GB812267A - The manufacture of carotenoids - Google Patents

The manufacture of carotenoids

Info

Publication number
GB812267A
GB812267A GB39466/56A GB3946656A GB812267A GB 812267 A GB812267 A GB 812267A GB 39466/56 A GB39466/56 A GB 39466/56A GB 3946656 A GB3946656 A GB 3946656A GB 812267 A GB812267 A GB 812267A
Authority
GB
United Kingdom
Prior art keywords
betacarotene
trimethyl
cis
bisdehydro
diyne
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
GB39466/56A
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 GB812267A publication Critical patent/GB812267A/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
    • C07C403/24—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 six-membered non-aromatic rings, e.g. beta-carotene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/21—Alkatrienes; Alkatetraenes; Other alkapolyenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
    • 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
    • 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
    • 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
    • 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
    • C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Abstract

The invention comprises the 11, 12; 111, 121-dicis form of betacarotene and its 3,4; 31, 41-bisdehydro-derivative and the 4,41-disubstituted derivatives of the 11,12; 111,121-dicis form of betacarotene in which each substituent is a hydroxy or acyloxy group, 11,12; 111,121-dicis - zeaxanthine, and 1,18 - disubstituted-3,7,12,16 - tetramethyl - octadecaheptaene - (1,3,7,9,11,15,17) - diyne - (5,13) in which each of the substituents in the 1- and 18-positions 2,6,6 - trimethyl - cyclohexadien - (1,3) - yl radical or the 2,6,6-trimethyl-cyclohexen-(1)-yl radical which contains in the 4-position a hydroxy or acyloxy group, and a process for the preparation of carotenoids by bilaterally condensing 3,8 - dimethyl - decatriene - (3,5,7)-diyne - (1,9) with a 4-substituted 2-methyl-buten-(2)-al-(1), the 4-substituent being the 2,6,6 - trimethyl - cyclohexadiene - (1,3) - yl radical or a 2,6,6-trimethyl-cyclohexen-(1)-yl or a 2,6,6 - trimethyl - cyclohexylidene radical which may contain in the 4-position a hydroxy or acyloxy group, in an alkali metal or Grignard reaction, hydrolysing the metal containing compound so formed, eliminating the elements of 2 molecules of water from the resulting 1,18-disbustituted - 3,7,12,16 - tetramethyl - 4,15-dihydroxy - octadecapentaene - (2,7,9,11,16)-diyne - (5,13), hydrolysing any 41 - acyloxy groups in the product if desired, catalytically hydrogenating the triple bonds in the resulting 1,18 - disubstituted - 3,7,12,16 - tetramethyl-octadecaheptaene - (1,3,7,9,11,15,17) - diyne - (5,13) to double bonds and, if desired, isomerizing the resulting di-cis carotenoid to the corresponding all-trans carotenoid. The dimetal-containing compound formed may be the dilithium, disodium or di-(halogeno-magnesium) derivative. The bilateral condensation may be carried out in an inert solvent, e.g. diethyl ether or benzene, or in liquid ammonia. The removal of 2 molecules of water may be carried out directly, or the diol may be esterified, e.g. by acetylation or by treatment with aqueous or anhydrous hydrohalic acid, and two molecules of an acid eliminated. The elimination of acid or water may be carried out with phosphorus oxychloride in pyridine, or in the case of dihalide esters, the dihalide may be treated with water or a basic compound. The hydrogenation step may be carried out in suspension, for example, in petroleum ether or toluene, preferably using a lead-inhibited palladium catalyst in the presence of quinoline. The isomerization step is preferably carried out by healing the di-cis carotenoid in petroleum ether. In the examples: (1) betacarotene is prepared by removing the elements of 2 molecules of water from 1,18 - di - [21,61,61 - trimethyl - cyclohexen - (11) - yl - (11)] - 3,7,12,16 - tetramethyl - 4,15 - dihydroxy - octadecapentaene-(2,7,9,11,16) - diyne - (5,13) using hydrobromic acid as the reactant, to form 11,12; 111,121-bisdehydro - betacarotene, hydrogenating this compound to form 11,12; 11,12-di-cis-betacarotene, and isomerizing the di-cis compound to betacarotene; (2) by a similar series of steps as in (1), 3,4; 31,41-bisdehydro-betacarotene is prepared, the intermediates being 3,4; 31,41; 11,12; 111,121 - tetradehydro - betacarotene, and 3,4; 31,41 - bisdehydro - 11,12; 111,121 - di-cis-beta-carotene; and (3) by a similar series of steps as in (1), all-trans-zeaxanthine is prepared, the intermediates being 3,31-diacetoxy-11,12; 111,121 - bisdehydro - betacarotene and the corresponding 3,31-dihydroxy compound, and 11,12; 111,121-di-cis-zeaxanthine. Specifications 775,060, 789,693, 797,200, 802,136, 812,268 and 812,269 are referred to.
GB39466/56A 1955-12-29 1956-12-28 The manufacture of carotenoids Expired GB812267A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH812267X 1955-12-29

Publications (1)

Publication Number Publication Date
GB812267A true GB812267A (en) 1959-04-22

Family

ID=4538605

Family Applications (1)

Application Number Title Priority Date Filing Date
GB39466/56A Expired GB812267A (en) 1955-12-29 1956-12-28 The manufacture of carotenoids

Country Status (1)

Country Link
GB (1) GB812267A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103940A (en) * 1997-06-04 2000-08-15 Basf Aktiengesellschaft Preparation of zeaxanthin, intermediates for this preparation, and the preparation thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103940A (en) * 1997-06-04 2000-08-15 Basf Aktiengesellschaft Preparation of zeaxanthin, intermediates for this preparation, and the preparation thereof

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