CN100338004C - Process for preparing cantharis yellow - Google Patents
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- CN100338004C CN100338004C CNB200510062146XA CN200510062146A CN100338004C CN 100338004 C CN100338004 C CN 100338004C CN B200510062146X A CNB200510062146X A CN B200510062146XA CN 200510062146 A CN200510062146 A CN 200510062146A CN 100338004 C CN100338004 C CN 100338004C
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- canthaxanthin
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- canthaxanthine
- drip
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- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 241000131283 Cantharis Species 0.000 title 1
- FDSDTBUPSURDBL-LOFNIBRQSA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1/C=C/C(/C)=C/C=C/C(/C)=C/C=C/C=C(C)C=CC=C(C)C=CC1=C(C)C(=O)CCC1(C)C FDSDTBUPSURDBL-LOFNIBRQSA-N 0.000 claims abstract description 77
- 235000012682 canthaxanthin Nutrition 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- OOUTWVMJGMVRQF-DOYZGLONSA-N Phoenicoxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(=O)C(O)CC1(C)C)C=CC=C(/C)C=CC2=C(C)C(=O)CCC2(C)C OOUTWVMJGMVRQF-DOYZGLONSA-N 0.000 claims abstract description 36
- 229940008033 canthaxanthin Drugs 0.000 claims abstract description 36
- 239000001659 canthaxanthin Substances 0.000 claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000012044 organic layer Substances 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 230000002829 reductive effect Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 150000001707 canthaxanthins Chemical class 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- -1 washing Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- FDSDTBUPSURDBL-DKLMTRRASA-N canthaxanthin Chemical compound CC=1C(=O)CCC(C)(C)C=1\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(=O)CCC1(C)C FDSDTBUPSURDBL-DKLMTRRASA-N 0.000 abstract 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract 2
- 239000007818 Grignard reagent Substances 0.000 abstract 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 abstract 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 abstract 1
- 230000007935 neutral effect Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 9
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000000178 monomer Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000007239 Wittig reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- VRLIPUYDFBXWCH-UHFFFAOYSA-N hydridocarbon(.) Chemical compound [CH] VRLIPUYDFBXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- GYZWNQLEQAGWGD-DKLMTRRASA-N Isozeaxanthin Chemical compound CC=1C(O)CCC(C)(C)C=1\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(O)CCC1(C)C GYZWNQLEQAGWGD-DKLMTRRASA-N 0.000 description 1
- GYZWNQLEQAGWGD-LOFNIBRQSA-N all-trans-Isozeaxanthin Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)C(O)CCC1(C)C)C=CC=C(/C)C=CC2=C(C)C(O)CCC2(C)C GYZWNQLEQAGWGD-LOFNIBRQSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HTSABYAWKQAHBT-UHFFFAOYSA-N trans 3-methylcyclohexanol Natural products CC1CCCC(O)C1 HTSABYAWKQAHBT-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to a process for preparing canthaxanthin, which comprises the following procedures: 1) C22 enyne (Q) is used as an initial raw material, the Grignard exchange reaction of C22 enyne (Q) and C2H5MgBr is firstly carried out in a tetrahydrofuran solvent to prepare a double C22 enyne Grignard reagent (B), temperature is increased, the tetrahydrofuran solution of a compound (A) is dropped, the temperature is maintained after dropping is finished, the temperature is lowered, dilute sulfuric acid with the concentration of 10% is dropped to the reaction liquid until the pH value is lower than 3, the reaction liquid is extracted and washed with water, and pressure is reduced for solvent removal to obtain didehydro canthaxanthine (C); 2) didehydro canthaxanthine (C) is dissolved in CH2Cl2 or CHCl3, the solution is cooled and is stirred violently while excessive zinc powder is added, excessive acetic acid is dropped, and temperature is maintained after dropping is finished; the solution is filtered, the filtrate is neutralized to be neutral, an organic layer is separated out, washed with water, dried, concentrated under reduced pressure and crystallized, the crystal is filtered, and the filter residue is dried to obtain the product canthaxanthine (D). The present invention has the advantages that the C22 enyne double Grignard reagent is adopted as an initial raw material, canthaxanthine is synthesized by two reactions, and the total yield is high; in the synthesis of canthaxanthine, the selectivity of the reaction is good; the process has simple technology and convenient operation.
Description
Technical field
The present invention relates to a kind of preparation method of canthaxanthin.
Background technology
Canthaxanthin is a kind of in the carotenoid, and natural canthaxanthin is present in some mushroom, crustaceans, fish, algae, egg, blood, the liver, and canthaxanthin is mainly used in the breed of bird.The synthetic method of bibliographical information canthaxanthin mainly contains following several:
1.Jaedicke Deng having proposed the synthetic canthaxanthin (D) of one-step oxidation process [US 4212827 (1977), and DE 2657477 (1978)], this route obtains canthaxanthin by isozeaxanthin (E) by oxidizing reaction.Reaction formula is as follows:
In addition, US 4212827/1977 also has report that β-Hu Luobusu (F) is obtained canthaxanthin, yield 70% with one step of sodium chlorate oxidation.
Though these two kinds of method reactions steps are short, processing ease; But shortcoming is that impurity in products is many by (E) to (D) and (F) many to the oxygen of (D) reaction side reaction, and purification ratio is difficulty.
2.Rosenberger Deng the C that proposes
15+ C
10+ C
15Route [PureAppl.Chem.51 (4), 871-86,1979], this route are reported that by Roche company α-Zi Luolantong (G) and six carbyne alcohol carry out condensation reaction and obtain C
15Monomer (H), two molecule C then
15Monomer (H) and a part C
10Dialdehyde (I) obtains canthaxanthin (D) through the Wittig reaction.Reaction formula is as follows:
Many, the complicated operation of this route reaction step, total recovery about 40%.
3.Luca Deng the C that proposes
15+ C
10+ C
15Route [EP31875], via the synthetic canthaxanthin of Wittig reaction.Corresponding 3-methyl cyclohexanol diketone (K) and six carbyne alcohol (L) carry out condensation reaction and obtain C
15Monomer (M), two molecule C then
15Monomer (H) and a part C
10Dialdehyde (I) carries out the Wittig reaction and obtains canthaxanthin (D).Reaction formula is as follows:
Though this route is the actual production route of Roche company, it is many also to exist reactions steps, shortcomings such as complicated operation.
Summary of the invention
The objective of the invention is the problem that exists in the above-mentioned route, a kind of preparation method of canthaxanthin is provided.The step of method is as follows:
1) with C
22Eneyne (Q) is a starting raw material, elder generation and C under 30-35 ℃ of condition in tetrahydrofuran solvent
2H
5MgBr carries out the Ge Shi permutoid reaction and makes C
22The two Grignard reagents (B) of eneyne are warming up to 50-55 ℃ then, drip the tetrahydrofuran solution of compound (A), drip Bi Baowen 8-12 hour, are cooled to below 20 ℃, drip 10% dilute sulphuric acid then in reaction solution, to PH＜3, use CH
2Cl
2Extraction, CH
2Cl
2Layer is washed to neutrality, and decompression removes CH
2Cl
2, get two dehydrogenation canthaxanthins (C);
2) two dehydrogenation canthaxanthins (C) are dissolved in CH
2Cl
2Or CHCl
3In, be chilled to below 20 ℃, add excessive zinc powder under the violent stirring, drip excessive acetic acid, dripped Bi Baowen 1-2 hour; Solids removed by filtration, filtrate adds 20%Na
2CO
3The aqueous solution is neutralized to neutrality, tells organic layer, washing, organic layer MgSO
4Drying, concentrating under reduced pressure adds the anhydrous diethyl ether crystallization, is cooled to below 20 ℃, filters, and drying gets product canthaxanthin (D);
Its reaction formula is as follows:
Described pair of grignard compound (B) is 1: 2～10 with the mol ratio of compound (A).The mol ratio of two grignard compounds (B) and compound (A) is 1: 3～6 preferable.In the reaction of two dehydrogenation canthaxanthins (C) reduction preparation canthaxanthins (D), used reductive agent is a zinc powder, and reducing medium is an acetic acid, and solvent is CH
2Cl
2Or CHCl
3Solvent is CH
2Cl
2Preferable.
Advantage of the present invention is: 1) adopt C
22The two Grignard reagents of eneyne are starting raw material, through the synthetic canthaxanthin of two-step reaction, total recovery height.2) in canthaxanthin synthetic, good reaction selectivity, by product is few.3) this method technology is simpler, easy to operate.
Embodiment
The present invention adopts following method to synthesize target product canthaxanthin (D): be raw material with two grignard compounds (B) promptly, obtain two dehydrogenation canthaxanthins (C) with compound (A) reaction, obtain canthaxanthin (D) through reduction.
Reaction formula is as follows:
Below in conjunction with embodiment the present invention is described in detail.
Embodiment 1
A. the preparation of two dehydrogenation canthaxanthins (C)
In the 1000ml flask, add THF300ml, Mg 2.6g, the 2g monobromethane, 0.1g iodine, heating makes it to cause, and control reaction temperature is 30～35 ℃ then, drips remaining 12g monobromethane, drips to finish, and insulation reaction is until the Mg completely dissolve.In above-mentioned reaction solution, add 14.4g (0.05mol) C then in batches
22Conjugation diine polyenic compounds (Q) (preparation method sees CN200410073427.0), insulation reaction is until forming uniform viscous soln.Be warming up to 50 ℃, drip the 200ml THF solution that contains 21g (0.10moL) compound (A), drip and finish, insulation reaction 8 hours is cooled to below 20 ℃, drips 10% dilute sulphuric acid 100ml, 3 * 400ml CH then in reaction solution
2Cl
2Extraction, CH
2Cl
2Layer reduces pressure and removes CH with 3 * 400 washings
2Cl
2, get two dehydrogenation canthaxanthin (C) 18.3g, yield 79.5%.
B. the preparation of canthaxanthin (D)
In the 1000ml flask, add two dehydrogenation canthaxanthin (C) 18.3g, CH
2Cl
2400ml, stirring and dissolving is cooled to below 20 ℃, adds the 12g zinc powder under the violent stirring, drips the 60ml Glacial acetic acid, about 1 hour dropping time, drips Bi Baowen 1 hour.The solids removed by filtration thing, filtrate adds 20%Na
2CO
3Be neutralized to neutrality, tell organic layer, 2 * 300ml washing, the anhydrous MgSO of 13g
4Drying is evaporated to 60ml, adds anhydrous diethyl ether 100ml, is cooled to below 20 ℃, filters, and drying gets canthaxanthin (D) 17.2g, yield 93.2%.
Embodiment 2
A. the preparation of two dehydrogenation canthaxanthins (C)
In the 1000ml flask, add THF300ml, Mg 2.6g, the 2g monobromethane, 0.1g iodine, heating makes it to cause, and control reaction temperature is 30～35 ℃ then, drips remaining 12g monobromethane, drips to finish, and insulation reaction is until the Mg completely dissolve.In above-mentioned reaction solution, add 14.4g (0.05mol) C then in batches
22Conjugation diine polyenic compounds (Q), insulation reaction is until forming uniform viscous soln.Be warming up to 50 ℃, drip the 300ml THF solution that contains 42g (0.2mol) compound (A), drip and finish, insulation reaction 8 hours is cooled to below 20 ℃, drips 10% dilute sulphuric acid 100ml, 3 * 400ml CH then in reaction solution
2Cl
2Extraction, CH
2Cl
2Layer reduces pressure and removes CH with 3 * 400 washings
2Cl
2, get two dehydrogenation canthaxanthin (C) 19.6g, yield 85.2%.
B. the preparation of canthaxanthin (D)
In the 1000ml flask, add two dehydrogenation canthaxanthin (C) 19.6g, CHCl
3850ml, stirring and dissolving is cooled to below 20 ℃, adds the 13g zinc powder under the violent stirring, drips the 65ml Glacial acetic acid, about 1 hour dropping time, drips Bi Baowen 1 hour.The solids removed by filtration thing, filtrate adds 20%Na
2CO
3Be neutralized to neutrality, tell organic layer, 2 * 300ml washing, the anhydrous MgSO of 13g
4Drying is evaporated to 90ml, adds anhydrous diethyl ether 100ml, is cooled to below 20 ℃, filters, and drying gets canthaxanthin (D) 18.3g, yield 92.6%.
Embodiment 3
A. the preparation of two dehydrogenation canthaxanthins (C)
In the 1000ml flask, add THF300ml, Mg 2.6g, the 2g monobromethane, 0.1g iodine, heating makes it to cause, and control reaction temperature is 30～35 ℃ then, drips remaining 12g monobromethane, drips to finish, and insulation reaction is until the Mg completely dissolve.In above-mentioned reaction solution, add 14.4g (0.05mol) C then in batches
22Conjugation diine polyenic compounds (Q), insulation reaction is until forming uniform viscous soln.Be warming up to 50 ℃, drip the 500ml THF solution that contains 84g (0.4mol) compound (A), drip and finish, insulation reaction 8 hours is cooled to below 20 ℃, drips 10% dilute sulphuric acid 100ml, 3 * 400ml CH then in reaction solution
2Cl
2Extraction, CH
2Cl
2Layer reduces pressure and removes CH with 3 * 400 washings
2Cl
2, get two dehydrogenation canthaxanthin (C) 20.8g, yield 90.4%.
B. the preparation of canthaxanthin (D)
In the 1000ml flask, add two dehydrogenation canthaxanthin (C) 20.8g, CH
2Cl
2450ml, stirring and dissolving is cooled to below 20 ℃, adds the 14g zinc powder under the violent stirring, drips the 70ml Glacial acetic acid, about 1 hour dropping time, drips Bi Baowen 1 hour.The solids removed by filtration thing, filtrate adds 20%Na
2CO
3Be neutralized to neutrality, tell organic layer, 2 * 300ml washing, the anhydrous MgSO of 13g
4Drying is evaporated to 90ml, adds anhydrous diethyl ether 100ml, is cooled to below 20 ℃, filters, and drying gets canthaxanthin (D) 19.2g, yield 91.5%.
Claims (4)
1. the preparation method of a canthaxanthin is characterized in that, the step of method is as follows:
1) with C
22Eneyne (Q) is a starting raw material, elder generation and C under 30-35 ℃ of condition in tetrahydrofuran solvent
2H
5MgBr carries out the Ge Shi permutoid reaction and makes C
22The two Grignard reagents (B) of eneyne are warming up to 50-55 ℃ then, drip the tetrahydrofuran solution of compound (A), drip Bi Baowen 8-12 hour, are cooled to below 20 ℃, drip 10% dilute sulphuric acid then in reaction solution, to PH＜3, use CH
2Cl
2Extraction, CH
2Cl
2Layer is washed to neutrality, and decompression removes CH
2Cl
2, get two dehydrogenation canthaxanthins (C);
2) two dehydrogenation canthaxanthins (C) are dissolved in CH
2Cl
2Or CHCl
3In, be chilled to below 20 ℃, add excessive zinc powder under the violent stirring, drip excessive acetic acid, dripped Bi Baowen 1-2 hour; Solids removed by filtration, filtrate adds 20%Na
2CO
3The aqueous solution is neutralized to neutrality, tells organic layer, washing, organic layer MgSO
4Drying, concentrating under reduced pressure adds the anhydrous diethyl ether crystallization, is cooled to below 20 ℃, filters, and drying gets product canthaxanthin (D);
Reaction formula is as follows:
2. according to the preparation method of the described a kind of canthaxanthin of claim 1, it is characterized in that two grignard compounds (B) are 1: 2～10 with the mol ratio of compound (A).
3. according to the preparation method of the described a kind of canthaxanthin of claim 1, it is characterized in that two grignard compounds (B) are 1: 3～6 with the mol ratio of compound (A).
4. according to the preparation method of the described a kind of canthaxanthin of claim 1 (D), it is characterized in that in the reaction of two dehydrogenation canthaxanthins (C) reduction preparation canthaxanthins (D), solvent is CH
2Cl
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510062146XA CN100338004C (en) | 2005-12-21 | 2005-12-21 | Process for preparing cantharis yellow |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200510062146XA CN100338004C (en) | 2005-12-21 | 2005-12-21 | Process for preparing cantharis yellow |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1821204A CN1821204A (en) | 2006-08-23 |
| CN100338004C true CN100338004C (en) | 2007-09-19 |
Family
ID=36922805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB200510062146XA Active CN100338004C (en) | 2005-12-21 | 2005-12-21 | Process for preparing cantharis yellow |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100338004C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777599A (en) * | 2014-12-26 | 2016-07-20 | 上虞新和成生物化工有限公司 | Method for preparing canthaxanthin through oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5378229A (en) * | 1976-12-18 | 1978-07-11 | Basf Ag | Method of producing canthaxanthene |
| EP1059290A1 (en) * | 1999-06-09 | 2000-12-13 | Kuraray Co., Ltd. | Process for producing canthaxanthin |
-
2005
- 2005-12-21 CN CNB200510062146XA patent/CN100338004C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5378229A (en) * | 1976-12-18 | 1978-07-11 | Basf Ag | Method of producing canthaxanthene |
| EP1059290A1 (en) * | 1999-06-09 | 2000-12-13 | Kuraray Co., Ltd. | Process for producing canthaxanthin |
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| Publication number | Publication date |
|---|---|
| CN1821204A (en) | 2006-08-23 |
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| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 310027 Hangzhou, Zhejiang Province, Zhejiang Road, No. 38 Co-patentee after: Zhejiang Xinhecheng Co., Ltd. Patentee after: Zhejiang University Co-patentee after: Shangyu Xinhecheng Bio-Chemical Co., Ltd. Co-patentee after: Zhejiang NHU Pharmaceutical Co., Ltd. Address before: 310027 Hangzhou, Zhejiang Province, Zhejiang Road, No. 38 Co-patentee before: Zhejiang Xinhecheng Co., Ltd. Patentee before: Zhejiang University |