GB744582A - Improvements in and relating to the production of unsaturated acids and esters - Google Patents
Improvements in and relating to the production of unsaturated acids and estersInfo
- Publication number
- GB744582A GB744582A GB1017754A GB1017754A GB744582A GB 744582 A GB744582 A GB 744582A GB 1017754 A GB1017754 A GB 1017754A GB 1017754 A GB1017754 A GB 1017754A GB 744582 A GB744582 A GB 744582A
- Authority
- GB
- United Kingdom
- Prior art keywords
- ester
- acid
- hydroxy
- esters
- 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
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/56—Crotonic acid esters; Vinyl acetic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
a ,b -unsaturated acids or esters, either alone or in admixture with b ,g -unsaturated acids or esters, are prepared by heating at a temperature of at least 150 DEG C., a b -hydroxy acid or ester having at least one hydrogen on the a -carbon atom, and containing in solution 0.01 to 5 per cent by weight, based on the amount of b -hydroxy acid or ester employed, of a salt. Generally a ,b -unsaturated acids or esters are obtained but b ,g -compounds are also formed when the hydroxyl group is attached to a carbon atom to which no hydrogen is attached. The process may be applied to aliphatic p-hydroxy acids or esters such as ethyl b -hydroxy butyrate or to cyclic p-hydroxy acids or esters such as cis-methyl hexahydrosalicylate and dimethyl cyclohexane-2:5-diol-1:4-dicarboxylate. The reaction is preferably carried out in a hydroxylic solvent such as water, or an alcohol containing up to 4 carbon atoms and preferably the alcohol corresponding to the ester. The solvent diminishes the formation of the lactone, 4-carbomethoxy - 2 - hydroxy - 6 - oxabicyclo-[3:2:1] - octa - 7 - one which tends to form when dimethyl cyclohexane-2:5-diol-1:4-carboxylate is converted. In general, when a diester, acid ester, or monoester is reacted in the absence of a solvent or in the presence of water, an unsaturated monoester or free acid may be formed, and if a diester is reacted in an alcohol which does not correspond to the ester, a mixed ester may be obtained. The salt used must be sufficiently soluble under the reaction conditions to enable it to be present to the extent of at least 0.01 per cent by weight of the acid or ester employed, and salts which are not soluble to this extent such as silver iodide and barium sulphate do not facilitate the reaction. Specified salts are the chlorides, bromides and iodides of the alkali or alkaline earth metals, nickel or ferric chlorides, and sodium acetate or benzoate. The preferred salts are those which correspond to the acid or ester to be dehydrated for example sodium b -hydroxy butyrate in the conversion of methyl b -hydroxy butyrate. Such salts may be formed in situ by the addition of alkali metal hydroxide to the acid or ester. The reaction temperature is preferably about 200 DEG C., but is less than the critical temperature of the solvent, and pressure is used to maintain the solvent in liquid phase. In examples: (1) cis-methyl hexahydrosalicylate was heated alone and with sodium hexahydrosalicylate to give cyclohex-1-ene-1-carboxylic acid and methyl ester; (2) as in (1) but using potassium acetate; (3) ethyl b -hydroxy butyrate was heated alone and with sodium b -hydroxy butyrate to give a mixture of ethyl crotonate and crotonic acid; (4) dimethyl cyclohexane-2:5-diol-1:4-dicarboxylate was dissolved in methanol and heated in separate runs with ferric, nickel and sodium chlorides, and the iron and nickel salts of cyclohexane - 2:5 - diol - 1:4 - dicarboxylic acid to yield dimethyl cyclohexa-1:4-diene-1:4-dicarboxylate. Specification 740,388 is referred to.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1017754A GB744582A (en) | 1953-05-01 | 1953-05-01 | Improvements in and relating to the production of unsaturated acids and esters |
FR1106305D FR1106305A (en) | 1953-05-01 | 1954-05-03 | Production of unsaturated acids and esters |
DEI8612A DE947793C (en) | 1953-05-01 | 1954-05-04 | Process for the production of ª ‡ -ª ‰ -unsaturated acids and their esters |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB1017754A GB744582A (en) | 1953-05-01 | 1953-05-01 | Improvements in and relating to the production of unsaturated acids and esters |
Publications (1)
Publication Number | Publication Date |
---|---|
GB744582A true GB744582A (en) | 1956-02-08 |
Family
ID=9962967
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB1017754A Expired GB744582A (en) | 1953-05-01 | 1953-05-01 | Improvements in and relating to the production of unsaturated acids and esters |
Country Status (3)
Country | Link |
---|---|
DE (1) | DE947793C (en) |
FR (1) | FR1106305A (en) |
GB (1) | GB744582A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7687661B2 (en) | 2006-03-15 | 2010-03-30 | Battelle Memorial Institute | Method for conversion of β-hydroxy carbonyl compounds |
US20140364643A1 (en) * | 2002-03-25 | 2014-12-11 | Cargill, Incorporated | Methods of manufacturing derivatives of beta-hydroxycarboxylic acids |
US10239819B2 (en) | 2014-10-17 | 2019-03-26 | Cargill, Incorporated | Methods for producing an ester of an alpha, beta-unsaturated carboxylic acid |
US10710955B2 (en) | 2013-10-17 | 2020-07-14 | Cargill, Incorporated | Methods for producing alkyl hydroxyalkanoates |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE369636C (en) * | 1920-07-03 | 1923-02-22 | Elek Zitaetswerk Lonza | Process for the production of crotonic acid from crotonaldehyde |
FR899779A (en) * | 1942-11-24 | 1945-06-11 | Wacker Chemie Gmbh | Process for preparing crotonic acid |
-
1953
- 1953-05-01 GB GB1017754A patent/GB744582A/en not_active Expired
-
1954
- 1954-05-03 FR FR1106305D patent/FR1106305A/en not_active Expired
- 1954-05-04 DE DEI8612A patent/DE947793C/en not_active Expired
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140364643A1 (en) * | 2002-03-25 | 2014-12-11 | Cargill, Incorporated | Methods of manufacturing derivatives of beta-hydroxycarboxylic acids |
US7687661B2 (en) | 2006-03-15 | 2010-03-30 | Battelle Memorial Institute | Method for conversion of β-hydroxy carbonyl compounds |
US10710955B2 (en) | 2013-10-17 | 2020-07-14 | Cargill, Incorporated | Methods for producing alkyl hydroxyalkanoates |
US11332429B2 (en) | 2013-10-17 | 2022-05-17 | Cargill, Incorporated | Methods for producing alkyl hydroxyalkanoates |
US11332428B2 (en) | 2013-10-17 | 2022-05-17 | Cargill, Incorporated | Methods for producing alkyl hydroxy alkanoates |
US11691941B2 (en) | 2013-10-17 | 2023-07-04 | Cargill, Incorporated | Methods for producing alkyl hydroxyalkanoates |
US12103912B2 (en) | 2013-10-17 | 2024-10-01 | Cargill, Incorporated | Methods for producing alkyl hydroxyalkanoates |
US10239819B2 (en) | 2014-10-17 | 2019-03-26 | Cargill, Incorporated | Methods for producing an ester of an alpha, beta-unsaturated carboxylic acid |
US10633326B2 (en) | 2014-10-17 | 2020-04-28 | Cargill, Incorporated | Methods for producing an ester of an alpha, beta-unsaturated carboxylic acid |
US10774026B2 (en) | 2014-10-17 | 2020-09-15 | Cargill, Incorporated | Methods for producing an ester of an alpha, beta-unsaturated carboxylic acid |
US11242308B2 (en) | 2014-10-17 | 2022-02-08 | Cargill, Incorporated | Methods for producing an ester of an alpha, beta-unsaturated carboxylic acid |
Also Published As
Publication number | Publication date |
---|---|
FR1106305A (en) | 1955-12-16 |
DE947793C (en) | 1956-08-23 |
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