GB935006A - Improvements in or relating to isoprene derivatives of trimethyl cyclohexene - Google Patents

Improvements in or relating to isoprene derivatives of trimethyl cyclohexene

Info

Publication number
GB935006A
GB935006A GB21182/60A GB2118260A GB935006A GB 935006 A GB935006 A GB 935006A GB 21182/60 A GB21182/60 A GB 21182/60A GB 2118260 A GB2118260 A GB 2118260A GB 935006 A GB935006 A GB 935006A
Authority
GB
United Kingdom
Prior art keywords
beta
compound
ketone
acetone
methyl
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
GB21182/60A
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.)
Adisseo France SAS
Original Assignee
AEC Societe de Chimie Organique and Biologique SA
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 AEC Societe de Chimie Organique and Biologique SA filed Critical AEC Societe de Chimie Organique and Biologique SA
Publication of GB935006A publication Critical patent/GB935006A/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
    • C07C403/14—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
    • 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
    • C07C403/10—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 etherified 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
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Landscapes

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

Abstract

The three aldehydes P-(Is)n-CHO where P represents the 2,6,6-trimethyl-cyclohexene-1-yl group, Is is the isoprene residue <FORM:0935006/IV(a)/1> and n is 1, 2 or 3, are produced by a series of reactions starting from the appropriate methyl ketone P-(Is)n-1-CH=CH-CO-CH3 which is condensed with an alkyl formate, in the presence of a catalyst such as a metal alcoholate, to give a salt of the beta-ketoenol P-(Is)n-1-CH=CH-CO-CH=CHOH (II) Compound II is converted into the acetal of the tautomeric beta-keto-aldehyde form <FORM:0935006/IV(a)/2> where R2 and R3 are lower alkyl groups, which is treated with methyl lithium or a methyl magnesium halide or a methyl zinc halide to obtain <FORM:0935006/IV(a)/3> and this compound VI is then dehydrated and hydrolysed in order to obtain the required aldehyde P-(Is)n-CHO. The starting ketone is beta-ionone for the preparation of beta-ionylidene-acetaldehyde; and the C18 ketone (n=2) is the starting ketone for the preparation of retinene. The C18 ketone can be obtained by condensing beta-ionylidene-acetaldehyde with acetone in the presence of an alkali metal alcoholate or an alkali metal hydroxide. Similarly the C23 ketone, required for the preparation of the C25 aldehyde, is obtained by condensing retinene with acetone. The C18 and C23 ketones may be purified by molecular distillation, chromatography, or by the formation of the cyanacethydrazone. The beta-keto-enol II, or its sodium salt, may be converted into the acetal V by raacting it with a lower alcohol containing a small amount of dissolved hydrogen chloride and a formate, or acetate, of the alcohol. Alternatively, the enol or its sodium salt is first acylated (e.g. with acetyl chloride or acetic anhydride) or etherified (e.g. with methyl sulphate before treatment with the alcohol. The dehydration and hydrolysis of compound VI to obtain P-(Is)n-CHO may be carried out in one stage by the action of aqueous hydrochloric acid on a solution of compound VI in acetone; alternatively the compound VI may first be dehydrated by means of a trace of acid or an alcoholic solution of the compound, and the dehydration-product is then hydrolysed with aqueous hydrochloric acid in acetone.
GB21182/60A 1959-07-06 1960-06-16 Improvements in or relating to isoprene derivatives of trimethyl cyclohexene Expired GB935006A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR799395A FR1243824A (en) 1959-07-06 1959-07-06 Process for the preparation of isoprenic compounds of the carotenoid family and novel intermediates resulting therefrom

Publications (1)

Publication Number Publication Date
GB935006A true GB935006A (en) 1963-08-21

Family

ID=8716838

Family Applications (1)

Application Number Title Priority Date Filing Date
GB21182/60A Expired GB935006A (en) 1959-07-06 1960-06-16 Improvements in or relating to isoprene derivatives of trimethyl cyclohexene

Country Status (3)

Country Link
CH (1) CH411821A (en)
FR (1) FR1243824A (en)
GB (1) GB935006A (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1053680A (en) * 1963-01-02
FR2434136A1 (en) * 1978-08-22 1980-03-21 Aec Chim Organ Biolog NEW ETHYLENIC KETONES, THEIR PREPARATION AND THEIR USE
US4523042A (en) * 1983-07-29 1985-06-11 Usv Pharmaceutical Derivatives of alpha-alkyl polyolefinic carboxylic acid useful in the treatment of psoriasis
FR2728260B1 (en) * 1994-12-16 1997-03-14 Centre Nat Rech Scient BETA-METHYLENE ALDEHYDES USEFUL IN PARTICULAR FOR THE PREPARATION OF COMPOUNDS OF INTEREST SUCH AS RETINOIDS OR CAROTENOIDS AND PREPARATION OF COMPOUNDS OF INTEREST BY MEANS OF SAID BETA-METHYLENE ALDEHYDES

Also Published As

Publication number Publication date
FR1243824A (en) 1960-10-21
CH411821A (en) 1966-04-30

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