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 esters

Info

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
Application number
GB1017754A
Inventor
Peter Smith
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to GB1017754A priority Critical patent/GB744582A/en
Priority to FR1106305D priority patent/FR1106305A/en
Priority to DEI8612A priority patent/DE947793C/en
Publication of GB744582A publication Critical patent/GB744582A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/56Crotonic 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.
GB1017754A 1953-05-01 1953-05-01 Improvements in and relating to the production of unsaturated acids and esters Expired GB744582A (en)

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)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Cited By (11)

* Cited by examiner, † Cited by third party
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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