GB813490A - Production of tertiary acetylenic alcohols - Google Patents

Production of tertiary acetylenic alcohols

Info

Publication number
GB813490A
GB813490A GB29781/56A GB2978156A GB813490A GB 813490 A GB813490 A GB 813490A GB 29781/56 A GB29781/56 A GB 29781/56A GB 2978156 A GB2978156 A GB 2978156A GB 813490 A GB813490 A GB 813490A
Authority
GB
United Kingdom
Prior art keywords
alkali metal
ketone
methyl
alcohol
methyl ethyl
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
GB29781/56A
Inventor
Richard Norman Lacey
Hubert Jowitt
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.)
Distillers Co Yeast Ltd
Distillers Co Ltd
Original Assignee
Distillers Co Yeast Ltd
Distillers Co Ltd
Filing date
Publication date
Application filed by Distillers Co Yeast Ltd, Distillers Co Ltd filed Critical Distillers Co Yeast Ltd
Publication of GB813490A publication Critical patent/GB813490A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01Preparation of ethers
    • C07C41/05Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/24Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00Ethers; Compounds having groups, groups or groups
    • C07C43/02Ethers
    • C07C43/03Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14Unsaturated ethers
    • C07C43/15Unsaturated ethers containing only non-aromatic carbon-to-carbon double bonds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Tertiary acetylenic alcohols are produced by reacting acetylene with a ketone under substantially anhydrous conditions and in the presence of an alkali metal alkoxyethoxide of formula ROCH2CH2OM in solution in an alkoxyethanol of formula ROCH2CH2OH, where R in each case represents an alkyl group of one to six carbon atoms, to form the alkali metal derivative of a tertiary acetylenic alcohol, and recovering the alcohol from its alkali metal derivative. Preferably the alkali metal alkoxyethoxide is in solution in the corresponding alkoxyethanol, in which case the solution may be prepared by adding aqueous alkali metal hydroxide to an excess of alkoxyethanol at a subatmospheric pressure, maintaining the mixture at boiling point, and removing water by distillation with a hydrocarbon entraining agent, such as benzene or toluene. A preferred condensing agent is potassium n-butoxyethoxide in n-butoxyethanol. Suitable ketones for carrying out the process are acetone, methyl ethyl ketone, methyl propyl ketone, diethyl ketone, methyl amyl ketone, di-isopropyl ketone, cyclohexanone, and methylheptenone. The molar ratio of ketone to alkoxyethoxide is suitably from 0.30: 1 to 0.95: 1, preferably about 0.75: 1. The condensation may be carried out at below 60 DEG C., preferably 0-30 DEG C. The pressure may be atmospheric or superatmospheric. The tertiary acetylenic alcohol may be liberated from its alkali metal derivative by (i) adding water, extracting with a solvent at a comparatively low temperature, and recovering the free alcohol from the solvent; (ii) hydrolysis, treating with CO2, removing alkali metal carbonate, and solvent extraction; (iii) adding water, removing or neutralizing alkali metal hydroxide, and distilling; (iv) washing the crude product with water, converting the alkali metal derivative to free alcohol, neutralizing alkali metal hydroxide and distilling; (v) (where acetone or methyl ethyl ketone is used) distilling the crude reaction product, after adding water, at not above 60 DEG C. under reduced pressure, e.g. 100-150 mm., to obtain the free alcohol. In Examples (1) and (2) acetone is reacted with acetylene to produce 2-methyl-but-3-yn-2-ol; (3), (4), (5) and (8) methyl ethyl ketone produces 3-methyl-pent-1-yn-3-ol; (6) and (7) 6-methylhept-5-ene-2-one produces dehydrolinalol (all using potassium n-butoxyethoxide in n-butoxyethanol); and methyl ethyl ketone produces 3-methyl-pent-1-yn-3-ol, using (a) potassium n-propoxyethoxide in n-propoxyethanol; and (10) sodium n-butoxyethoxide in n-butoxyethanol.
GB29781/56A 1956-09-29 Production of tertiary acetylenic alcohols Expired GB813490A (en)

Publications (1)

Publication Number Publication Date
GB813490A true GB813490A (en) 1959-05-21

Family

ID=1741774

Family Applications (1)

Application Number Title Priority Date Filing Date
GB29781/56A Expired GB813490A (en) 1956-09-29 Production of tertiary acetylenic alcohols

Country Status (1)

Country Link
GB (1) GB813490A (en)

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