GB773863A - A method for the production of vitamin a and esters thereof - Google Patents

A method for the production of vitamin a and esters thereof

Info

Publication number
GB773863A
GB773863A GB35098/55A GB3509855A GB773863A GB 773863 A GB773863 A GB 773863A GB 35098/55 A GB35098/55 A GB 35098/55A GB 3509855 A GB3509855 A GB 3509855A GB 773863 A GB773863 A GB 773863A
Authority
GB
United Kingdom
Prior art keywords
trimethyl
cyclohexadiene
methyl
acid
compound
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
GB35098/55A
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 GB773863A publication Critical patent/GB773863A/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
    • C07C403/08—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 hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C401/00—Irradiation products of cholesterol or its derivatives; Vitamin D derivatives, 9,10-seco cyclopenta[a]phenanthrene or analogues obtained by chemical preparation without irradiation
    • 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

Abstract

The invention comprises Vitamin A2 acetate and a process for the production of Vitamin A2 esters by condensing 4-[21,61,61-trimethyl -cyclohexadiene - (11,31) - yl - (11)] - 2 - methyl - buten - (2) - al - (1) with 1 - hydroxy - 3 - methylpenten - (2) - ine - (4) in a metallo - organic reaction, partially hydrogenating the triple bond of the 1,6-dihydroxy-3,7-dimethyl-9-[21,61,61 -trimethyl - cyclohexadiene - (11,31) - yl - (11)]-nonadien-(2,7)-ine-(4) so obtained, esterifying the resulting nonatriene by treatment with an acylating agent and dehydrating or splitting off acid from (while simultaneously effecting allyl rearrangement) the ester so obtained. The reduction and esterification stages may be effected in reverse order. In the metalloorganic reaction there may be used an alkali compound, e.g. lithium or phenyl lithium, or alkali magnesium halide, e.g. ethyl magnesium bromide. The reduction may be effected by catalytic hydrogenation, e.g. in the presence of palladium, or by means of lithium aluminium hydride. Esterification may be effected with an acid chloride or anhydride. The final dehydration or splitting off of acid may be effected with phosphorus oxychloride, pyridine hydrochloride or by boiling with a strong organic acid, e.g. phthalic acid. Alternatively, splitting off of acid may be effected by treatment with aqueous hydrohalic acid and treating the reaction product with water or a basic compound. The Vitamin A2 esters thus obtained may be saponified to free Vitamin A2 and reesterified. In examples 4-[21,61,61-trimethyl -cyclohexadiene - (11,31) - yl - (11)] - 2 - methyl - buten - (2) - al - (1) is condensed with 1-hydroxy - 3 - methyl - penten - (2) - ine - (4) to produce 1,6 - dihydroxy - 3,7 - dimethyl - 9 - [21,61, 61 - trimethyl - cyclohexadiene - (11,31) - yl-(1)1]-nonadiene-2,7-ine-4, which compound is hydrogenated to produce the corresponding (2,4,7)-nonatriene, which compound is esterified to produce 1-acetoxy-6-hydroxy- and 1,6-diacetoxy - 3,7 - dimethyl - 9 - [21,61,61 - trimethyl-cyclohexadiene (11,31) - yl - (11)] - nonatriene - (2,4,7) which compounds are dehydrated and deacetylated respectively. Starting compound. 4 - [21,61,61 - Trimethyl -cyclohexadiene - (11,31) - yl - (11)] - 2 - methyl - buten - (2) - al - (1) is obtained by brominating 4 - [21,61,61 - trimethyl - cyclohexen - (11) - yl - (11)] 2 - methyl - buten - (2) - al - (1), splitting HBr from the product to form 4-[21,61,61-trimethyl - cyclohex - 21 - ylidene - (11)] 2 - methylbuten - (2) - al - (1), which compound is treated with isopropenyl acetate to produce 4-[21,61,61-trimethyl - cyclohexadiene - (11,31) - yl - (11)] - 2 - methyl - 1 - acetoxy - butadiene - (1,3) which is hydrolysed.
GB35098/55A 1954-12-22 1955-12-07 A method for the production of vitamin a and esters thereof Expired GB773863A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH773863X 1954-12-22

Publications (1)

Publication Number Publication Date
GB773863A true GB773863A (en) 1957-05-01

Family

ID=4535649

Family Applications (1)

Application Number Title Priority Date Filing Date
GB35098/55A Expired GB773863A (en) 1954-12-22 1955-12-07 A method for the production of vitamin a and esters thereof

Country Status (1)

Country Link
GB (1) GB773863A (en)

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