DK2957565T3 - Fremgangsmåder til fremstilling af lycopener ud fra C-15-Wittig-salte og fremgangsmåder til oprensning af C15-Wittig-salte med højt all-E-indhold og højt 6Z-indhold - Google Patents
Fremgangsmåder til fremstilling af lycopener ud fra C-15-Wittig-salte og fremgangsmåder til oprensning af C15-Wittig-salte med højt all-E-indhold og højt 6Z-indhold Download PDFInfo
- Publication number
- DK2957565T3 DK2957565T3 DK14172968.1T DK14172968T DK2957565T3 DK 2957565 T3 DK2957565 T3 DK 2957565T3 DK 14172968 T DK14172968 T DK 14172968T DK 2957565 T3 DK2957565 T3 DK 2957565T3
- Authority
- DK
- Denmark
- Prior art keywords
- wittig salts
- wittig
- salts
- cis
- lycopene
- Prior art date
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- 150000003839 salts Chemical class 0.000 title claims description 95
- 239000001751 lycopene Substances 0.000 title claims description 73
- 229960004999 lycopene Drugs 0.000 title claims description 72
- 235000012661 lycopene Nutrition 0.000 title claims description 54
- OAIJSZIZWZSQBC-GYZMGTAESA-N lycopene 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\C=C(/C)CCC=C(C)C OAIJSZIZWZSQBC-GYZMGTAESA-N 0.000 title claims description 49
- UPYKUZBSLRQECL-UKMVMLAPSA-N Lycopene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1C(=C)CCCC1(C)C)C=CC=C(/C)C=CC2C(=C)CCCC2(C)C UPYKUZBSLRQECL-UKMVMLAPSA-N 0.000 title claims description 46
- JEVVKJMRZMXFBT-XWDZUXABSA-N Lycophyll Natural products OC/C(=C/CC/C(=C\C=C\C(=C/C=C/C(=C\C=C\C=C(/C=C/C=C(\C=C\C=C(/CC/C=C(/CO)\C)\C)/C)\C)/C)\C)/C)/C JEVVKJMRZMXFBT-XWDZUXABSA-N 0.000 title claims description 45
- ZCIHMQAPACOQHT-ZGMPDRQDSA-N trans-isorenieratene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/c1c(C)ccc(C)c1C)C=CC=C(/C)C=Cc2c(C)ccc(C)c2C ZCIHMQAPACOQHT-ZGMPDRQDSA-N 0.000 title claims description 45
- 238000000034 method Methods 0.000 title claims description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 72
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 66
- 239000000203 mixture Substances 0.000 claims description 54
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 33
- 239000000010 aprotic solvent Substances 0.000 claims description 31
- 238000003786 synthesis reaction Methods 0.000 claims description 27
- 230000015572 biosynthetic process Effects 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 11
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007239 Wittig reaction Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000001914 filtration Methods 0.000 description 19
- 150000004714 phosphonium salts Chemical class 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 150000002664 lycopenes Chemical class 0.000 description 8
- 241000235553 Blakeslea trispora Species 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- HNZUNIKWNYHEJJ-UHFFFAOYSA-N geranyl acetone Natural products CC(C)=CCCC(C)=CCCC(C)=O HNZUNIKWNYHEJJ-UHFFFAOYSA-N 0.000 description 7
- JXJIQCXXJGRKRJ-KOOBJXAQSA-N pseudoionone Chemical compound CC(C)=CCC\C(C)=C\C=C\C(C)=O JXJIQCXXJGRKRJ-KOOBJXAQSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000003556 assay Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000012266 salt solution Substances 0.000 description 5
- 239000011877 solvent mixture Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- AYODHZHFDRRQEZ-UHFFFAOYSA-N 2,7-dimethylocta-2,4,6-trienedial Chemical compound O=CC(C)=CC=CC=C(C)C=O AYODHZHFDRRQEZ-UHFFFAOYSA-N 0.000 description 4
- 241000227653 Lycopersicon Species 0.000 description 4
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 235000021466 carotenoid Nutrition 0.000 description 3
- 150000001747 carotenoids Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- QSGIPTUSRASGRK-UHFFFAOYSA-M triphenyl(3,7,11-trimethyldodeca-2,4,6,10-tetraenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC=C(C)C=CC=C(C)CCC=C(C)C)C1=CC=CC=C1 QSGIPTUSRASGRK-UHFFFAOYSA-M 0.000 description 3
- UIMSQVVHHIUQOZ-UHFFFAOYSA-N 3,7,11-trimethyldodeca-1,4,6,10-tetraen-3-ol Chemical compound CC(C)=CCCC(C)=CC=CC(C)(O)C=C UIMSQVVHHIUQOZ-UHFFFAOYSA-N 0.000 description 2
- 241000219109 Citrullus Species 0.000 description 2
- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 description 2
- OAIJSZIZWZSQBC-OUUYXACASA-N cis-lycopene Natural products CC(=CCCC(=CC=CC(=C/C=C/C(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C=C(C)/CCC=C(C)C)/C)C)C)C OAIJSZIZWZSQBC-OUUYXACASA-N 0.000 description 2
- 208000029078 coronary artery disease Diseases 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 210000003679 cervix uteri Anatomy 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical compound ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 208000024348 heart neoplasm Diseases 0.000 description 1
- IJMWREDHKRHWQI-UHFFFAOYSA-M magnesium;ethene;chloride Chemical compound [Mg+2].[Cl-].[CH-]=C IJMWREDHKRHWQI-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 210000002307 prostate Anatomy 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 210000003491 skin Anatomy 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 210000003932 urinary bladder Anatomy 0.000 description 1
Classifications
-
- 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
- C07F9/5449—Polyphosphonium compounds
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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Claims (14)
1. Fremgangsmåde til oprensning af C15-Wittig-salte, der kan anvendes til syntese af lycopener for at opnå høje all-E-indhold, omfattende de følgende trin: at opnå en cis/trans-blanding af C15-Wittig-salte, at oprense cis-/trans-blandingen af C15-Wittig-salte for at fjerne opløsningsmidler; at tilsætte et aprotisk opløsningsmiddel til cis/trans-blandingen af C15-Wittig-salte ved en temperatur på 0°C til 55°C for at ekstrahere 6Z-C15-Wittig-salte fra blandingen; at fjerne 6Z-C15-Wittig-saltene fra blandingen for at opnå rester; og at oprense de opnåede rester for at opnå C15-Wittig-salte med høje all-E- indhold; kendetegnet ved, at det aprotiske opløsningsmiddel omfatter acetone.
2. Fremgangsmåde til oprensning af C15-Wittig-salte, der kan anvendes til syntese af lycopener for at opnå høje 6Z-indhold, omfattende de følgende trin: at opnå en cis/trans-blanding af C15-Wittig-salte, at oprense cis-/trans-blandingen af C15-Wittig-salte for at fjerne opløsningsmidler; at tilsætte et aprotisk opløsningsmiddel til cis/trans-blandingen af C15-Wittig-salte ved en temperatur på 0°C til 55°C for at ekstrahere 6Z-C15-Wittig-salte fra blandingen; og at oprense 6Z-C15-Wittig-saltene for at opnå C15-Wittig-salte med høje 6Z-indhold; kendetegnet ved, at det aprotiske opløsningsmiddel omfatter acetone.
3. Fremgangsmåde ifølge krav 1 eller 2, hvor oprensningen af cis/trans-blandingen af C15-Wittig-salte omfatter at tilsætte et aprotisk opløsningsmiddel til cis/trans-blandingen af C15-Wittig-salte og at omrøre sammensætningen ved 30°C i over 10 timer.
4. Fremgangsmåde ifølge krav 3, hvor det aprotiske opløsningsmiddel til oprensning af cis/trans-blandingen af C15-Wittig-salte omfatter mindst en ud valgt fra gruppen bestående af ethylacetat, chloroform, acetone, methylethyl-keton og methylisobutylketon.
5. Fremgangsmåde ifølge krav 4, hvor det aprotiske opløsningsmiddel til oprensning af cis/trans-blandingen af C15-Wittig-salte omfatter ethylacetat.
6. Fremgangsmåde ifølge krav 1, hvor oprensningen af resten omfatter at tilsætte et aprotisk opløsningsmiddel til cis/trans-blandingen af C15-Wittig-salte og at omrøre sammensætningen ved 25°C til -30°C i over 10 timer.
7. Fremgangsmåde ifølge krav 6, hvor det aprotiske opløsningsmiddel til oprensning af rest omfatter mindst en udvalgt fra gruppen bestående af ethylacetat, chloroform, acetone, methylethylketon og methylisobutylketon.
8. Fremgangsmåde ifølge krav 7, hvor det aprotiske opløsningsmiddel til oprensning af resten omfatter ethylacetat.
9. Fremgangsmåde ifølge krav 1 eller 2, hvor cis/trans-blandingen af C15-Wittig-salte opnås ved at reagere vinyl-pseudoionol og triphenylphosphin med en uorganisk eller organisk syre.
10. Fremgangsmåde ifølge krav 9, hvor den uorganiske eller organiske syre er mindst en udvalgt fra gruppen bestående af hydrochlorsyre, hydrobromsy-re, svovlsyre, phosphorsyre og sulfonsyre.
11. Fremgangsmåde ifølge krav 2, hvor oprensningen af 6Z-C15-Wittig-saltene omfatter at tilsætte et aprotisk opløsningsmiddel til cis/trans-blandingen af C15-Wittig-salte og at omrøre sammensætningen ved 0°C til 55°C, for at opnå krystalliserede 6Z-C15-Wittig-salte.
12. Fremgangsmåde ifølge krav 11, hvor det aprotiske opløsningsmiddel til oprensning af 6Z-C15-Wittig-salte omfatter acetone.
13. Fremgangsmåde ifølge et af kravene 1-12, yderligere omfattende et trin, hvor de opnåede C15-Wittig-salte reageres med C10-dialdehyd i en dobbelt Wittig-reaktion til syntese af lycopener.
14. Fremgangsmåde ifølge krav 13, hvor syntesereaktionen udføres i en basisk reaktant.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP14172968.1A EP2957565B1 (en) | 2014-06-18 | 2014-06-18 | 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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DK2957565T3 true DK2957565T3 (da) | 2018-05-22 |
Family
ID=50943216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK14172968.1T DK2957565T3 (da) | 2014-06-18 | 2014-06-18 | Fremgangsmåder til fremstilling af lycopener ud fra C-15-Wittig-salte og fremgangsmåder til oprensning af C15-Wittig-salte med højt all-E-indhold og højt 6Z-indhold |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP2957565B1 (da) |
| DK (1) | DK2957565T3 (da) |
| ES (1) | ES2670671T3 (da) |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1041904B (it) | 1974-08-21 | 1980-01-10 | Hoffmann La Roche | Procedimento per la preparazione di derivati del cicloesano otticamente attivi |
| US5166445A (en) | 1989-02-10 | 1992-11-24 | Hoffman-La Roche Inc. | Method for the manufacture of carotinoids and the novel intermediates |
| US5208381A (en) | 1989-02-10 | 1993-05-04 | Hoffmann-La Roche Inc. | Method for the manufacture of carotinoids and novel intermediates |
| DE4344148A1 (de) | 1993-12-23 | 1995-08-24 | Basf Ag | Verfahren zur Herstellung von 9-(Z)-Retinsäure |
| DE19517422A1 (de) | 1995-05-12 | 1996-11-14 | Basf Ag | Verfahren zur Herstellung von beta-Carotin-Präparaten mit hohem 9(Z)-Gehalt |
| DE19734446A1 (de) | 1997-08-08 | 1999-02-11 | Basf Ag | Verfahren zur Herstellung von Phosphoniumsalzen |
| US6150561A (en) | 1997-10-03 | 2000-11-21 | Roche Vitamins Inc. | Method of making carotenoids |
| DE10009459C1 (de) | 2000-03-02 | 2001-06-07 | Basf Ag | Verfahren zur Herstellung von Phosphoniumsalzen |
| DE10103708A1 (de) | 2001-01-26 | 2002-08-01 | Basf Ag | Thermische Isomerisierung von Lycopin |
| DE10254809A1 (de) | 2002-11-22 | 2004-06-03 | Basf Ag | Verfahren zur Herstellung von Carotinoiden |
-
2014
- 2014-06-18 ES ES14172968.1T patent/ES2670671T3/es active Active
- 2014-06-18 EP EP14172968.1A patent/EP2957565B1/en active Active
- 2014-06-18 DK DK14172968.1T patent/DK2957565T3/da active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2957565B1 (en) | 2018-03-07 |
| EP2957565A1 (en) | 2015-12-23 |
| ES2670671T3 (es) | 2018-05-31 |
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