CN101081829A - Synthesizing technique for beta-carotene - Google Patents
Synthesizing technique for beta-carotene Download PDFInfo
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- CN101081829A CN101081829A CN 200610051814 CN200610051814A CN101081829A CN 101081829 A CN101081829 A CN 101081829A CN 200610051814 CN200610051814 CN 200610051814 CN 200610051814 A CN200610051814 A CN 200610051814A CN 101081829 A CN101081829 A CN 101081829A
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Abstract
The present invention discloses new coupling reaction process for preparing beta-carotene. Organic phosphine salt is first prepared through reacting vitamin A derivative and triphenyl phosphine, and then made to produce coupling reaction in the presence of oxidant to obtain beta-carotene. The present invention features that the coupling reaction is completed in a two phase system of water phase and water insoluble organic solvent phase, so that the produced beta-carotene is extracted constantly by the organic solvent phase, decreasing the possibility of oxidizing produced beta-carotene and raising beta-carotene yield.
Description
Technical field
The present invention relates to the preparation of VITAMIN, specifically a kind of method of utilizing linked reaction to obtain β-Hu Luobusu.
Background technology
Beta carotene is a medicine important in the retinoid, and its market outlook are very good.Is the important intermediate for preparing β-Hu Luobusu by the retinol or derivatives thereof by reacting the organic phosphonium salt that obtains with triphenylphosphine, it can further prepare β-Hu Luobusu (Joachim Buddrus with axerophthal by the Wittig condensation reaction, et al., USP.3,634,518, Process for Preparing Alkylidene Phosphoranes, [P] 1972; Badische Anlin ﹠amp; Soda-FabrikAktiengesellschaft, DE 974,890, Production of Compounds of the Axerophthylidene Series, [P] 1964).The condensation reaction that also can carry out between the organic phosphonium salt of two molecules prepares β-Hu Luobusu (Bernhard Schulz, etal., USP.4,105,855, Manufacture of Symmetrical Carotenoids, [P] 1978):
Or:
Because the symmetrical structure of β-Hu Luobusu, the method for carrying out the preparation of condensation linked reaction between the organic phosphonium salt of two molecules seems more succinct.In people's such as Bernhard Schulz method, make the methanol-water solution of vitamin A triphenylphosphine salt earlier, after removing low polar impurity with normal heptane extraction, be lower than 30 ℃ earlier and remove methyl alcohol under reduced pressure, carry out linked reaction between the organic phosphonium salt of two molecules with 30% hydrogen peroxide then, filter the mixture that obtains product β-Hu Luobusu crude product and by product after reaction is good earlier, again this solid mixture is carried out recrystallization or rinsing to remove the triphen phosphine oxide.There is following shortcoming in this reaction: hydrogen peroxide (or other oxygenant) used during linked reaction has very strong oxidisability, oxidation destroys the product β-Hu Luobusu that generates easily, if with easy and miscible solvent systems of water such as alcohols, then product is easier to be oxidized, so just cause the yield of product low, it is big to produce fluctuation, and charge ratio is difficult to problems such as control.
Summary of the invention
Technical problem to be solved by this invention is to overcome the defective that above-mentioned prior art exists, provide a kind of product β-Hu Luobusu to avoid the preparation method who contacts with oxygenant, to significantly reduce the oxidized destructive probability of product β-Hu Luobusu, improve the yield of product.
For this reason, the present invention adopts following technical scheme: the synthesis technique of β-Hu Luobusu, react the organic phosphonium salt that obtains by vitamin A derivatives and triphenylphosphine, in the presence of oxygenant, carry out obtaining β-Hu Luobusu after the linked reaction, it is characterized in that: described linked reaction water and with the two-phase system of the immiscible organic solvent of water in the presence of carry out.In case the product β-Hu Luobusu generates, it will constantly be extracted and enter organic phase, thereby has avoided and the contacting of oxygenant (it stays aqueous phase), and has significantly reduced the oxidized destructive probability of product β-Hu Luobusu, has improved the yield of product.
As further technical scheme of the present invention, the weight ratio of described water and organic phosphonium salt can be between 3: 1 to 20: 1, and preferably between 5: 1 to 10: 1, the water yield can make organic phosphonium salt dissolving bad very little, the influence reaction is carried out, and the water yield can reduce throughput too much; The volume ratio of organic solvent and water is between 0.5: 1 to 3: 1, and between preferred 0.8: 1 to 1.5: 1, too little solvent can make the product β-Hu Luobusu not dissolve fully fast and break away from water, and solvent can reduce throughput too much.
As further technical scheme of the present invention, described temperature of reaction is at-20 ℃ to 30 ℃, preferably between 0 ℃ to 10 ℃.
As further technical scheme of the present invention, can be halide-containings such as ester classes such as ethyl acetate, methylene dichloride, chloroform, ethylene dichloride with the not miscible organic solvent of water in the reaction system, aromatic compounds such as toluene, benzene, alkane such as hexanaphthene; Halide-containing such as preferred methylene dichloride, chloroform, ethylene dichloride and benzene or by the mixture of these solvent compositions.
As further technical scheme of the present invention, described vitamin A derivatives is retinol, retinyl acetate or both mixtures, also can be resulting crystalline mother solution behind preparation pure product retinol or the retinyl acetate.Contain multiple cis-trans-isomer in the crystalline mother solution, can save the rearrangement treating processes of portion of product when making raw material with it, and turn waste into wealth (mostly do the waste material processing in the past or do the fuel use).
As further technical scheme of the present invention, used oxygenant is halide-containings such as hypochlorite, oxymuriate, peralcohol such as hydrogen peroxide, SPC-D or oxygen, air.
As further technical scheme of the present invention, the last handling process of reaction is as follows: the mixed solution layering that obtains after the linked reaction, the red solid that obtains behind organic layer washing, the concentrated recovery solvent is the mixture of β-Hu Luobusu crude product and triphenyl phosphine oxide composition, this mixture can be used alcohols (as methyl alcohol) eccysis deoxidation triphenyl phosphine, further carry out recrystallization then or in solvent heating carry out various cis mixtures to the rearrangement processing of alltrans structure etc.
The present invention in the presence of the oxygenant in water and with the immiscible organic solvent two-phase system of water in the presence of carry out linked reaction, have following beneficial effect: the product β-Hu Luobusu is constantly entered organic phase by organic solvent extraction, avoided the product β-Hu Luobusu to contact with the oxygenant of staying aqueous phase, significantly reduce the oxidized destructive probability of product β-Hu Luobusu, improved the yield of product; It is little to produce fluctuation, and charge ratio is easy to control.
Embodiment
The invention will be further described below in conjunction with embodiment.
Analytical instrument of using among the embodiment and equipment:
The Agilent 1100series high performance liquid chromatograph of Agilent company;
UNIC UV-4802 type ultraviolet-visible pectrophotometer.
Embodiment 1: the preparation of vitamin A triphenylphosphine salt
Put 50 gram vitamin A (VA in 1000 milliliters of there-necked flasks, pale yellow crystal, 2,800,000 IU, 0.147 mole), 39 gram triphenylphosphine (0.149 mole) and 500 ml methanol, stirring down, ice-water bath is cooled to 10 ℃, keep and slowly splash into the 15 gram vitriol oils below 15 ℃, added in about 1 hour, continued insulated and stirred afterwards 12 hours, reaction solution becomes orange transparent liquid.Add 80 gram deionized waters, with each 100 ml n-hexane extracting twice, lower floor is the methanol-water solution of VA triphenylphosphine salt, is lower than 30 ℃ of decompression and solvent recovery methyl alcohol up to there being solid to separate out (this moment, mixed system weighed 130 grams), adds 600 gram water then solid is dissolved as clear solution.
Embodiment 2: linked reaction prepares β-Hu Luobusu
The aqueous solution of the VA triphenylphosphine salt that obtains among the embodiment 1 is put in 2000 milliliters of four-hole bottles, add 600 milliliters of chloroforms, cryosel is bathed and is as cold as 0 ℃, keep and drip aqueous sodium hypochlorite solution 150 grams that contain 10% available chlorine below 5 ℃, also drip saturated aqueous sodium carbonate simultaneously and finish back pH value between 8-10 to guarantee reaction, added in about 1 hour, insulation continues to stir 1 hour.
Layering obtains red organic layer with 200 milliliters of washings, is lower than 55 ℃ and reclaims solvent, obtains red finely powdered thing, adds 200 ml methanol, refluxes 10 minutes, and filter and obtain crude product β-Hu Luobusu 68 grams, heavy 61.2 grams behind the vacuum drying, content detection is 68%.With the 12 hours postcooling that in normal heptane, reflux under this crude product nitrogen protection, filter, dry to such an extent that scarlet crystallization 40 restrains content 98.2%, total recovery 50.8%.
Embodiment 3: prepare β-Hu Luobusu with the VA crystalline mother solution
With 110 gram content is the VA crystalline mother solution (liquid-phase chromatographic analysis: alltrans VA acetic ester 42% of 1,300,000 IU; 13-cis VA acetic ester 40%, trans VA alcohol 13%) replace the VA crystal among the embodiment 1, other condition is identical, makes the aqueous solution of VA triphenylphosphine salt.
The aqueous solution of this VA triphenylphosphine salt is put in 2000 milliliters of four-hole bottles, add 600 milliliters of chloroforms, cryosel is bathed and is as cold as 0 ℃, keep hydrogen peroxide 30 grams that add content 30% below 5 ℃, keep then below 10 ℃ drip saturated aqueous sodium carbonate up to the pH of system value greater than 9, added in about 1 hour, insulation continues to stir 1 hour.
Layering obtains red organic layer with 200 milliliters of washings, is lower than 55 ℃ and reclaims solvent, obtains red finely powdered thing, adds 200 ml methanol, refluxes 10 minutes, and filter and obtain crude product β-Hu Luobusu 78 grams, heavy 70.5 grams behind the vacuum drying, content detection is 62%.With the 12 hours postcooling that in normal heptane, reflux under this crude product nitrogen protection, filter, dry to such an extent that scarlet crystallization 41.5 restrains content 96.7%, total recovery 51.9%.
Embodiment 4: prepare β-Hu Luobusu with the VA crystalline mother solution
The preparation of VA triphenylphosphine salt brine solution is with embodiment 3, and conditions such as linked reaction and aftertreatment just replace chloroform with methylene dichloride with embodiment 3, gets product 38.5 grams, content 97.5%, total recovery 48.5%.
Embodiment 5: prepare β-Hu Luobusu with the VA crystalline mother solution
The preparation of VA triphenylphosphine salt brine solution is with embodiment 3, condition such as linked reaction and aftertreatment is with embodiment 2, just replace chloroform with ethylene dichloride, oxygenant uses the solution that is made into by 25 gram sodium chlorate and 150 ml waters to replace 150 grams to contain the aqueous sodium hypochlorite solution of 10% available chlorine, get product 39.5 grams, content 97.7%, total recovery 49.9%.
Embodiment 6: prepare β-Hu Luobusu with the VA crystalline mother solution
Other condition is with embodiment 5, and solvent is changed to benzene by ethylene dichloride, gets product 39.1 grams, content 96.5%, total recovery 48.8%.
Embodiment 7: prepare β-Hu Luobusu with the VA crystalline mother solution
The preparation of VA triphenylphosphine salt brine solution is with embodiment 3, condition such as linked reaction and aftertreatment is with embodiment 2, just oxygenant uses the solution that is made into by 30 gram SPC-D and 200 ml waters to replace 150 grams to contain the aqueous sodium hypochlorite solution of 10% available chlorine, get product 44.5 grams, content 97.9%, total recovery 56.3%.
Embodiment 8: prepare β-Hu Luobusu with the VA crystalline mother solution
The preparation of VA triphenylphosphine salt brine solution is with embodiment 3, condition such as linked reaction and aftertreatment is with embodiment 2, just oxygenant replaces 150 grams to contain the aqueous sodium hypochlorite solution of 10% available chlorine with oxygen, led to oxygen 2 hours with 2.5 liters/speed at one hour rating, get product 38.5 grams, content 97.5%, total recovery 48.5%.
Comparative Examples 1: linked reaction prepares β-Hu Luobusu
The methanol-water formulations prepared from solutions of VA triphenylphosphine salt is with embodiment 1, do not steam methyl alcohol, it is put in 1000 milliliters of four-hole bottles, cryosel is bathed and is as cold as 0 ℃, keep and drip aqueous sodium hypochlorite solution 150 grams that contain 10% available chlorine below 5 ℃, also drip saturated aqueous sodium carbonate simultaneously and finish back pH value between 8-10 to guarantee reaction, added in about 1 hour, insulation continues to stir 1 hour.
Filter, obtain red finely powdered crude product β-Hu Luobusu 58 grams, heavy 50.2 grams behind the vacuum drying, carrying out content detection with ultraviolet-visible pectrophotometer is 65%.With the 12 hours postcooling that in normal heptane, reflux under this crude product nitrogen protection, filter, dry to such an extent that scarlet crystallization 30 restrains content 98.2%, total recovery 38.1%.
Comparative Examples 2: prepare β-Hu Luobusu with the VA crystalline mother solution
The methanol-water formulations prepared from solutions of VA triphenylphosphine salt is with embodiment 3.Carry out linked reaction according to the condition in the Comparative Examples 1 again, get β-Hu Luobusu elaboration 28.9 grams of content 96.7%, total recovery 36.7%.
Comparative Examples 3: linked reaction prepares β-Hu Luobusu
The methanol-water solution of VA triphenylphosphine salt is pressed method and the proportioning preparation of embodiment 1, and the linked reaction condition is identical with embodiment 3, does not just add organic solvent.Reaction finishes the back and adds 500 milliliters of chloroforms, stirs solid is all dissolved the back layering, and chloroform is reclaimed in organic layer washing back, add the heating of 200 ml methanol again and make the dissolving of triphen phosphine oxide, cooling, filtration, filter cake is washed with methyl alcohol, dry to such an extent that scarlet crystallization 35 restrains content 98.5%, total recovery 44.4%.
Comparative Examples 4: linked reaction prepares β-Hu Luobusu
The methanol-water solution of VA triphenylphosphine salt is pressed method and the proportioning preparation of embodiment 1, and the linked reaction condition is identical with embodiment 5, does not just add organic solvent.Reaction finishes the back and adds 500 milliliters of chloroforms, stirs solid is all dissolved the back layering, and chloroform is reclaimed in organic layer washing back, add the heating of 200 ml methanol again and make the dissolving of triphen phosphine oxide, cooling, filtration, filter cake is washed with methyl alcohol, dry to such an extent that scarlet crystallization 25 restrains content 97.3%, total recovery 31.5%.
Comparative Examples 5: linked reaction prepares β-Hu Luobusu
The methanol-water solution of VA triphenylphosphine salt is pressed method and the proportioning preparation of embodiment 1, and the linked reaction condition is identical with embodiment 8, and logical oxygen reacts, and does not just add organic solvent.Reaction finishes the back and adds 500 milliliters of chloroforms, stirring is all dissolved the back layering with solid, chloroform is reclaimed in organic layer washing back, add the heating of 200 ml methanol again and make the dissolving of triphen phosphine oxide, cooling, filtration, filter cake is washed with methyl alcohol, dries to such an extent that scarlet crystallization 15 restrains, it is 85.5% that ultraviolet-visible pectrophotometer carries out content detection, yield 16.6%.
Claims (10)
1, the synthesis technique of β-Hu Luobusu, react the organic phosphonium salt that obtains by vitamin A derivatives and triphenylphosphine, in the presence of oxygenant, carry out obtaining β-Hu Luobusu after the linked reaction, it is characterized in that: described linked reaction water and with the two-phase system of the immiscible organic solvent of water in the presence of carry out.
2, the synthesis technique of β-Hu Luobusu according to claim 1, the weight ratio that it is characterized in that water and organic phosphonium salt is between 3: 1 to 20: 1, the volume ratio of organic solvent and water is between 0.5: 1 to 3: 1.
3, the synthesis technique of β-Hu Luobusu according to claim 2, the weight ratio that it is characterized in that water and organic phosphonium salt is between 5: 1 to 10: 1, the volume ratio of organic solvent and water is between 0.8: 1 to 1.5: 1.
4, the synthesis technique of β-Hu Luobusu according to claim 3 is characterized in that described temperature of reaction is between-20 ℃ to 30 ℃.
5, the synthesis technique of β-Hu Luobusu according to claim 4 is characterized in that described temperature of reaction is between 0 ℃ to 10 ℃.
6, according to the synthesis technique of each described β-Hu Luobusu among the claim 1-5, it is characterized in that in the reaction system with the not miscible organic solvent of water be ester compound, halide-containing, aromatic compound, alkane compound or their mixture.
7, the synthesis technique of β-Hu Luobusu according to claim 6 is characterized in that described organic solvent is methylene dichloride, chloroform, ethylene dichloride, benzene or their mixture.
8, the synthesis technique of β-Hu Luobusu according to claim 7, it is characterized in that described vitamin A derivatives is retinol, retinyl acetate or both mixtures, or be resulting crystalline mother solution behind the pure product retinol of preparation, the retinyl acetate.
9, the synthesis technique of β-Hu Luobusu according to claim 8 is characterized in that used oxygenant is hypochlorite, oxymuriate, hydrogen peroxide, SPC-D, oxygen or air.
10, the synthesis technique of β-Hu Luobusu according to claim 9, it is characterized in that the last handling process that reacts is as follows: layering after reaction is good, the red solid that obtains behind organic layer washing, the concentrated recovery solvent is the mixture of β-Hu Luobusu crude product and triphenyl phosphine oxide composition, this mixture washs with alcoholic solvent, remove triphenyl phosphine oxide, further carry out recrystallization then or in solvent heating carry out various cis mixtures and handle to the rearrangement of alltrans structure.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047112A (en) * | 2017-12-29 | 2018-05-18 | 厦门金达威维生素有限公司 | A kind of method of vitamin A one pot process beta carotene |
| CN108822015A (en) * | 2018-07-24 | 2018-11-16 | 厦门金达威集团股份有限公司 | The synthetic method of beta carotene |
| CN110452147A (en) * | 2019-07-30 | 2019-11-15 | 万华化学集团股份有限公司 | A kind of preparation method of beta carotene |
| CN112262126A (en) * | 2020-09-18 | 2021-01-22 | 厦门金达威维生素有限公司 | Preparation method of beta-carotene |
| CN113292467A (en) * | 2021-06-09 | 2021-08-24 | 安徽智新生化有限公司 | Method for purifying vitamin A oil mother liquor by using alcohol-containing alkali liquor |
| CN113321604A (en) * | 2021-06-23 | 2021-08-31 | 万华化学集团股份有限公司 | Preparation method of beta-carotene with high all-trans content |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090271A (en) * | 1993-09-20 | 1994-08-03 | 郑庆泉 | A kind of chemical synthesis process of β-Hu Luobusu |
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2006
- 2006-06-02 CN CNB2006100518143A patent/CN100564356C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047112A (en) * | 2017-12-29 | 2018-05-18 | 厦门金达威维生素有限公司 | A kind of method of vitamin A one pot process beta carotene |
| CN108047112B (en) * | 2017-12-29 | 2020-02-21 | 厦门金达威维生素有限公司 | Method for synthesizing β -carotene by vitamin A one-pot method |
| CN108822015A (en) * | 2018-07-24 | 2018-11-16 | 厦门金达威集团股份有限公司 | The synthetic method of beta carotene |
| CN108822015B (en) * | 2018-07-24 | 2020-09-11 | 厦门金达威集团股份有限公司 | Method for synthesizing beta-carotene |
| CN110452147A (en) * | 2019-07-30 | 2019-11-15 | 万华化学集团股份有限公司 | A kind of preparation method of beta carotene |
| CN110452147B (en) * | 2019-07-30 | 2021-07-23 | 万华化学集团股份有限公司 | Preparation method of beta-carotene |
| CN112262126A (en) * | 2020-09-18 | 2021-01-22 | 厦门金达威维生素有限公司 | Preparation method of beta-carotene |
| WO2022056827A1 (en) * | 2020-09-18 | 2022-03-24 | 厦门金达威维生素有限公司 | METHOD FOR PREPARING β-CAROTENE |
| CN113292467A (en) * | 2021-06-09 | 2021-08-24 | 安徽智新生化有限公司 | Method for purifying vitamin A oil mother liquor by using alcohol-containing alkali liquor |
| CN113321604A (en) * | 2021-06-23 | 2021-08-31 | 万华化学集团股份有限公司 | Preparation method of beta-carotene with high all-trans content |
| CN113321604B (en) * | 2021-06-23 | 2023-01-13 | 万华化学集团股份有限公司 | Preparation method of beta-carotene |
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