GB1014153A - A process for the preparation of alpha,beta-unsaturated carboxylic acids - Google Patents

A process for the preparation of alpha,beta-unsaturated carboxylic acids

Info

Publication number
GB1014153A
GB1014153A GB3489162A GB3489162A GB1014153A GB 1014153 A GB1014153 A GB 1014153A GB 3489162 A GB3489162 A GB 3489162A GB 3489162 A GB3489162 A GB 3489162A GB 1014153 A GB1014153 A GB 1014153A
Authority
GB
United Kingdom
Prior art keywords
methyl
butan
carboxylic acid
acetoxy
catalyst
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
GB3489162A
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.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of GB1014153A publication Critical patent/GB1014153A/en
Expired legal-status Critical Current

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
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • 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
    • C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton

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

Alpha beta unsaturated carboxylic acids are made by a process which comprises reacting a ketone of the general formula <FORM:1014153/C2/1> in which one of the R1 and R2 groups is a hydrogen atom and the other a carboxylic acid racid radical, an ether group or an amino group, at most one of the groups R1 and R5 is a hydrogen atom, and the groups R3, R4 and R5, are each a hydrogen atom, an organic radical having a carbon link to a chain carbon atom or linked to a chain carbon atom through an ether group, a carboxylic acid radical or an amino group, an R6 is an alkyl group containing up to three carbon atoms and have a nonquaternary carbon linked to the carbonyl group, in particular methyl (beta-acetoxy-isopropyl) ketone, in the liquid phase and in the presence of an oxidation catalyst, especially an organic salt of manganese or copper, or a mixture thereof and preferably manganese acetate and/or copper acetate, with molecular oxygen or a molecular oxygen containing gas, and converting, by heating the carboxylic acid formed in this reaction of the general formula <FORM:1014153/C2/2> into an alpha, beta-unsaturated carboxylic acid of the general formula <FORM:1014153/C2/3> It is preferred to carry out the reaction in a solvent for example, a carboxylic acid and most preferably a mixture of acetic acid and acetic anhydride. The starting material in the form of a ketone, of which the following are named, 1 - acetoxy - butan - 3 - one, acetoxy - 2-methyl - butan - 3 - one, methyl - 1 - dimethylamino - 2 - methyl - butan - 3 - one and 1 methoxy - 2 - methyl - butan - 3 - one, are preferably made by reacting a ketone of which the carbonyle group is linked, on one side, to an alkyl radical, having up to three carbon atoms, the carbon atom thereof linked to the carbonyl group being non-quaternary, and on the other side, to an alkyl radical having at least one hydrogen atom at the alpha carbon atom, with an aldehyde and a carboxylic acid and/or a carboxylic anhydride, or with an aldehyde and an alcohol or a primary or secondary amine, in the presence of an alkaline or weakly acid catalyst. 1-Acetoxy-2-methyl-butan-3-one is preferably prepared by reacting methyl-ethylketone with formaldehyde and either methanol in the presence of an alkaline catalyst, or with acetic acid acetic anhydride in the presence of zinc chloride as catalyst. The examples describes the oxidation of 1-acetoxy-2-methyl-butan-3-one with a mixed copper acetate/manganese acetate catalyst in acetic acid and acetic anhydride mixture at a temperature of between 85 DEG and 130 DEG C. to yield methacrylic acid. Specification 404,983 is referred to.
GB3489162A 1961-09-14 1962-09-12 A process for the preparation of alpha,beta-unsaturated carboxylic acids Expired GB1014153A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL269224 1961-09-14

Publications (1)

Publication Number Publication Date
GB1014153A true GB1014153A (en) 1965-12-22

Family

ID=19753279

Family Applications (1)

Application Number Title Priority Date Filing Date
GB3489162A Expired GB1014153A (en) 1961-09-14 1962-09-12 A process for the preparation of alpha,beta-unsaturated carboxylic acids

Country Status (3)

Country Link
DE (1) DE1290137B (en)
GB (1) GB1014153A (en)
NL (1) NL269224A (en)

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1069614B (en) * 1959-11-26 Knapsack-Griesheim Aktiengesellschaft, Knapsack bei Köln Process for the preparation of aliphatic a, / i-unsaturated carboxylic acids and / or their derivatives
DE597973C (en) * 1933-01-20 1934-06-02 I G Farbenindustrie Akt Ges Process for the production of acids from ketones
DE657377C (en) * 1933-08-03 1938-03-11 Ici Ltd Process for the preparation of esters or nitriles of unsaturated aliphatic ª ‡ -ª ‰ -monocarboxylic acids
DE670782C (en) * 1935-10-29 1939-01-27 Wacker Chemie Gmbh Process for the production of acrylic acid
DE698970C (en) * 1939-03-02 1940-11-20 I G Farbenindustrie Akt Ges Process for the production of carboxylic acids by catalytic oxidation of ketones
US2379625A (en) * 1940-08-16 1945-07-03 Du Pont Manufacture of methacrylic acid
DE724722C (en) * 1940-11-29 1942-09-07 Ig Farbenindustrie Ag Process for the production of carboxylic acids
DE868297C (en) * 1944-12-08 1953-02-23 Distillers Co Yeast Ltd Process and device for the continuous catalytic oxidation of aldehydes and ketones
GB585527A (en) * 1945-02-26 1947-02-10 Distillers Co Yeast Ltd Improvements in or relating to the oxidation of mesityl oxide
GB647094A (en) * 1948-03-31 1950-12-06 Amber Pharmaceuticals Ltd Improvements in and relating to the manufacture of isovaleric acid
DE932368C (en) * 1949-02-19 1955-08-29 British Petroleum Co Process for the production of carboxylic acids
DE871147C (en) * 1949-03-25 1953-03-19 Distillers Co Yeast Ltd Process for the production of ª ‡ -neopentyl acrylic acid
US2744929A (en) * 1952-09-26 1956-05-08 Shell Dev Production of unsaturated carboxylic acids
DE1062696B (en) * 1952-11-06 1959-08-06 Minnesota Mining & Mfg Process for the production of acrylic acid or its alkyl esters from lactic acid or lactic acid alkyl esters
BE528694A (en) * 1953-05-08
DE1018410B (en) * 1954-01-14 1957-10-31 Rhone Poulenc Sa Process for the production of acetic acid, formic acid and formaldehyde by the catalytic oxidation of acetone
US2847464A (en) * 1955-12-29 1958-08-12 Escambia Chem Corp Preparation of lactic acid
US2811545A (en) * 1956-07-23 1957-10-29 Escambia Chem Corp Production of alpha-hydroxy isobutyric and methacrylic acids and their esters
US2811546A (en) * 1956-09-11 1957-10-29 Escambia Chem Corp Production of alpha-hydroxy isobutyric and methacrylic acids and their esters
US2993373A (en) * 1956-09-18 1961-07-25 Kritz Jack Ultrasonic flowmeters and transducers therefor
US2847465A (en) * 1957-01-15 1958-08-12 Escambia Chem Corp Production of alpha hydroxyisobutyric acid
DE1174177B (en) * 1957-03-01 1964-07-16 Xaver Fendth & Co Maschinen Un Motor vehicle engine, preferably for agricultural towing vehicles
US2858330A (en) * 1957-04-29 1958-10-28 Shell Dev Preparation of acrylate esters
US2971981A (en) * 1957-05-10 1961-02-14 Robert S Aries Preparation of alpha-hydroxyisobutyric acid
US2945058A (en) * 1957-09-11 1960-07-12 Eastman Kodak Co Manufacture of crotonic acid
DE1118193B (en) * 1957-09-17 1961-11-30 Knapsack Ag Process for the production of methacrylic acid esters by catalytic elimination of water from ª ‡ -oxyisobutyric acid esters
FR1210246A (en) * 1957-09-17 1960-03-07 Knapsack Ag Alpha-hydroxy-isobutyrate dehydration process
FR1215702A (en) * 1957-10-29 1960-04-20 Escambia Chem Corp Improvements in the production of methacrylic acid and its esters
FR75653E (en) * 1958-03-25
BE579270A (en) * 1958-06-03
DE1124482B (en) * 1958-06-25 1962-03-01 Wacker Chemie Gmbh Process for the preparation of acrylic acid esters and ª ‡ -alkylacrylic acid esters by splitting off alcohol from ª ‰ -alkoxymonocarboxylic acid esters
FR1247411A (en) * 1958-12-24 1960-12-02 Du Pont Vapor phase oxidation of unsaturated compounds, in particular alkenes-1 to acrylic and alkacrylic acids

Also Published As

Publication number Publication date
DE1290137B (en) 1969-03-06
NL269224A (en)

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