GB695313A - Improved process for the production of unsaturated ketones - Google Patents

Improved process for the production of unsaturated ketones

Info

Publication number
GB695313A
GB695313A GB437751A GB437751A GB695313A GB 695313 A GB695313 A GB 695313A GB 437751 A GB437751 A GB 437751A GB 437751 A GB437751 A GB 437751A GB 695313 A GB695313 A GB 695313A
Authority
GB
United Kingdom
Prior art keywords
acetoacetate
alcohol
allyl
pyrolysis
methallyl
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
GB437751A
Inventor
Richard Norman Lacey
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.)
British Industrial Solvents Ltd
Original Assignee
British Industrial Solvents 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 British Industrial Solvents Ltd filed Critical British Industrial Solvents Ltd
Priority to GB437751A priority Critical patent/GB695313A/en
Publication of GB695313A publication Critical patent/GB695313A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups

Landscapes

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

Abstract

Ketones of the formula R1.CH=CR2.CHR3.CH2.CO.CH2.R4 (R1-R4=hydrogen or C1-C4 alkyl) are obtained by pyrolyzing esters <FORM:0695313/IV (b)/1> in the vapour phase at 300-600 DEG C. The esters may be formed previously or in situ by reacting the alkenol R3.CH=CR2.CHR1.OH with an alkyl acylacetate or (when R4=H) with diketene in the presence of an alkaline catalyst such as a tertiary amine. Preferably the pyrolysis mixture contains an excess of the alkenol. Suitable conditions for the pyrolysis are 0.5-15 seconds at 450-550 DEG C.; the pressure may be normal or sub- or superatmospheric. The desired ketone is separated from the products by distillation, and any unchanged ester may be recycled. In the examples: (1) allyl acetoacetate is made from allyl alcohol, diketene and triethylamine, and pyrolysed to give allylacetone, allyl alcohol and and dehydracetic acid; extra allyl alcohol may be added to the pyrolysis mixture; (2) a mixture of methyl acetoacetate and allyl alcohol is pyrolysed, yielding allylacetone, allyl acetoacetate and methanol; (3) methallyl acetoacetate is made from methallyl alcohol, diketene and triethylamine; it is then pyrolysed to yield methallyl-acetone and methallyl alcohol; (4) crotyl alcohol is similarly converted into crotyl acetoacetate; pyrolysis of this gives 3-methyl-hex-1-en-5-one, crotyl alcohol and low-boiling products; (5) methylvinylcarbinyl acetoacetate on pyrolysis yields hept-2-en-6-one, methylvinylcarbinol and hydrocarbons, mainly butadiene. Other suitable keto-esters are the acetoacetates of pent-1-en-3-ol, hex-2-en-4-ol, 2 - methylpent - 2 - en - 1 - ol and 3 - methyl - pent-2-en-4-ol and allyl propionoacetate. According to the Provisional Specification the groups R may be alkyl in general and the 2-position of the acylacetic group may also be alkylated.
GB437751A 1951-02-23 1951-02-23 Improved process for the production of unsaturated ketones Expired GB695313A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB437751A GB695313A (en) 1951-02-23 1951-02-23 Improved process for the production of unsaturated ketones

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB437751A GB695313A (en) 1951-02-23 1951-02-23 Improved process for the production of unsaturated ketones

Publications (1)

Publication Number Publication Date
GB695313A true GB695313A (en) 1953-08-05

Family

ID=9776016

Family Applications (1)

Application Number Title Priority Date Filing Date
GB437751A Expired GB695313A (en) 1951-02-23 1951-02-23 Improved process for the production of unsaturated ketones

Country Status (1)

Country Link
GB (1) GB695313A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2795617A (en) * 1957-06-11
DE1026743B (en) * 1955-03-31 1958-03-27 Basf Ag Process for the production of unsaturated ketones
DE1040539B (en) * 1954-12-07 1958-10-09 Hoffmann La Roche Process for the production of new unsaturated ketones with special fragrance properties
DE1046029B (en) * 1955-08-24 1958-12-11 Hoffmann La Roche Process for the production of new unsaturated ketones with special fragrance properties
US5874635A (en) * 1996-11-14 1999-02-23 Basf Aktiengesellschaft Preparation of γ, δ-unsaturated ketones by the carroll reaction in cyclic carbonates or γ-lactones

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2795617A (en) * 1957-06-11
DE1040539B (en) * 1954-12-07 1958-10-09 Hoffmann La Roche Process for the production of new unsaturated ketones with special fragrance properties
DE1026743B (en) * 1955-03-31 1958-03-27 Basf Ag Process for the production of unsaturated ketones
DE1046029B (en) * 1955-08-24 1958-12-11 Hoffmann La Roche Process for the production of new unsaturated ketones with special fragrance properties
US5874635A (en) * 1996-11-14 1999-02-23 Basf Aktiengesellschaft Preparation of γ, δ-unsaturated ketones by the carroll reaction in cyclic carbonates or γ-lactones

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