GB799797A - An improved process for the manufacture of unsaturated ketones - Google Patents

An improved process for the manufacture of unsaturated ketones

Info

Publication number
GB799797A
GB799797A GB11631/56A GB1163156A GB799797A GB 799797 A GB799797 A GB 799797A GB 11631/56 A GB11631/56 A GB 11631/56A GB 1163156 A GB1163156 A GB 1163156A GB 799797 A GB799797 A GB 799797A
Authority
GB
United Kingdom
Prior art keywords
methyl
acetoacetate
dimethyl
allyl acetoacetate
heptene
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
GB11631/56A
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.)
F Hoffmann La Roche AG
Original Assignee
F Hoffmann La Roche AG
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 F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Publication of GB799797A publication Critical patent/GB799797A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/02—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains containing only carbon and hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
    • C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
    • C07C403/14—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms
    • C07C403/16—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by doubly-bound oxygen atoms not being part of —CHO groups
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B9/00—Essential oils; Perfumes
    • C11B9/0026—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring
    • C11B9/0034—Essential oils; Perfumes compounds containing an alicyclic ring not condensed with another ring the ring containing six carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Unsaturated ketones having the general formula <FORM:0799797/IV (b)/1> wherein R1 represents an acyclic or cyclic alkenyl (including acyclic alkapolenyl) or alkyl radical or phenyl and R2 represents an alkyl radical having up to 4 carbon atoms, or R1 and R2 together with their shared carbon atom represent cyclohexylidene, and R3 represents hydrogen or an alkyl radical containing up to 4 carbon atoms, are prepared by eliminating the elements of CO2 from acetoacetic esters having the general formula <FORM:0799797/IV (b)/2> in which the R's are as defined above, by heating the esters in the presence of an aluminium trialkoxide containing up to 4 carbon atoms in each alkyl radical. The process may be effected by heating the reaction mixture with agitation at a sufficiently high temperature to cause a steady evolution of CO2. The aluminium trialkoxide is preferably used in amounts of about 8-25 millimoles. per mol. of acetoacetic ester. An inert solvent may be present. Examples describe the conversion of (1), (6) and (7) 1,1-dimethyl-allylacetoacetate to 6-methyl-heptene-5 - one - 2, (2) 1,1,2 - trimethyl - allyl acetoacetate to 5,6 - dimethyl - heptene - 5 - one - 2, (3) 1 - methyl - 1 - isobutyl - allyl acetoacetate to 6,8 - dimethyl - nonene - 5 - one - 2, (4) 1-methyl - 1 - (41 - methyl - pentene - 31 - yl)-allyl acetoacetate to 6,10 - dimethyl - hendecadiene-5,9 - one - 2, (5) 1 - methyl - 1(41, 81 - dimethyl - nonyl)-allyl acetoacetate to 6,10,14-trimethyl-pentadecene - 5 - one - 2, (8) 1 - methyl - 1 -phenyl-allyl acetoacetate to 6-phenyl-heptene-5-one-2, (9) 1-vinyl cyclohexyl acetoacetate to 5 - cyclohexylidene - pentanone - 2, (10) 3,7,9-trimethyl - decadiene - 1,6 - yl - 3 acetoacetate to 6,10,12 - trimethyl - tridecadiene - 5,9 - one-2 and (11) 6-cyclohexylidene-3-methyl-hexene-1-yl-3 acetoacetate to 9-cyclohexylidene-6-methyl-nonene-5-one-2, by heating the specified acetoacetate with aluminium tri-isoproxide, ethoxide or butoxide at temperatures ranging from 120 DEG to 175 DEG C. The product is purified by fractional distillation and/or washing with acid or alkaline washes. 1,1-Diethyl allyl acetoacetate, 1-methyl - 1 - ethyl - allyl acetoacetate, 1-methyl-1 - (41, 61 - dimethyl - heptene - 3 - yl - allyl acetoacetate and 1-methyl-1-(41, 81-dimethyl-nonadiene-3,7-yl) allyl acetoacetate are other specified acetoacetic reagents and a table lists additional values for the R's in the above ester formula. Aluminium tri-methoxide and -isobutoxide are further specified alkoxides. The acetoacetates used as starting materials in the examples are prepared by reacting diketene with appropriate carbinols in petroleum ether solution in the presence of pyridine and acetic acid at 25-30 DEG C. followed by a specified working up to isolate the resulting acetoacetates. Specifications 702,647, 725,621, 737,512, 785,086 and 787,350, [Group XL (c)], are referred to.
GB11631/56A 1955-04-19 1956-04-17 An improved process for the manufacture of unsaturated ketones Expired GB799797A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US50252655A 1955-04-19 1955-04-19

Publications (1)

Publication Number Publication Date
GB799797A true GB799797A (en) 1958-08-13

Family

ID=23998229

Family Applications (1)

Application Number Title Priority Date Filing Date
GB11631/56A Expired GB799797A (en) 1955-04-19 1956-04-17 An improved process for the manufacture of unsaturated ketones

Country Status (4)

Country Link
BE (1) BE547084A (en)
DE (1) DE1053498B (en)
FR (1) FR1205812A (en)
GB (1) GB799797A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2928944A1 (en) * 1979-07-18 1981-02-12 Basf Ag IMPROVED METHOD FOR PRODUCING HIGHER UNSATURATED KETONES
DE19647117A1 (en) * 1996-11-14 1998-05-28 Basf Ag Process for the production of gamma, delta-unsaturated ketones by Caroll reaction in cyclic carbonates or gamma-lactones as solvents
DE10123066A1 (en) 2001-05-11 2002-11-14 Basf Ag Process for the production of higher alpha, beta-unsaturated alcohols

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2638484A (en) * 1951-06-05 1953-05-12 Hoffmann La Roche Preparation of an octenone
US2662920A (en) * 1952-06-10 1953-12-15 Hoffmann La Roche Process for preparing 2, 3-dimethylheptene-2-one-6
FR1079408A (en) * 1952-06-10 1954-11-30 Hoffmann La Roche Process for the preparation of unsaturated ketones

Also Published As

Publication number Publication date
DE1053498B (en) 1959-03-26
FR1205812A (en) 1960-02-04
BE547084A (en) 1956-10-17

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