CN112262126B - Preparation method of beta-carotene - Google Patents
Preparation method of beta-carotene Download PDFInfo
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- CN112262126B CN112262126B CN202080002023.XA CN202080002023A CN112262126B CN 112262126 B CN112262126 B CN 112262126B CN 202080002023 A CN202080002023 A CN 202080002023A CN 112262126 B CN112262126 B CN 112262126B
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- C07—ORGANIC CHEMISTRY
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- 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
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Abstract
The invention belongs to the field of compound preparation, and particularly relates to a preparation method of beta-carotene, which comprises the following steps: mixing vitamin A organic phosphine salt shown in formula (1) with hydrogen peroxideCarrying out oxidative coupling reaction in an alkaline system of the nano silver colloid; r1、R2And R3Each independently an aliphatic group, an alicyclic group, or an aromatic group; x is an organic or inorganic strong acid group. The preparation method of the beta-carotene provided by the invention takes the nano silver colloid as the stabilizer and the catalyst, and can obviously improve the yield of the beta-carotene.
Description
Technical Field
The invention belongs to the field of compound preparation, and particularly relates to a preparation method of beta-carotene.
Background
The beta-carotene is a vitamin A source substance, can be used in the industries of medicines, foods, cosmetics, feed additives and dyes, and has good market application prospect. The currently disclosed preparation methods of beta-carotene are many, and the process for synthesizing the beta-carotene by taking the vitamin A and the derivatives thereof as starting raw materials mainly comprises Wittig condensation reaction and oxidative coupling.
The specific process of the Wittig condensation reaction is to react vitamin A alcohol or derivatives thereof with triarylphosphine to obtain organic phosphonium salt, and then the organic phosphonium salt is further condensed with vitamin A aldehyde through the Wittig reaction to obtain beta-carotene, wherein the specific reaction process is shown as a formula (1). The Wittig reaction requires no water and oxygen, the conditions are harsh, and the chemical property of the vitamin A aldehyde is unstable, so that the vitamin A aldehyde is not easy to industrially prepare.
(1)
The specific process of the oxidative coupling is to react vitamin A alcohol or derivatives thereof with triarylphosphine to obtain organic phosphonium salt, and then to perform oxidative coupling on two molecules of the organic phosphonium salt to obtain the beta-carotene, wherein the specific reaction process is shown as a formula (2). Because the structure of the beta-carotene is symmetrical, the process route for preparing the beta-carotene by carrying out the oxidative coupling reaction between two molecules of organic phosphonium salt is simpler.
Both CN101081829A and CN101041631A disclose that vitamin a alcohol or organic phosphonium salt of its derivatives undergo oxidative coupling reaction in the presence of an oxidant to obtain β -carotene, wherein the oxidant used is hypochlorite, chlorate, hydrogen peroxide, sodium percarbonate, oxygen or air. However, the reaction yields of β -carotene are low.
Disclosure of Invention
The invention aims to overcome the defect of low reaction yield of beta-carotene obtained by the existing method, and provides a preparation method capable of improving the yield of beta-carotene.
Aiming at a reaction system for synthesizing beta-carotene by oxidizing coupling reaction of vitamin A organic phosphine salt, when hydrogen peroxide is used as an oxidant, the reasons for lower reaction yield are mainly attributed to the following two points: firstly, under the alkaline condition, particularly under the condition of high-valence metal ions, hydrogen peroxide can be subjected to uncontrollable decomposition, and one part of the added hydrogen peroxide is subjected to uncontrollable decomposition while the other part is subjected to uncontrollable decomposition, so that the reaction is uncontrollable; and secondly, the vitamin A organic phosphonium salt has more side reactions under the oxidation of hydrogen peroxide. The inventor of the invention finds that after extensive and intensive research, the nano silver colloid is added into a hydrogen peroxide oxidative coupling reaction system of the vitamin A organic phosphonium salt, and the nano silver colloid simultaneously plays the roles of a stabilizer and a catalyst, so that the stability of the hydrogen peroxide can be improved, the problem of uncontrollable decomposition of the hydrogen peroxide under an alkaline condition can be solved, the probability of side reaction can be reduced, and the selectivity of oxidizing the vitamin A organic phosphonium salt into beta-carotene can be improved. Based on this, the present invention has been completed.
Specifically, the invention provides a preparation method of beta-carotene, which comprises the following steps: carrying out oxidative coupling reaction on vitamin A organic phosphonium salt shown in formula (1) and hydrogen peroxide in an alkaline system containing nano silver colloid;
in the formula (1), R1、R2And R3Each independently being an aliphatic, cycloaliphatic or aromatic radical, preferably each independently being C1～C10Substituted or unsubstituted alkyl, C3～C10Substituted or unsubstituted cycloalkane group of (A) or (C)6～C10Substituted or unsubstituted aryl of (a); x is an organic or inorganic strong acid group, preferably halogen, sulfate, hydrogen sulfate, phosphate, tetrafluoroborate, acetate, tosylate or benzenesulfonate.
Further, the mode of the oxidative coupling reaction is as follows: dissolving vitamin A organic phosphonium salt and alkali in a solvent to form a mixed solution, then dripping the mixed solution of nano silver colloid and hydrogen peroxide into the mixed solution, and stirring until the oxidative coupling reaction is complete.
Further, the mass concentration of the nano silver colloid in the mixed liquid of the nano silver colloid and hydrogen peroxide is 0.01-0.1%.
Furthermore, the particle size of the nano silver colloid is 2-100 nm.
Furthermore, the molar ratio of the vitamin A organic phosphine salt to the alkali is 1 (1-10), and preferably 1 (2-4).
Furthermore, the molar ratio of the vitamin A organic phosphine salt to the hydrogen peroxide is 1 (1-10), and preferably 1 (2-4).
Further, the solvent is selected from at least one of water, methanol and ethanol, and is preferably water.
Further, the base is selected from at least one of ammonia, ammonium carbonate, alkali metal hydroxide, alkaline earth metal hydroxide, and alkali metal alkoxide.
Further, the alkali metal carbonate is sodium carbonate and/or potassium carbonate.
Further, the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide.
Further, the alkaline earth metal hydroxide is barium hydroxide.
Further, the alkali metal alcoholate is selected from at least one of sodium methylate, potassium methylate, sodium ethylate and potassium ethylate.
Further, the conditions of the oxidative coupling reaction comprise that the reaction temperature is-20 ℃ to 60 ℃, preferably 0 ℃ to 30 ℃, and the reaction time is 0.5 h to 6h, preferably 1h to 2 h.
Furthermore, the preparation method of the beta-carotene provided by the invention also comprises the steps of sequentially filtering, washing with water, washing with alcohol and recrystallizing the oxidation coupling reaction product to obtain beta-carotene crystals.
In the process of oxidizing vitamin A organic phosphonium salt by hydrogen peroxide to obtain the beta-carotene, the nano silver colloid is used as a stabilizer and a catalyst, so that the selectivity and the yield of the beta-carotene can be remarkably improved. The beta-carotene prepared by the method can be used in the fields of medicines, foods, cosmetics, feed additives, dyes and the like.
The inventor of the present invention has found, after extensive and intensive research, that when nano silver colloid is mixed with hydrogen peroxide and added, the hydrogen peroxide can be pre-stabilized before an oxidative coupling reaction system is added, and a large amount of nano silver colloid is closely distributed around the hydrogen peroxide in the adding process or the oxidative coupling reaction process, so that the nano silver colloid can be protected from decomposition, the whole oxidative coupling reaction process is ensured to be carried out controllably, and the selectivity and the yield of beta-carotene are improved.
Detailed Description
In the present invention, the vitamin A organophosphine salt has a structure represented by formula (1):
in the formula (1), R1、R2And R3Each independently being an aliphatic, cycloaliphatic or aromatic radical, preferably each independently being C1～C10Substituted or unsubstituted alkyl, C3～C10Substituted or unsubstituted cycloalkane group of (A) or (C)6～C10More preferably each independently is C1～C5Substituted or unsubstituted alkyl, C3～C8Substituted or unsubstituted cycloalkane group of (A) or (C)6～C10Substituted or unsubstituted aryl of (a); x is a strong organic or inorganic acid group, preferably halogen, sulfate, hydrogen sulfate, phosphate, tetrafluoroborate, acetate, tosylate or benzenesulfonate, more preferably chlorine, bromine or hydrogen sulfate.
Said C is1～C5Specific examples of the substituted or unsubstituted alkyl group of (a) include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl and the like. Said C is3～C8Specific examples of the substituted or unsubstituted cycloalkane group include, but are not limited to: cyclopropane, cyclobutane, cyclopentane, cyclohexane and the like. Said C is6～C10Specific examples of substituted or unsubstituted aryl groups include, but are not limited to: phenyl, o-tolyl, m-tolyl, p-tolyl, o-ethylphenyl, m-ethylphenyl, p-ethylphenyl, naphthyl and the like.
In one embodiment, R1、R2And R3Are both phenyl groups, and X is hydrogen sulfate.
In one embodiment, R1、R2And R3Are all cyclohexyl, and X is bromine.
In one embodiment, R1、R2And R3Are both tolyl radicals, and X is hydrogen sulfate.
In one embodiment, R1、R2And R3Are all phenyl groups, and X is chlorine.
In one embodiment, R1、R2And R3Are all n-butyl, and X is a bromhydric acid radical.
In one embodiment, R1、R2And R3Are both phenyl groups, and X is sulfate.
In one embodiment, R1、R2And R3Are all phenyl, and X is benzene sulfonate.
The vitamin a organophosphine salt can be obtained commercially or prepared according to various methods, for example, the vitamin a alcohol and/or vitamin a fatty acid ester can be obtained by reacting with organophosphine, and the specific reaction process and reaction conditions are well known in the art and will not be described herein.
In the invention, the nano silver colloid simultaneously plays a role of a stabilizer and a catalyst, so that on one hand, hydrogen peroxide can be promoted to stably exist under an alkaline condition to solve the problem that oxidative coupling reaction is uncontrollable due to uncontrollable decomposition of hydrogen peroxide under the alkaline condition, and on the other hand, the selectivity of oxidizing vitamin A organic phosphonium into beta-carrot can be promoted, and the occurrence of side reaction can be reduced. The particle size of the nano silver colloid is 1-100 nm, and preferably 2-100 nm. The nano silver colloid can be added independently, can also be mixed with vitamin A organic phosphonium salt, hydrogen peroxide or a solvent, and is particularly preferably mixed with hydrogen peroxide.
In a preferred embodiment, the oxidative coupling reaction is carried out by: dissolving vitamin A organic phosphonium salt and alkali in a solvent to form a mixed solution, then dripping the mixed solution of nano silver colloid and hydrogen peroxide into the mixed solution, and stirring until the oxidative coupling reaction is complete. Wherein the molar ratio of the vitamin A organic phosphine salt to the alkali is preferably 1 (1-10), and more preferably 1 (2-4). The molar ratio of the vitamin A organic phosphine salt to the hydrogen peroxide is preferably 1 (1-10), and more preferably 1 (2-4). The mass concentration of the nano silver colloid in the mixed liquid of the nano silver colloid and hydrogen peroxide is preferably 0.01-0.1%.
The solvent is an inert liquid reaction medium capable of dissolving vitamin A organic phosphonium salt, alkali and hydrogen peroxide, can be water and/or an organic solvent capable of being mutually dissolved with water, and specifically can be water and C1～C6Alcohol of (2), and the like. Wherein, the C1～C6Specific examples of alcohols of (a) include, but are not limited to: methanol, ethanol, n-propanol, isopropanol, 1-butanol, 1-pentanol, 1-hexanol, and the like. From the viewpoint of the wide range of raw material sources, the solvent is preferably at least one selected from the group consisting of water, methanol and ethanol, and particularly preferably water.
The base may be selected from at least one of ammonia, ammonium carbonate, alkali metal carbonates, alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal alkoxides. The alkali metal carbonate may be sodium carbonate and/or potassium carbonate. The alkali metal hydroxide may specifically be sodium hydroxide and/or potassium hydroxide. The alkaline earth metal hydroxide may specifically be barium hydroxide. The alkali metal alkoxide may specifically be at least one selected from sodium methoxide, potassium methoxide, sodium ethoxide, and potassium ethoxide.
The conditions of the oxidative coupling reaction are not particularly limited in the present invention as long as the two molecules of the vitamin A organophosphine salt can be reacted to produce beta-carotene, and for example, the conditions of the oxidative coupling reaction include that the reaction temperature can be-20 to 60 ℃, preferably 0 to 30 ℃; the reaction time can be 0.5-6 h, preferably 1-2 h. When the hydrogen peroxide is added into the reaction system in a dropwise manner, the temperature of the system in the dropwise addition process also needs to be controlled within the above range, and the above reaction time refers to the time for continuing the reaction after the dropwise addition is finished.
The preparation method of the beta-carotene further comprises the steps of sequentially filtering, washing with water, washing with alcohol and recrystallizing the oxidation coupling reaction product to obtain the high-purity beta-carotene crystal. Wherein the temperature of the water washing and the alcohol washing are respectively and independently 50-70 ℃. The alcohol used in the alcohol washing can be methanol and/or ethanol. The solvent used for the recrystallization may be dichloromethane.
The present invention will be described in detail below by way of examples.
Example 1
500mL of a 0.5mol/L potassium carbonate aqueous solution and 250mL of 0.1mol/L vitamin A triphenylphosphine hydrogen sulfate (having a structure represented by formula (1), R1、R2And R3Phenyl and X is hydrogen sulfate) aqueous solution, 0.1mol of hydrogen peroxide (30%/w%) is added dropwise at 15 ℃, the hydrogen peroxide contains 0.01% (w%) of nano silver colloid (2-100 nm), and the reaction temperature is kept at 15 ℃ for reaction for 1 hour after the dropwise addition. And after the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove triphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 4.48g of beta-carotene crystals. According to the detection of GB 8821-2011-
The same applies below).
Example 2
500mL of a 0.5mol/L potassium hydroxide aqueous solution and 250mL of 0.1mol/L vitamin A tricyclohexyl hydrobromide (having a structure represented by formula (1), R1、R2And R3All cyclohexyl and X is bromine) aqueous solution, 0.05mol of hydrogen peroxide (30%/w%) is added dropwise at 15 ℃, the hydrogen peroxide contains 0.01% (w%) of nano silver colloid (2-100 nm), and the reaction temperature is kept at 15 ℃ for reaction for 2 hours after the dropwise addition. And after the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove triphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 3.66g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 98.0 percent (w percent), and the total yield is 53.5 percent (based on the yield of the phosphonium salt).
Example 3
500mL of an aqueous solution of sodium carbonate having a concentration of 0.25mol/L and 250mL of vitamin A tritolylphosphine hydrogensulfate having a concentration of 0.1mol/L (represented by the formula (1))Structure R1、R2And R3Both tolyl radicals and X hydrogen sulfate) were mixed. Dropwise adding 0.125mol of hydrogen peroxide (30%/w%) at 15 ℃, wherein the hydrogen peroxide contains 0.1% (w%) of nano silver colloid (2-100 nm), and keeping the reaction temperature at 15 ℃ for reacting for 2 hours after dropwise adding. And after the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove trimethylphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 5.16g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 98.4 percent (w percent), and the total yield is 75.6 percent (based on the yield of the phosphonium salt).
Example 4
500mL of a 0.1mol/L sodium methoxide methanol solution and 250mL of a 0.1mol/L vitamin A triphenylphosphine hydrochloride (having a structure shown in formula (1), R)1、R2And R3All phenyl, X is chlorine) in methanol. Dropwise adding 0.15mol of hydrogen peroxide (30%/w%) at-20 ℃, wherein the hydrogen peroxide contains 0.05% (w%) of nano silver colloid (2-100 nm), and keeping the reaction temperature at-20 ℃ for reaction for 3 hours after dropwise adding. After the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove trimethylphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 3.35g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 97.4 percent (w percent), and the total yield is 48.6 percent (based on the yield of the phosphonium salt).
Example 5
500mL of a 0.25mol/L potassium carbonate solution (ethanol: water volume ratio ═ 1:1) and 250mL of a 0.1mol/L vitamin A triphenylphosphine hydrochloride (having a structure represented by formula (1), R1、R2And R3All phenyl groups and X is chlorine) solution (ethanol: water volume is 1:1), 0.25mol of hydrogen peroxide (30%/w%) is added dropwise at 60 ℃, the hydrogen peroxide contains 0.1% (w%) of nano silver colloid (2-100 nm), and the reaction temperature is kept at 60 ℃ after the dropwise addition for reaction for 2 hours. After the reaction is completed, the precipitate is filtered out and treated with 65 DEG CWashing with warm water, filtering, washing with methanol at 50-60 deg.C to remove trimethylphenylphosphine oxide, dissolving beta-carotene in dichloromethane, concentrating, crystallizing, and drying to obtain 3.59g of beta-carotene crystal. According to the detection of GB8821-2011, the content of the beta-carotene is 98.4 percent (w percent), and the total yield is 52.6 percent (based on the yield of the phosphonium salt).
Example 6
500mL of 0.25mol/L ammonium carbonate aqueous solution and 250mL of 0.1mol/L vitamin A tributyl phosphine hydrobromide (having the structure shown in formula (1), R1、R2And R3All n-butyl and X is bromine). Dropwise adding 0.25mol of hydrogen peroxide (30%/w%) at the temperature of 5 ℃, wherein the hydrogen peroxide contains 0.1% (w%) of nano silver colloid (2-100 nm), and keeping the reaction temperature at 5 ℃ for reaction for 4 hours after dropwise adding. After the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove trimethylphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 3.53g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 98.1 percent (w percent), and the total yield is 51.6 percent (based on the yield of the phosphonium salt).
Example 7
250mL of 0.1mol/L ammonium carbonate aqueous solution and 250mL of 0.1mol/L vitamin A triphenyl sulfate (having a structure shown in formula (1), R1、R2And R3All phenyl, X is sulfate) aqueous solution. Dropwise adding 0.05mol of hydrogen peroxide (30%/w%) at 0 ℃, wherein the hydrogen peroxide contains 0.1% (w%) of nano silver colloid (2-100 nm), and keeping the reaction temperature at 5 ℃ for reaction for 5 hours after dropwise adding. After the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove trimethylphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 3.29g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 95.1 percent (w percent), and the total yield is 46.6 percent (based on the yield of the phosphonium salt).
Example 8
500mL of 0.2mol/L ammonium carbonate aqueous solution and 250mL of 0.1mol/L vitamin A triphenylbenzene sulfonate (having a structure shown in formula (1), R1、R2And R3All phenyl, X is benzene sulfonate) aqueous solution. Dropwise adding 0.15mol of hydrogen peroxide (30%/w%) at 30 ℃, wherein the hydrogen peroxide contains 0.1% (w%) of nano silver colloid (2-100 nm), and keeping the reaction temperature at 30 ℃ for reacting for 6 hours after dropwise adding. After the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove trimethylphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 3.08g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 92.1 percent (w percent), and the total yield is 42.3 percent (based on the yield of the phosphonium salt).
Comparative example 1
25.5g of sodium hypochlorite aqueous solution with 10 percent of available chlorine and saturated sodium carbonate aqueous solution are simultaneously dripped into 250mL of methanol-water-1: 1(w: w) solution of vitamin A triphenyl benzene sulfate with the concentration of 0.1mol/L at the temperature of 5 ℃, the amount of the saturated sodium carbonate aqueous solution is ensured that the pH value is between 8 and 10 after the reaction is finished, and the reaction temperature is kept at 5 ℃ for reaction for 4 hours after the dripping is finished. And after the reaction is finished, filtering out the precipitate, washing with 65 ℃ warm water, filtering, washing with methanol at 50-60 ℃ to remove trimethylphenylphosphine oxide, dissolving the beta-carotene into dichloromethane, concentrating, crystallizing and drying to obtain 2.75g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 98.2 percent (w percent), and the total yield is 40.2 percent (based on the yield of the phosphonium salt).
Comparative example 2
Beta-carotene was prepared by the same procedure as in example 3, except that no nano-silver colloid was added to hydrogen peroxide, and the other conditions were the same as in example 3, to obtain 2.87g of beta-carotene crystals. According to the detection of GB8821-2011, the content of the beta-carotene is 92.5 percent (w percent), and the total yield is 39.5 percent (based on the yield of the phosphonium salt).
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (9)
1. A method for preparing beta-carotene, which is characterized by comprising the following steps: carrying out oxidative coupling reaction on vitamin A organic phosphonium salt shown in formula (1) and hydrogen peroxide in an alkaline system containing nano silver colloid;
in the formula (1), R1、R2And R3Each independently is C1-C10 unsubstituted alkyl, C3-C10 unsubstituted naphthenic base or C6-C10 unsubstituted aryl; x is halogen, sulfate radical, hydrogen sulfate radical, phosphate radical, tetrafluoroborate radical, acetate radical, toluene sulfonate radical or benzene sulfonate radical;
the particle size of the nano silver colloid is 2-100 nm;
the molar ratio of the vitamin A organic phosphine salt to the hydrogen peroxide is 1 (1-10);
the molar ratio of the vitamin A organic phosphine salt to the alkali is 1 (1-10);
the mode of the oxidative coupling reaction is as follows: dissolving vitamin A organic phosphonium salt and alkali in a solvent to form a mixed solution, then dripping the mixed solution of nano silver colloid and hydrogen peroxide into the mixed solution, and stirring until the oxidative coupling reaction is complete; the base is selected from at least one of ammonia, ammonium carbonate, alkali metal hydroxide, alkaline earth metal hydroxide and alkali metal alkoxide;
the conditions of the oxidative coupling reaction comprise that the reaction temperature is-20-60 ℃, and the reaction time is 0.5-6 h.
2. The method for preparing beta-carotene according to claim 1, wherein the mass concentration of the nano silver colloid in the mixed solution of the nano silver colloid and hydrogen peroxide is 0.01-0.1%.
3. The method for preparing beta-carotene according to claim 1, wherein the molar ratio of the vitamin A organophosphine salt to the alkali is 1 (2-4).
4. The preparation method of beta-carotene according to claim 1, wherein the molar ratio of the vitamin A organic phosphine salt to the hydrogen peroxide is 1 (2-4).
5. The method of claim 1, wherein the solvent is at least one selected from the group consisting of water, methanol, and ethanol.
6. The method for producing β -carotene according to claim 1, wherein said alkali metal carbonate is sodium carbonate and/or potassium carbonate; the alkali metal hydroxide is sodium hydroxide and/or potassium hydroxide; the alkaline earth metal hydroxide is barium hydroxide; the alkali metal alcoholate is at least one selected from the group consisting of sodium methylate, potassium methylate, sodium ethylate and potassium ethylate.
7. The method for producing beta-carotene according to any one of claims 1 to 6, wherein the conditions of said oxidative coupling reaction include a reaction temperature of 0 ℃ to 30 ℃.
8. The method for producing beta-carotene according to any one of claims 1 to 6, wherein the conditions of said oxidative coupling reaction include a reaction time of 1 to 2 hours.
9. The method for producing β -carotene according to any one of claims 1 to 6, further comprising subjecting the oxidative coupling reaction product to filtration, water washing, alcohol washing, and recrystallization in this order to obtain β -carotene crystals.
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| DE2505869C3 (en) * | 1975-02-12 | 1978-05-18 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of symmetrical carotenoids |
| RU2225394C2 (en) * | 2000-12-22 | 2004-03-10 | Общество С Ограниченной Ответственностью "Научно-Технологическая Фармацевтическая Фирма "Полисан" | METHOD FOR PREPARING β-CAROTENE |
| CN101041631B (en) * | 2006-03-24 | 2010-05-12 | 浙江医药股份有限公司维生素厂 | Improved synthesizing technique for beta-carotene |
| CN100564356C (en) * | 2006-06-02 | 2009-12-02 | 浙江医药股份有限公司新昌制药厂 | The synthesis technique of β-Hu Luobusu |
| 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 |
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