GB775060A - Unsaturated compounds and the manufacture thereof - Google Patents

Unsaturated compounds and the manufacture thereof

Info

Publication number
GB775060A
GB775060A GB23534/55A GB2353455A GB775060A GB 775060 A GB775060 A GB 775060A GB 23534/55 A GB23534/55 A GB 23534/55A GB 2353455 A GB2353455 A GB 2353455A GB 775060 A GB775060 A GB 775060A
Authority
GB
United Kingdom
Prior art keywords
aldehyde
enol
trimethyl
retrodehydro
iso
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
GB23534/55A
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 GB775060A publication Critical patent/GB775060A/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
    • C07C403/06—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
    • 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

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

Abstract

The invention comprises 2-[21,61,61-trimethylcyclohexen - (11) - yl] - 1 - acyloxy - ethylenes, 4 - [21,61,61 - trimethyl - cyclohexen - (11) - yl] - 1 - acyloxy - 2 - methyl - butadiene - (1,3)s and [2,6,6 - trimethyl - cyclohexen - (1) - yl] - acetaldehyde, and the corresponding compounds having a double bond also in the 3,4-position. It also comprises a process for the manufacture of the enol-esters specified and their conversion into unsaturated aldehydes by converting [2,6,6 - trimethyl - cyclohexylidene - (1)] - acetaldehyde or 4-[21,61,61-trimethyl-cyclohexylidene - (11)] - 2 - methyl - butene - (2) - al - (1) or the corresponding compounds having a double bond in the 2,3- or 21,31-position as the case may be (referred to respectively as iso-C11-aldehyde, iso - C14 - aldehyde, retrodehydro - C11 - aldehyde and retrodehydro-C14-aldehyde) in a manner known per se for the preparation of enol-esters from unsaturated aldehydes, and, if desired, hydrolysing the resulting enol-esters under mild conditions. The enol-ester may be obtained by treating the specified aldehydes with an aliphatic carboxylic acid anhydride containing up to 4 carbon atoms in each of its acyl groups in the presence of an acidic agent such as p-toluene-sulphonic acid or zinc chloride or of an alkali or alkaline earth metal salt of the corresponding acid. Alternatively the aldehyde is heated in the presence of an acid condensing agent with an enol-ester of a lower boiling ketone, e.g. isopropenyl acetate, while distilling off the ketone formed. The hydrolysis may be effected with an alkali-metal or alkaline earth metal carbonate, bicarbonate or hydroxide in aqueous medium preferably also containing methanol, phenol or dioxane. In examples: (1) iso-C11-aldehyde is heated with acetic anhydride to give 2-[21,61,61-trimethyl -(11)-yl]-1-acetoxy-ethylene which on hydrolysis with aqueous methanolic sodium bicarbonate gives b -C11-aldehyde; (2) retrodehydro-C11-aldehyde is converted to the enol-acetate, reaction of which with potassium hydroxide at 20 DEG to 25 DEG C. gives b - dehydro - C11 - aldehyde; (3) iso - C14 -aldehyde is converted to the enol-acetate by heating with isopropenyl acetate and p-toluene sulphonic acid and the product is hydrolysed to b -C14-aldehyde; (4) retrodehydro-C14-aldehyde is converted to the enol-acetate by reaction with isopropenyl acetate and the product on hydrolysis with aqueous methanolic bicarbonate to give b -dehydro-C14-aldehyde. The aldehydes are characterized as their phenyl semicarbazones. The iso-C11-aldehyde can be prepared by condensation of ethoxy-acetylene with 2,6,6-trimethyl-cyclohexanone-(1), hydrogenation of the acetylenic carbinol obtained to the olefinic compound and treatment of the latter with an acid. Retrodehydro-C11-aldehyde is similarly obtained, starting from 2,6,6-trimethyl-cyclohexen-(2)-one-(1). These compounds by conversion to acetals by condensation with a propenyl ether and treatment with acid give the other two compounds employed as starting materials. iso-C14-Aldehyde can also be obtained by the method described in Specification 719,450. Retrodehydro-C14-aldehyde can also be prepared by condensing b -ionone with ethyl chloroacetate, hydrolysing the resulting glycidic-ester with alkali, treating the 4-[21,61,61-trimethylcyclohexen - (11) - yl] - 2 - methyl - buten-(2)-al-(1) obtained with N-bromo-succinimide and splitting off hydrogen bromide from the resulting product.
GB23534/55A 1954-08-16 1955-08-16 Unsaturated compounds and the manufacture thereof Expired GB775060A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH775060X 1954-08-16

Publications (1)

Publication Number Publication Date
GB775060A true GB775060A (en) 1957-05-15

Family

ID=4535749

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23534/55A Expired GB775060A (en) 1954-08-16 1955-08-16 Unsaturated compounds and the manufacture thereof

Country Status (1)

Country Link
GB (1) GB775060A (en)

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