GB1508195A - Process for the manufacture of optically active cyclohexane derivatives - Google Patents
Process for the manufacture of optically active cyclohexane derivativesInfo
- Publication number
- GB1508195A GB1508195A GB34605/75A GB3460575A GB1508195A GB 1508195 A GB1508195 A GB 1508195A GB 34605/75 A GB34605/75 A GB 34605/75A GB 3460575 A GB3460575 A GB 3460575A GB 1508195 A GB1508195 A GB 1508195A
- Authority
- GB
- United Kingdom
- Prior art keywords
- hydroxy
- give
- retinyl
- converted
- halide
- 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
Links
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 title 1
- 150000004820 halides Chemical class 0.000 abstract 15
- 239000001775 zeaxanthin Substances 0.000 abstract 10
- 229940043269 zeaxanthin Drugs 0.000 abstract 10
- 229960000342 retinol acetate Drugs 0.000 abstract 9
- 239000011770 retinyl acetate Substances 0.000 abstract 9
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 abstract 7
- 238000006317 isomerization reaction Methods 0.000 abstract 7
- QPRQNCDEPWLQRO-ZCEAMUHZSA-N (3R)-all-trans-3-hydroxyretinal Chemical compound O=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)C[C@@H](O)CC1(C)C QPRQNCDEPWLQRO-ZCEAMUHZSA-N 0.000 abstract 5
- 239000002253 acid Substances 0.000 abstract 5
- 238000006243 chemical reaction Methods 0.000 abstract 5
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 5
- 239000011707 mineral Substances 0.000 abstract 5
- 239000004212 Cryptoxanthin Substances 0.000 abstract 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 4
- OBODKGDXEIUEIH-ZCEAMUHZSA-N (1r)-4-[(1e,3e,5e,7e)-9-hydroxy-3,7-dimethylnona-1,3,5,7-tetraenyl]-3,5,5-trimethylcyclohex-3-en-1-ol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)C[C@@H](O)CC1(C)C OBODKGDXEIUEIH-ZCEAMUHZSA-N 0.000 abstract 3
- 150000001298 alcohols Chemical class 0.000 abstract 3
- 230000002207 retinal effect Effects 0.000 abstract 3
- ODZTXUXIYGJLMC-UHFFFAOYSA-N 2-hydroxycyclohexan-1-one Chemical compound OC1CCCCC1=O ODZTXUXIYGJLMC-UHFFFAOYSA-N 0.000 abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract 2
- JKQXZKUSFCKOGQ-LQFQNGICSA-N Z-zeaxanthin Natural products C([C@H](O)CC=1C)C(C)(C)C=1C=CC(C)=CC=CC(C)=CC=CC=C(C)C=CC=C(C)C=CC1=C(C)C[C@@H](O)CC1(C)C JKQXZKUSFCKOGQ-LQFQNGICSA-N 0.000 abstract 2
- QOPRSMDTRDMBNK-RNUUUQFGSA-N Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCC(O)C1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C QOPRSMDTRDMBNK-RNUUUQFGSA-N 0.000 abstract 2
- JKQXZKUSFCKOGQ-LOFNIBRQSA-N all-trans-Zeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)CC(O)CC2(C)C JKQXZKUSFCKOGQ-LOFNIBRQSA-N 0.000 abstract 2
- 235000002360 beta-cryptoxanthin Nutrition 0.000 abstract 2
- DMASLKHVQRHNES-ITUXNECMSA-N beta-cryptoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)CCCC2(C)C DMASLKHVQRHNES-ITUXNECMSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 235000019244 cryptoxanthin Nutrition 0.000 abstract 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract 2
- -1 phosphonium halide Chemical class 0.000 abstract 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 2
- KBPHJBAIARWVSC-XQIHNALSSA-N trans-lutein Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CC(O)CC1(C)C)C=CC=C(/C)C=CC2C(=CC(O)CC2(C)C)C KBPHJBAIARWVSC-XQIHNALSSA-N 0.000 abstract 2
- 235000010930 zeaxanthin Nutrition 0.000 abstract 2
- CSPVUHYZUZZRGF-RNFRBKRXSA-N (4R,6R)-hydroxy-2,2,6-trimethylcyclohexanone Chemical compound C[C@@H]1C[C@@H](O)CC(C)(C)C1=O CSPVUHYZUZZRGF-RNFRBKRXSA-N 0.000 abstract 1
- NNHZRFWALNMRKS-YLXHPXFOSA-N (4r,6r)-1-(3-hydroxybut-1-ynyl)-2,2,6-trimethylcyclohexane-1,4-diol Chemical compound CC(O)C#CC1(O)[C@H](C)C[C@@H](O)CC1(C)C NNHZRFWALNMRKS-YLXHPXFOSA-N 0.000 abstract 1
- AYJXHIDNNLJQDT-UHFFFAOYSA-N 2,6,6-Trimethyl-2-cyclohexene-1,4-dione Chemical compound CC1=CC(=O)CC(C)(C)C1=O AYJXHIDNNLJQDT-UHFFFAOYSA-N 0.000 abstract 1
- UBFBTMRIJJRZOA-UHFFFAOYSA-N 2,7-dimethylocta-2,4,6-triene Chemical compound CC(C)=CC=CC=C(C)C UBFBTMRIJJRZOA-UHFFFAOYSA-N 0.000 abstract 1
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 abstract 1
- QXJSYJRWEUENRT-PSAUJTBTSA-N 4,9-dimethyldodeca-2,4,6,8,10-pentaenedial Chemical compound O=C/C=C/C(/C)=C/C=C/C=C(\C)/C=C/C=O QXJSYJRWEUENRT-PSAUJTBTSA-N 0.000 abstract 1
- WFLRJRATQLPRDT-UHFFFAOYSA-N 4,9-dimethyldodeca-2,4,8,10-tetraen-6-ynedial Chemical compound O=CC=CC(C)=CC#CC=C(C)C=CC=O WFLRJRATQLPRDT-UHFFFAOYSA-N 0.000 abstract 1
- PCYSRECLJVMEPX-UHFFFAOYSA-N 8,8-diethoxy-3,7-dimethylocta-2,4,6-trienal Chemical compound CCOC(OCC)C(C)=CC=CC(C)=CC=O PCYSRECLJVMEPX-UHFFFAOYSA-N 0.000 abstract 1
- 101000653791 Bos taurus Protein S100-A12 Proteins 0.000 abstract 1
- SPBPMWXNKPPVSX-KXOLNMLNSA-N Citraurin Natural products CC(=C/C=C/C(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=CC(O)CC1(C)C)C)/C)C=O SPBPMWXNKPPVSX-KXOLNMLNSA-N 0.000 abstract 1
- TXHARUYWUGDGQT-WPZCJLIBSA-N [(1r)-4-(3-acetyloxybut-1-ynyl)-3,5,5-trimethylcyclohex-3-en-1-yl] acetate Chemical compound CC(=O)OC(C)C#CC1=C(C)C[C@@H](OC(C)=O)CC1(C)C TXHARUYWUGDGQT-WPZCJLIBSA-N 0.000 abstract 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract 1
- 150000001241 acetals Chemical class 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- LQAJUQDHCUNJJY-OVWFGJEDSA-N all-trans-1,6-seco-1,2-didehydroretinal Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=O LQAJUQDHCUNJJY-OVWFGJEDSA-N 0.000 abstract 1
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 abstract 1
- 150000001746 carotenes Chemical class 0.000 abstract 1
- 235000005473 carotenes Nutrition 0.000 abstract 1
- 235000021466 carotenoid Nutrition 0.000 abstract 1
- 150000001747 carotenoids Chemical class 0.000 abstract 1
- 150000001934 cyclohexanes Chemical class 0.000 abstract 1
- 229930002839 ionone Natural products 0.000 abstract 1
- 150000002499 ionone derivatives Chemical class 0.000 abstract 1
- HVHHZSFNAYSPSA-ZCFIWIBFSA-N levodione Chemical compound C[C@@H]1CC(=O)CC(C)(C)C1=O HVHHZSFNAYSPSA-ZCFIWIBFSA-N 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- ABTRFGSPYXCGMR-AXXBKCDFSA-N rubixanthin Chemical compound CC(C)=CCC\C(C)=C\C=C\C(\C)=C\C=C\C(\C)=C\C=C\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)C[C@@H](O)CC1(C)C ABTRFGSPYXCGMR-AXXBKCDFSA-N 0.000 abstract 1
Classifications
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- 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
- 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
- C07C403/02—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 containing only carbon and hydrogen 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
- C07C403/08—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
- C07C403/14—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
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- 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
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- 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
- C07C45/64—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 introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/385—Saturated compounds containing a keto group being part of a ring
- C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
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- 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
- C07F9/5428—Acyclic unsaturated phosphonium compounds
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
- C12P7/26—Ketones
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- 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
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- 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)
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- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Biotechnology (AREA)
- Molecular Biology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- Genetics & Genomics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
1508195 Cyclohexane derivatives; carotenes F HOFFMANN-LA ROCHE & CO AG 20 Aug 1975 [21 Aug 1974 1 Nov 1974] 34605/75 Headings C2C C2V and C2P The invention comprises [6R]-2,2,6-trimethyl- 1,4-cyclohexanedione and [4R,6R]-4-hydroxy- 2,2,6 - trimethyl - cyclohexanone. The dione may be prepared by fermentatively hydrogenating ketoisophorone. The dione may be reduced to give the hydroxy cyclohexanone which may then be converted to an optically active carotenoid. Thus the hydroxy cyclohexanone is reacted with isopropenylmethyl ether to give [4R, 4<SP>1</SP>R] - 4,4<SP>1</SP> - (isopropylidenedioxy) - bis - {[6R] - 2,2,6 - trimethylcyclohexanone}, the product is reacted with but-3-yn-2-ol, the resulting 2 - hydroxy - 4 - {[4R,6R] - 1,4 - dihydroxy - 2,2,6 - trimethyl - cyclohex - 1 - yl} - but-3-yne is acetylated to give 2-acetoxy-4- {[4R,6R] - acetoxy - 1 - hydroxy - 2,2,6 - trimethylcyclohex - 1 - yl} - but - 3 - yne, said diacetate is dehydrated to give 2-acetoxy-4- {[4R] - 4 - acetoxy - 2,6,6 - trimethyl - cyclohex- 1 - en - 1 - yl} - but - 3 - yne and the acetylenic bond present is hydrogenated to an ethylenic bond, the resulting [3R]-3-hydroxy-#-ionol is converted by reaction with a triarylphosphonium halide or with a triaryl phosphine in the presence of a mineral acid into a 4-{[4R]-4- hydroxy - 2,6,6 - trimethyl - cyclohex - 1 - en - 1- yl} -but-3-ene-2-triarylphosphonium halide and this Wittig salt is condensed with l-acetoxy-3- methyl - hexa - 2,4 - dien - 6 - al to give [3R]- 3-hydroxy-retinyl acetate, the cis form obtained is converted into the trans form by isomerization, the one half of the [3R]-3-hydroxy-retinyl acetate is converted by reaction with a triarylphosphonium halide or with a triaryl phosphine in the presence of a mineral acid into a [3R]-3- hydroxy - retinyl - triarylphosphonium halide and the other half of the [3R]-3-hydroxy-retinyl acetate is saponified to give [3R]-3-hydroxyretinol and this alcohol is oxidized to give [3R]- 3 - hydroxy - retinal whereafter said [3R] - 3- hydroxy-retinyl-triarylphosphonium halide is either condensed with retinal or with [3R]-3- hydroxy-retinal to give [3R]-#-cryptoxanthin or [3R,31R] - zeaxanthin. Alternatively the Wittig salt 4 - {[4R] - 4 - hydroxy - 2,6,6 - trimethyl - cyclohex - 1 - en - 1 - yl} - but - 3 - ene- 2-triarylphosphonium halide is condensed with (a) 4,9 - dimethyl - dodeca - 2,4,8,10 - tetraen- 6-yne-1,12-dial and the resulting [3R,31R]- 15,15<SP>1</SP>-didehydro-zeaxanthin, after isomerization of cis form obtained to trans form, is converted by partial hydrogenation into [3R,3<SP>1</SP>R]- zeaxanthin, or (b) 4,9-dimethyl-dodeca-2,4,6,8, 10-pentaene-1,12-dial to give [3R,3<SP>1</SP>R]-zeaxanthin and cis form obtained is converted into trans form by isomerization. In a further alternative [3R]-3-hydroxy-#-ionol is converted by oxidation into [3R]-3-hydroxy-#-ionone, said ionone is reacted with an alkali metal acetylide to give [3R] - 3 - hydroxy - ethynyl - # - ionol, this latter compound is catalytically hydrogenated and the resulting [3R]-3-hydroxy-vinyl-#-ionol is converted by reaction with a triarylphosphonium halide or with a triarylphosphine in the presence of a mineral acid into a [3R]-3- hydroxy - # - ionylidenethyl - triaryl - phosphonium halide, said phosphonium halide is condensed with (a) 2,7-dimethyl-octa-2,4-dien-4- yne-1,10-dial and the resulting [3R,3<SP>1</SP>R]-15,15<SP>1</SP>- didehydro-zeaxanthin, after isomerisation of cis form obtained to trans form, is converted by partial hydrogenation into [3R,3<SP>1</SP>R]-zeaxanthin or (b) 2,7-dimethylocta - 2,4,6 - triene - 1,10 - dial to give [3R,3<SP>1</SP>R]-zeaxanthin and cis form obtained is converted into trans form by isomerization. In a further alternative the [3R]-3-hydroxy-#- ionylidenethyl-triaryl phosphonium halide is reacted with γ-acetoxytiglic aldehyde to give [3R]-3-hydroxy-retinyl acetate, cis form obtained is converted into trans form by isomerization, the one half of the [3R]-3-hydroxy-retinyl acetate is converted by reaction with a triarylphosphonium halide or with a triarylphosphine in the presence of a mineral acid into a [3R]-3- hydroxy - retinyl - triarylphosphonium halide and the other half of the [3R]-3-hydroxyretinyl acetate is saponified to give [3R]-3- hydroxy-retinol and this alcohol is oxidized to give [3R] - 3 - hydroxy - retinyl, whereafter said [3R] - 3 - hydroxy - retinyl - triarylphosphonium halide is either condensed with retinal or with [3R]-3-hydroxy-retinal to give [3R]-#- cryptoxanthin or [3R,3<SP>1</SP>R]-zeaxanthin. In a further alternative a [3R]-3-hydroxy-#-ionylidenethyl - triaryl - phosphonium halide is reacted with γ-acetoxy-tiglic aldehyde to give [3R]-3-hydroxy-retinyl acetate, said acetate is acetylated to give [3R]-3-acetoxy-retinyl acetate, cis form obtained is converted into trans form by isomerization, the one half of the [3R]-3- acetoxy-retinyl acetate is converted by reaction with a triarylphosphonium halide or with atriarylphosphine in the presence of a mineral acid into a [3R] - 3 - acetoxy - retinyl - triarylphosphonium halide and the other half of the [3R]-3- acetoxy-retinyl acetate is saponified to give [3R]-3-hydroxy-retinol and this alcohol is oxidized to give [3R]-3-hydroxy-retinal; whereafter said [3R] - 3 - acetoxy - retinyl - triarylphosphonium halide is reacted either with retinal or with [3R]-3-hydroxy-retinal to give [3R]-O-acetyl-#-cryptoxanthin or [3R,31R]- O-acetyl-zeaxanthin respectively and the latter compounds are saponified to give [3R]-#- cryptoxanthin or [3R,3<SP>1</SP>R]-zeaxanthin respectively. [3R]-Rubixanthin may be prepared by condensing a [3R]-3-hydroxy-retinyl-triarylphosphonium halide with γ-retinal. [3R]-#- Citraurin may be prepared by condensing a [3R] - 3 - hydroxy - retinyl - triarylphosphonium halide with 1,1 - diethoxy - 2,6 - dimethylocta - 2,4,6 - trien - 8 - al and saponifying the acetal obtained. [3R]-Reticulataxanthin may be prepared by condensing [3R]-#-citraurin with acetone.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH1143474A CH605533A5 (en) | 1974-08-21 | 1974-08-21 | |
CH1467474 | 1974-11-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1508195A true GB1508195A (en) | 1978-04-19 |
Family
ID=25708324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB34605/75A Expired GB1508195A (en) | 1974-08-21 | 1975-08-20 | Process for the manufacture of optically active cyclohexane derivatives |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPS587277B2 (en) |
AT (1) | AT347422B (en) |
DE (1) | DE2537060C3 (en) |
FR (3) | FR2303797A1 (en) |
GB (1) | GB1508195A (en) |
IT (1) | IT1041904B (en) |
NL (1) | NL169195C (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1293493A2 (en) * | 2001-09-13 | 2003-03-19 | Basf Aktiengesellschaft | Process for the preparation of meso-zeaxanthine |
EP2957565B1 (en) | 2014-06-18 | 2018-03-07 | Allied Biotech Corporation | Methods for preparation of lycopenes from C-15 Wittig salts and methods for purification of high all-E containing and high 6Z containing C15-Wittig salts |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4000198A (en) * | 1975-06-09 | 1976-12-28 | Hoffmann-La Roche Inc. | Hydroxy-acetylene-substituted cyclohexenone |
JPS61105975U (en) * | 1984-12-14 | 1986-07-05 | ||
DE19543619A1 (en) | 1995-11-23 | 1997-05-28 | Basf Ag | Process for the pure preparation of trans- and cis-4-hydroxy-2,2,6-trimethyl-cyclohexan-l-one from isomer mixtures |
DE19723480A1 (en) * | 1997-06-04 | 1998-12-10 | Basf Ag | Process for the preparation of zeaxanthin, intermediates for this process and process for its preparation |
ES2259224T3 (en) * | 1998-08-19 | 2006-09-16 | Dsm Ip Assets B.V. | ACTINOL MICROBIAL PRODUCTION. |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1167712A (en) * | 1955-07-22 | 1958-11-28 | Hoffmann La Roche | Process for the preparation of carotenoids |
FR1210619A (en) * | 1955-08-31 | 1960-03-09 | Hoffmann La Roche | Process for the preparation of carotenoids |
FR1165058A (en) * | 1955-10-11 | 1958-10-17 | Hoffmann La Roche | Process for the preparation of cyclic ketones |
-
1975
- 1975-08-18 IT IT7526389A patent/IT1041904B/en active
- 1975-08-19 FR FR7525631A patent/FR2303797A1/en active Granted
- 1975-08-19 JP JP50099888A patent/JPS587277B2/en not_active Expired
- 1975-08-20 AT AT645575A patent/AT347422B/en not_active IP Right Cessation
- 1975-08-20 DE DE2537060A patent/DE2537060C3/en not_active Expired
- 1975-08-20 GB GB34605/75A patent/GB1508195A/en not_active Expired
- 1975-08-21 NL NLAANVRAGE7509925,A patent/NL169195C/en not_active IP Right Cessation
-
1976
- 1976-06-03 FR FR7616822A patent/FR2303798A1/en active Granted
- 1976-06-03 FR FR7616821A patent/FR2303786A1/en active Granted
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1293493A2 (en) * | 2001-09-13 | 2003-03-19 | Basf Aktiengesellschaft | Process for the preparation of meso-zeaxanthine |
EP1293493A3 (en) * | 2001-09-13 | 2003-07-09 | Basf Aktiengesellschaft | Process for the preparation of meso-zeaxanthine |
US6743954B2 (en) | 2001-09-13 | 2004-06-01 | Basf Aktiengesellschaft | Process for the preparation of meso-zeaxanthin |
US6747177B2 (en) | 2001-09-13 | 2004-06-08 | Basf Aktiengesellschaft | Process for the preparation of meso-zeaxanthin |
EP2957565B1 (en) | 2014-06-18 | 2018-03-07 | Allied Biotech Corporation | Methods for preparation of lycopenes from C-15 Wittig salts and methods for purification of high all-E containing and high 6Z containing C15-Wittig salts |
Also Published As
Publication number | Publication date |
---|---|
FR2303797A1 (en) | 1976-10-08 |
ATA645575A (en) | 1978-05-15 |
DE2537060A1 (en) | 1976-03-04 |
DE2537060C3 (en) | 1980-01-17 |
FR2303797B1 (en) | 1980-07-25 |
JPS5182789A (en) | 1976-07-20 |
FR2303798A1 (en) | 1976-10-08 |
FR2303786B1 (en) | 1980-05-30 |
NL169195B (en) | 1982-01-18 |
DE2537060B2 (en) | 1979-05-23 |
IT1041904B (en) | 1980-01-10 |
NL169195C (en) | 1982-06-16 |
FR2303786A1 (en) | 1976-10-08 |
NL7509925A (en) | 1976-02-24 |
JPS587277B2 (en) | 1983-02-09 |
FR2303798B1 (en) | 1982-10-29 |
AT347422B (en) | 1978-12-27 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed | ||
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19920820 |