-06-11 DE DE8585107159T patent/DE3561197D1/en not_active Expired
- 1985-06-11 EP EP85107159A patent/EP0165540B1/en not_active Expired
- 1985-06-14 HU HU852353A patent/HU197869B/en not_active IP Right Cessation
- 1985-06-18 AU AU43802/85A patent/AU574473B2/en not_active Ceased
- 1985-06-18 CA CA000484369A patent/CA1231347A/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2014221198A1 (en) * | 2013-09-16 | 2015-04-02 | Armstrong World Industries, Inc. | Methods for preparing methacrylic acid from biobased starting materials |
| AU2014221199A1 (en) * | 2013-09-16 | 2015-04-02 | Armstrong World Industries, Inc. | Methods for preparing acrylic acid from biobased starting materials |
| AU2014221199B2 (en) * | 2013-09-16 | 2015-04-30 | Armstrong World Industries, Inc. | Methods for preparing acrylic acid from biobased starting materials |
| AU2014221198B2 (en) * | 2013-09-16 | 2015-05-07 | Armstrong World Industries, Inc. | Methods for preparing methacrylic acid from biobased starting materials |
Also Published As
| Publication number | Publication date |
|---|---|
| HUT42050A (en) | 1987-06-29 |
| AU4380285A (en) | 1986-01-02 |
| AU574473B2 (en) | 1988-07-07 |
| EP0165540B1 (en) | 1987-12-16 |
| DE3422672A1 (en) | 1985-12-19 |
| DE3561197D1 (en) | 1988-01-28 |
| HU197869B (en) | 1989-06-28 |
| EP0165540A1 (en) | 1985-12-27 |
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| DE4123322C2 (en) | 2-chloro-3,4,5-trifluorobenzoic acid 2,2'-dichloro-3,4,5-trifluoroacetophenone, 2,2 ', 2'-trichloro-3,4,5-trifluoroacetophenone, 5,2'-dichloro -2,3,4-trifluoroacetophenone and 5,2 ', 2'-trichloro-2,3,4-trifluoroacetophenone and process for the preparation of these compounds and the isomeric 5-chloro-2,3,4-trifluorobenzoic acid |
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