CN100494145C - Process for preparing cantharides xanthin - Google Patents
Process for preparing cantharides xanthin Download PDFInfo
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- CN100494145C CN100494145C CNB2005101019203A CN200510101920A CN100494145C CN 100494145 C CN100494145 C CN 100494145C CN B2005101019203 A CNB2005101019203 A CN B2005101019203A CN 200510101920 A CN200510101920 A CN 200510101920A CN 100494145 C CN100494145 C CN 100494145C
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- Prior art keywords
- preparation
- reaction
- luobusu
- halate
- solution
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- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 5
- 150000005826 halohydrocarbons Chemical group 0.000 claims description 5
- 238000005286 illumination Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 claims description 2
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 tin anhydride Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 241000131283 Cantharis Species 0.000 abstract 2
- 229940075420 xanthine Drugs 0.000 abstract 2
- OENHQHLEOONYIE-UKMVMLAPSA-N all-trans beta-carotene Natural products CC=1CCCC(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)CCCC1(C)C OENHQHLEOONYIE-UKMVMLAPSA-N 0.000 abstract 1
- 239000011648 beta-carotene Substances 0.000 abstract 1
- TUPZEYHYWIEDIH-WAIFQNFQSA-N beta-carotene Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC2=CCCCC2(C)C TUPZEYHYWIEDIH-WAIFQNFQSA-N 0.000 abstract 1
- 235000013734 beta-carotene Nutrition 0.000 abstract 1
- 229960002747 betacarotene Drugs 0.000 abstract 1
- 150000008282 halocarbons Chemical class 0.000 abstract 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- OENHQHLEOONYIE-JLTXGRSLSA-N β-Carotene Chemical compound CC=1CCCC(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)CCCC1(C)C OENHQHLEOONYIE-JLTXGRSLSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 235000021466 carotenoid Nutrition 0.000 description 2
- 150000001747 carotenoids Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000007715 potassium iodide Nutrition 0.000 description 2
- 229960004839 potassium iodide Drugs 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 241000272525 Anas platyrhynchos Species 0.000 description 1
- 244000124209 Crocus sativus Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 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 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229940008033 canthaxanthin Drugs 0.000 description 1
- 235000012682 canthaxanthin Nutrition 0.000 description 1
- 239000001659 canthaxanthin Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 210000002969 egg yolk Anatomy 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000015243 ice cream Nutrition 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a manufacture method for cantharis xanthine that dissolving beta-carotene into halogenated hydrocarbon adding oxidizing agent water solution that the ph value is adjusted to 2-5, irradiating under 200-800W lighting to make cantharis xanthine. The invention is easy to operate, stable reaction, mild reaction condition and low cost.
Description
Invention field
The invention belongs to the organic synthesis field, be specifically related to the preparation method of.
Background technology
Of the present invention (or claiming canthaxanthin) is a kind of carotenoid, be present in [Ling Guanting in some mushroom, crustaceans, fish, algae, egg, blood and the liver, foodstuff additive handbook [M], Beijing, Chemical Industry Press, second edition, 1997,0415-0416], FDA/WHO approval was listed foodstuff additive in and had been worked out quality standard in 1984.Can be used as foodstuff additive and is used for beverage, ice-creams, Hua Fuwu auxiliary material biscuit, flavouring paste, tomato processed goods and meat processing product etc.Is added in the feed of poultry such as chicken, duck, yolk is produced the safran [PAUT J.Recent Progress in Commercial Retinoids and and Carotenoids[J] that a kind of human consumer likes, Pure ﹠amp; ApplChem., 1991,63 (1) 45-48].
The preparation method of that United States Patent (USP) 4212827 is mentioned adopts halate in the presence of potassiumiodide or iodine, the oxidation β-Hu Luobusu.But the shortcoming that this method exists is difficulty of initiated oxidation, and the technology instability is used more potassiumiodide.
Summary of the invention
The object of the invention provides a kind of preparation method of of new reaction conditions gentleness.
Preparation method of the present invention utilizes oxygenant oxidation β-Hu Luobusu under illumination condition.
Reaction equation is as follows:
Preparation method of the present invention is dissolved in β-Hu Luobusu in the organic solvent, add aqueous oxidizing agent solution, be heated to 25～40 ℃ then, oxidation 4～7 hours preparation under illumination condition, wherein said illumination condition are that power is that the electric light source of 200～800W places in the reaction solution or on the liquid level.
Oxygenant of the present invention is this area oxygenant commonly used.For example Manganse Dioxide, tin anhydride, hydrogen peroxide and halate wherein one or both or two or more.
Oxygenant of the present invention better is a halate.Described halate be oxymuriate, bromate, iodate wherein one or both or two or more.
Oxymuriate of the present invention can be water-soluble salts such as sylvite, sodium salt, calcium salt.Oxymuriate of the present invention is Potcrate, sodium chlorate one or both mixtures wherein preferably.
The weight ratio of halate and water is 1:5～1:20 in the halate solution of the present invention.
Oxygenant consumption of the present invention is 1.5～3 times (weight ratios) of β-Hu Luobusu.
Aqueous oxidizing agent solution pH of the present invention is between 2～5.Wherein aqueous solution pH uses acidic substance such as sulfuric acid, hydrochloric acid to regulate.Sulfuric acid preferably wherein.
Preparation method's of the present invention temperature of reaction is 30～40 ℃, and the reaction times is 4～6 hours.
Organic solvent of the present invention is this area solvent commonly used, for example halohydrocarbon, ester and their mixed solvent.The best halohydrocarbon of organic solvent of the present invention.Described halohydrocarbon is methylene dichloride or trichloromethane preferably.Consumption of organic solvent of the present invention is 20～50 times (weight ratios) of β-Hu Luobusu.
Electric light source of the present invention can be an incandescent light, and mercury lamp and sodium lamp lamp are wherein a kind of.
It is simple that preparation method of the present invention has technological operation, stable reaction, reaction conditions gentleness, the advantage that cost is low.
Embodiment
Embodiment 1
Get the 10g β-Hu Luobusu and place the 500ml reactor, add the 250ml methylene dichloride, then, get 20g sodium chlorate 200ml water dissolution, use W (H again
2SO
4It is 3.5 that the solution of)=5% is transferred pH, adds in the reactor, and temperature is controlled at 40 ℃, place the reaction solution internal radiation with the 800W incandescent light, and vigorous stirring, reacted 4 hours, separate organic layer, wash with water 3 times, use anhydrous sodium sulfate drying again, filter, the solution rotating evaporation, residue is used the chloroform-methanol crystallization then with 200ml methanol wash secondary, obtain purple needle-like crystal 7.2g, yield 70.4%.Resulting crystalline fusing point is 206-208 ℃, measures according to the method for FAD/WHO, and quality product meets the codex alimentarius of FAD/WHO regulation.
Embodiment 2
The 10g β-Hu Luobusu places the 500ml reactor, adds the 250ml methylene dichloride, then, gets 25g sodium bromate 200ml water dissolution, uses W (H again
2SO
4It is 4 that the solution of)=5% is transferred pH, adds in the reactor, and temperature is controlled at 35 ℃, place reaction to shine on the liquid level with the 500W mercury lamp, and vigorous stirring, reacted 5 hours, separate organic layer, wash with water 3 times, use anhydrous sodium sulfate drying again, filter, the solution rotating evaporation, residue is used the chloroform-methanol crystallization then with 200ml methanol wash secondary, obtain purple needle-like crystal 7.6g, yield 74.3%.Resulting crystalline fusing point is 206-208 ℃.
Embodiment 3
Get the 10g β-Hu Luobusu and place the 500ml reactor, add the 300ml trichloromethane, then, get 20g sodium chlorate 200ml water dissolution, use W (H again
2SO
4It is 3 that the solution of)=5% is transferred pH, adds in the reactor, and temperature is controlled at 30 ℃, place the reaction solution internal radiation with the 200W sodium vapor lamp, and vigorous stirring, reacted 6 hours, separate organic layer, wash with water 3 times, use anhydrous sodium sulfate drying again, filter, the solution rotating evaporation, residue is used the chloroform-methanol crystallization then with 200ml methanol wash secondary, obtain purple needle-like crystal 6 .9g, yield 67.5%.Resulting crystalline fusing point is 206-208 ℃.
Embodiment 4
Get the 10g β-Hu Luobusu and place the 500ml reactor, add the 300ml trichloromethane, then, get 25g sodium chlorate 200ml water dissolution, use W (H again
2SO
4It is 2 that the solution of)=5% is transferred pH, adds in the reactor, and temperature is controlled at 25 ℃, place the irradiation of reaction liquid level with the 600W sodium vapor lamp, and vigorous stirring, reacted 7 hours, separate organic layer, wash with water 3 times, use anhydrous sodium sulfate drying again, filter, the solution rotating evaporation, residue is used the chloroform-methanol crystallization then with 200ml methanol wash secondary, obtain purple needle-like crystal 7.1g, yield 69.4%.Resulting crystalline fusing point is 206-208 ℃.
Claims (8)
1. the preparation method of, this method is that β-Hu Luobusu is dissolved in the organic solvent, add aqueous oxidizing agent solution, be heated to 25～40 ℃ then, oxidation 4～7 hours preparation under illumination condition, wherein said illumination condition are that power is that the electric light source of 200～800W places in the reaction solution or on the liquid level; Wherein, described oxygenant is one or more in Manganse Dioxide, tin anhydride, hydrogen peroxide and the halate, and described aqueous oxidizing agent solution pH is 2～5.
2. the preparation method of described of claim 1 is characterized in that described halate is one or more in oxymuriate, bromate and the iodate.
3. the preparation method of described of claim 2 is characterized in that described oxymuriate is a wherein a kind of or mixture of Potcrate, sodium chlorate.
4. the preparation method of described of claim 1 is characterized in that the oxygenant consumption is by weight 1.5～3 times for β-Hu Luobusu.
5. the preparation method of described of claim 1 is characterized in that temperature of reaction is 30～40 ℃, and the reaction times is 4～6 hours.
6. the preparation method of described of claim 1 is characterized in that organic solvent is a halohydrocarbon.
7. the preparation method of described of claim 6 is characterized in that described halohydrocarbon is methylene dichloride or trichloromethane.
8. the preparation method of described of claim 1 is characterized in that described electric light source is an incandescent light, and mercury lamp and sodium lamp lamp are wherein a kind of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101019203A CN100494145C (en) | 2005-12-08 | 2005-12-08 | Process for preparing cantharides xanthin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101019203A CN100494145C (en) | 2005-12-08 | 2005-12-08 | Process for preparing cantharides xanthin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1793098A CN1793098A (en) | 2006-06-28 |
| CN100494145C true CN100494145C (en) | 2009-06-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101019203A Expired - Fee Related CN100494145C (en) | 2005-12-08 | 2005-12-08 | Process for preparing cantharides xanthin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100494145C (en) |
Families Citing this family (3)
| 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 |
| CN108244060B (en) * | 2018-04-24 | 2020-03-24 | 四川省农业科学院植物保护研究所 | Breeding method of yellow black mylabris |
| CN114315677B (en) * | 2021-12-31 | 2022-11-08 | 万华化学集团股份有限公司 | Method for preparing canthaxanthin through photocatalytic oxidation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3790635A (en) * | 1967-08-28 | 1974-02-05 | Rhone Poulenc Sa | Process for the preparation of canthaxanthine |
| US4212827A (en) * | 1975-08-05 | 1980-07-15 | Basf Aktiengesellschaft | Manufacture of canthaxanthin |
-
2005
- 2005-12-08 CN CNB2005101019203A patent/CN100494145C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3790635A (en) * | 1967-08-28 | 1974-02-05 | Rhone Poulenc Sa | Process for the preparation of canthaxanthine |
| US4212827A (en) * | 1975-08-05 | 1980-07-15 | Basf Aktiengesellschaft | Manufacture of canthaxanthin |
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| Publication number | Publication date |
|---|---|
| CN1793098A (en) | 2006-06-28 |
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