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GB1173063A - Novel Polyene Compounds and a process for the manufacture and conversion thereof - Google Patents

Novel Polyene Compounds and a process for the manufacture and conversion thereof

Info

Publication number
GB1173063A
GB1173063A GB7095/67A GB709567A GB1173063A GB 1173063 A GB1173063 A GB 1173063A GB 7095/67 A GB7095/67 A GB 7095/67A GB 709567 A GB709567 A GB 709567A GB 1173063 A GB1173063 A GB 1173063A
Authority
GB
United Kingdom
Prior art keywords
trimethyl
methyl
hydroxy
give
cyclohex
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
GB7095/67A
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.)
Roche Products Ltd
Original Assignee
Roche Products Ltd
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 Roche Products Ltd filed Critical Roche Products Ltd
Priority to GB7095/67A priority Critical patent/GB1173063A/en
Publication of GB1173063A publication Critical patent/GB1173063A/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
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • A23L5/40—Colouring or decolouring of foods
    • A23L5/42—Addition of dyes or pigments, e.g. in combination with optical brighteners
    • A23L5/47—Addition of dyes or pigments, e.g. in combination with optical brighteners using synthetic organic dyes or pigments not covered by groups A23L5/43 - A23L5/46
    • 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
    • C07C403/06—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
    • C07C403/24—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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
    • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
    • 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)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Nutrition Science (AREA)
  • Engineering & Computer Science (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1,173,063. Polyene compounds. ROCHE PRODUCTS Ltd. and B. C. L. WEEDON. 15 March, 1968 [14 Feb., 1967], No. 7095/67. Heading C2C. The invention comprises compounds of formula wherein the broken line represents an optional bond and R is a group of formula The compounds are prepared by reacting a phosphonium salt of formula wherein R<SP>1</SP> is an aryl group and A<SP>-</SP> is the anion of a mineral acid, with an aldehyde of formula wherein R<SP>2</SP> is a formyl group or a group of formula in the presence of a proton acceptor and converting any acyloxy or oxo group in the resulting compound of the formula into an hydroxy group by reduction or hydrolysis. In Examples: (1) 7,8,7<SP>1</SP>,8<SP>1</SP>-bisdehydro-zeaxanthin is prepared by reacting together 3-methylpent-2-en-4-yn-1-ol and 4,4-ethylenedioxy-2,2,6- trimethyl-cyclohexane in a Grignard reaction to give 5 - (4,4 - ethylenedioxy - 1 - hydroxy - 2,2,6 - trimethyl - cyclohexyl) - 3 - methyl - pent - 2 - en - 4-yn-1-ol which is reacted with acetic acid to yield a mixture of 5-(1-hydroxy-4-oxo.2,2,6- trimethyl - cyclohexyl) - 3 - methyl - pent - 2 - en - 4- yn - 1 - ol and 5 - (1 - hydroxy - 4 - oxo - 2,2,6 - trimethyl - cyclohexyl) - 1 - acetoxy - 3- methyl - pent - 2 - en - 4 - yne, the latter compound is treated with LiAlH4 to give 5-(1,4- dihydroxy - 2,2,6 - trimethyl - cyclohexyl) - 3 - methyl - pent - 2 - en - 4 - yn - 1 - ol, which is refluxed with acetic acid/acetic anhydride to give 5 - (4 - acetoxy 2,2,6 - trimethyl - cyclohex - 6 - enyl) - 1 - acetoxy - 3 - methyl - -pent 2 - en - 4 - yne, which is treated with methanolic KOH to yield 5-(4-hydroxy-2,2,6-trimethyl-cyclohex-6- enyl) - 3 - methyl - pent - 2 - en - 4 - yn - 1- ol, which is reacted with triphenyl-phosphine hydrobromide to give [5-(4-hydroxy-2,2,6-trimethyl - cyclohex - 6 - enyl) - 3 - methyl - pent - 2 - en - 4 - yn - 1 - yl] - triphenyl phosphonium bromide (compound X) which is reacted with 2,7 - dimethyl - octa - 2,4,6 - triene - 1,8 - dial to yield 13-(4-hydroxy-2,2,6-trimethyl-cyclohex - 6 - enyl) - 2,7,11 - trimethyl trideca- 2,4,6,8,10 - pentaen - 12 - yn - 1 - al which is further reacted with compound X to give 7,8, 7<SP>1</SP>,8<SP>1</SP>-bisdehydro-zeaxanthin; catalytic hydrogenation of the bisdehydro-zeaxanthin gives zeaxanthin: (2) alphaionone is added to a mixture of Li, liq. NH 3 and ferric nitrate through which acetylene has been passed and 5 - (2,2,6 - trimethyl - cyclohex - 5 - enyl) - 3 - methyl - pent - 4 - en - 1 - yn - 3 - ol is isolated and catalytically hydrogenated to give 5- (2,2,6 - trimethyl - cyclohex - 5 - enyl) - 3 - methyl - penta-1,4-dien-3-ol, which is reacted with triphenyl-phosphine hydrobromide to give [5- (2,2,6 - trimethyl - cyclohex - 5 - enyl) - 3 - methyl - penta - 2,4 - dien - 1 - yl] - triphenyl - phosphonium bromide, which is reacted with 2,7- dimethyl - octa - 2,4,6 - triene - 1,8 - dial to give 13 - (2,2,6 - trimethyl - cyclohex - 5 - enyl) - 2,7,11 - trimethyl - trideca - 2,4,6,8,10,12 - hexaen - 1-al (α-apo-12<SP>1</SP>-carotenal), which is reacted with compound X to give 7,8-dehydro-3-hydroxy-α- carotene: 7,8-dehydro-zeaxanthin, 7,8-dehydrolutein and 7,8-dehydro-3-hydroxy-#-carotene may be similarly prepared.
GB7095/67A 1967-02-14 1967-02-14 Novel Polyene Compounds and a process for the manufacture and conversion thereof Expired GB1173063A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB7095/67A GB1173063A (en) 1967-02-14 1967-02-14 Novel Polyene Compounds and a process for the manufacture and conversion thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB7095/67A GB1173063A (en) 1967-02-14 1967-02-14 Novel Polyene Compounds and a process for the manufacture and conversion thereof

Publications (1)

Publication Number Publication Date
GB1173063A true GB1173063A (en) 1969-12-03

Family

ID=9826530

Family Applications (1)

Application Number Title Priority Date Filing Date
GB7095/67A Expired GB1173063A (en) 1967-02-14 1967-02-14 Novel Polyene Compounds and a process for the manufacture and conversion thereof

Country Status (1)

Country Link
GB (1) GB1173063A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2355819A1 (en) * 1975-06-09 1978-01-20 Hoffmann La Roche PROCESS FOR THE PREPARATION OF OXOCYCLIC COMPOUNDS
EP0004621A3 (en) * 1978-03-27 1980-04-16 F.Hoffmann-La Roche & Co. Aktiengesellschaft Process for the multi-step preparation of zeaxanthine and alloxanthine starting from derivatives of cyclohexanon and cyclohexanol; derivatives of cyclohexanon and cyclohexanol
US4532355A (en) * 1973-03-30 1985-07-30 Hoffmann-La Roche Inc. Substituted triaryl phosphonium derivatives
EP0454002A3 (en) * 1990-04-27 1992-05-06 F. Hoffmann-La Roche Ag Dehydration process
US6103940A (en) * 1997-06-04 2000-08-15 Basf Aktiengesellschaft Preparation of zeaxanthin, intermediates for this preparation, and the preparation thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4532355A (en) * 1973-03-30 1985-07-30 Hoffmann-La Roche Inc. Substituted triaryl phosphonium derivatives
FR2355819A1 (en) * 1975-06-09 1978-01-20 Hoffmann La Roche PROCESS FOR THE PREPARATION OF OXOCYCLIC COMPOUNDS
EP0004621A3 (en) * 1978-03-27 1980-04-16 F.Hoffmann-La Roche & Co. Aktiengesellschaft Process for the multi-step preparation of zeaxanthine and alloxanthine starting from derivatives of cyclohexanon and cyclohexanol; derivatives of cyclohexanon and cyclohexanol
EP0454002A3 (en) * 1990-04-27 1992-05-06 F. Hoffmann-La Roche Ag Dehydration process
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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Legal Events

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PS Patent sealed
PLNP Patent lapsed through nonpayment of renewal fees