CN100427497C - Method of chemical synthesizing hongjingtian glycoside - Google Patents
Method of chemical synthesizing hongjingtian glycoside Download PDFInfo
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- CN100427497C CN100427497C CNB2006100530357A CN200610053035A CN100427497C CN 100427497 C CN100427497 C CN 100427497C CN B2006100530357 A CNB2006100530357 A CN B2006100530357A CN 200610053035 A CN200610053035 A CN 200610053035A CN 100427497 C CN100427497 C CN 100427497C
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Abstract
The chemical process of synthesizing rhodiola glycoside includes the following steps: the Lewis acid catalyzed glycosidation between pentacetyl-beta-D-glucose and p-hydroxy phenethyl alcohol inside organic solvent to produce tetracetyl rhodiola glycoside; and the subsequent deacetylation of tetracetyl rhodiola glycoside inside the methanol solution of NaOCH3 to obtain rhodiola glycoside. Compared with traditional synthesis process, the present invention has the advantages of wide material source, less reaction steps and low preparation cost. The process of the present invention is suitable for industrial production.
Description
Technical field
The invention belongs to the medicine chemical field, be specifically related to the method for chemosynthesis rhodioside.
Background technology
Rhodiola Crassulaceae plant has nearly hundred kinds in the world, is distributed in the severe cold areas in the Northern Hemisphere more, and great majority are grown in about 3500 meters-5000m of height above sea level.Make the strengthening by means of tonics medicine Root of Kirilow Rhodiola place of production people with it, also be used for Ginseng Extract, keep out the cold; It has anti-ageing, antifatigue, anti-hypoxia, anti-pessimal stimulation, to the body two-ways regulation, suppress effect such as blood sugar increasing.The Soviet Union in 1976 as " adaptogen " sample medicine, is widely used in antifatigue, anti-ageing and improve aspects such as mental and physical function to Root of Kirilow Rhodiola.Utilized rhodiola plant successfully to develop the injection formulations of Root of Kirilow Rhodiola, oral liquid formulations and plurality kinds of health care product in China, its demand is in continuous expansion.
Root of Kirilow Rhodiola is the severe cold areas plant, because of the plateau ecology fragility, regenerative power is poor, naturally regeneration is very slow, generally need self-sow 7-8 to adopt, and it is quite big to produce the herb resource consumption that is consumed, and the wild resource reserves are fewer and feweri, the problem of resource exhaustion may will soon occur.Rhodioside is one of main effective constituent of Root of Kirilow Rhodiola.The extraction of natural salidroside not only needs complicated extraction process, and general extraction yield can only reach 0.4～0.8% of plant dry weight.Therefore developing alternate resources seems very important.Utilizing biotechnology and chemical synthesis process is the important means of development alternate resources.
Existing rhodioside synthetic method has biosynthesizing and chemosynthesis two classes.It is generally acknowledged that biosynthesizing has the reaction conditions gentleness, the stereoselectivity height, characteristics such as reaction process is simple, and is low in the pollution of the environment, but also exist reaction time long simultaneously, the low problem of tiring.The biosynthetic means of rhodioside generally is directly to utilize glucose as carrying out glycosylation reaction for sugared body and p-hydroxyphenylethanol.Reported method mainly contains: utilize Radix Rhodiolae cell (Rhodiola sachalinesis) suspending nutrient solution glucosides method to synthesize rhodioside (Xu Jianfeng; Su Zhiguo; Feng Piao sweet-smelling grass research and development of natural products 1998,10 (2), 8-14; Xu Jianfeng; Su Zhi state Botany Gazette, 1998,40,1129-1135; Wu, Shuangxiu; Zu, Yuangang; Wu, Madeline.J.Biotech.2003,106,33-43); Or carry out glycosylation reaction generation rhodioside (Jia Yanping with strains A bsidia sp.MS2 fermentation crude enzyme liquid catalysis glucose and p-hydroxyphenylethanol; Guo Hongyan; Zhang Chunzhi; Jin Feng is mediate; The Dalian Polytechnic College journal, 2004,23,97-99).Recently, Chinese patent CN 1560268A disclose a kind of with apple seed powder as glucose glycosidation enzyme, directly carry out the method that glucosides is combined to rhodioside with glucose and p-hydroxyphenylethanol.Though the transformation efficiency of this method glucose can reach 15.5%, p-hydroxyphenylethanol can be recycled, and exists the problem of growing p-hydroxyphenylethanol single utilization ratio too low (1.6%) and reaction time (5 days).It tires still lower, and the cost of suitability for industrialized production is still higher.Having report to utilize microorganism to carry out glucosides recently again is combined to the method for rhodioside (Chinese catalysis magazine 2006,27 (3) is given birth in Liu Yunnan for Wang Mengliang, Zhang Fang, and 233-236), but the transformation efficiency of p-hydroxyphenylethanol only reaches 8.2%.
The chemosynthesis of rhodioside has many researchs.As far back as the end of the sixties in last century, the Russianization scholar just utilizes tetrem acyl-D-glucose-1-bromo sugar and p-hydroxyphenylethanol to carry out glycosylation reaction under the catalysis of Lewis acid silver carbonate, generate method [Troshchenko, the A.T. of rhodioside then with the sodium methylate deprotection; Juodvirsis, A.Khim.Prir.Soe. (1969), 5 (4), 256-60.Synthesis of glycosides of 2-(p-hydroxyphenyl) ethanol], but the synthesis yield of this method is lower.Bao Dao certain methods is all similar with this method of condensing afterwards, all use tetrem acyl-D-glucose-1-bromo sugar as the sugared body of confession, and the phenolic hydroxyl group in the glycoside p-hydroxyphenylethanol need be protected in advance.As the p-hydroxyphenylethanol of phenolic hydroxyl group benzylization by the reaction of para hydroxybenzene ethyl ester obtain (Li Guoqing, Lee open up Chinese pharmaceutical chemistry magazine, 1996,6 (2), 136-138), or obtain by the p bromophenol reaction that (Zhang San is strange; Shang Gangwei; Li Zhongjun; Wang Anbang; Cai Mengshen; China's pharmaceutical chemistry magazine, 1997,7 (4), 256-257), or obtain (Zhang Lianji, LI XUEMEI, Tian Guanrong by the p-hydroxyphenylaceticacid reaction; Yanbian University's journal, natural science edition, 2002,28 (2), 97-98), or obtain (Ji Shufang by equal amido phenenyl acid reaction; Zhou Yaqing. Shenyang Pharmacy College's journal 1987,4 (3), 192-193).
Tetrem acyl in the aforesaid method-D-glucose-1-bromo sugar all need be obtained by pentacetyl-beta-D-glucose and Hydrogen bromide effect bromo; and will be with expensive precious metal salt silver carbonate as the glucosides catalyzer; the protecting group of glucosides product on sugar need be gone the protection; also need to remove protecting group on the phenolic hydroxyl group with methods such as palladium shortenings; therefore operation is more, and industrialized cost is higher.Recently; Chinese patent CN 1403467A discloses a kind of under the Louis acid catalysis of catalytic amount; as glucosides reagent and to acetoxyl group phenylethyl alcohol glycosylation reaction, slough the method for the synthetic rhodioside of protecting group with tetra-acetylated-alpha-D-glucose base tribromo-acetyl imines ester then.This method has higher productive rate, however the raw material in this method is tetra-acetylated-alpha-D-glucose base tribromo-acetyl imines ester need be transformed by pentacetyl-beta-D-glucose, and the phenolic hydroxyl group in the p-hydroxyphenylethanol also needs to protect in advance.
Summary of the invention
The purpose of this invention is to provide a kind of being beneficial to and reduce cost, be suitable for the method for industrialized chemosynthesis rhodioside.
The method of chemosynthesis rhodioside of the present invention, its step is as follows:
1) in the presence of molecular sieve, by Louis acid catalysis, with pentacetyl-beta-D-glucose and p-hydroxyphenylethanol in organic solvent, under 10-35 ℃ of temperature glycosylation reaction 0.5-5.0 hour, generate tetrem acyl rhodioside, p-hydroxybenzene alcoholic acid volumetric molar concentration is 0.1-1.0M, the equivalence ratio of pentacetyl-beta-D-glucose and p-hydroxyphenylethanol is 1.0-5.0, the molecular sieve consumption is 0.5-3.0 a times of pentacetyl-beta-D-glucose weight, and the equivalence ratio of Lewis acid and pentacetyl-beta-D-glucose is 0.5-3.0;
2) the tetrem acyl rhodioside that step 1) is obtained joins NaOCH
3Methanol solution in, the volumetric molar concentration of tetrem acyl rhodioside is 0.05-0.5M, NaOCH
3Volumetric molar concentration be 0.1-0.5M, under the room temperature reaction at least 12 hours, deacetylate obtains rhodioside.
In the glycosylation reaction of the present invention, the consumption of pentacetyl-beta-D-glucose reduces, and the productive rate of glucosidesization can reduce, when consumption increases then by product increase, the equivalence ratio of preferred pentacetyl-beta-D-glucose and p-hydroxyphenylethanol is 1.5-2.5.
If without molecular sieve, the glycosylation reaction productive rate obviously descends in glycosylation reaction.Used molecular sieve is the 4A molecular sieve preferably.The preferred molecular sieve consumption is 1.0-2.0 a times of pentacetyl-beta-D-glucose weight.
Glycosylation reaction among the present invention needs Louis acid catalysis, and used Louis is tin tetrachloride SnCl
4Or boron trifluoride BF
3, with SnCl
4For preferably.The equivalence ratio of Lewis acid and pentacetyl-beta-D-glucose is 0.5-3.0, and is preferential with 1.0-2.0.Consumption is very few, and reaction is slowed down, and productive rate obviously reduces.Consumption is excessive, and byproduct of reaction 1-chloro tetrem acyl-β-D-glucose obviously increases.
Used organic solvent can be methylene dichloride or ethylene dichloride among the present invention, or the mixed solvent of methylene dichloride and ether or tetrahydrofuran (THF), or the mixed solvent of ethylene dichloride and ether or tetrahydrofuran (THF).Consumption of organic solvent be for can make the volumetric molar concentration of p-hydroxyphenylethanol reach 0.1-1.0M, and is preferential with 0.2-0.4M.
The glycosylation reaction temperature has very big influence to reaction yield among the present invention, and when temperature was too low, reaction can be carried out very slowly even can not carry out, and when temperature was too high, the glycosidic link isomerization product obviously increased.Temperature of reaction is advisable with 10-35 ℃, and is good with 15-30 ℃.
There is tangible influence in the reaction times to reaction yield among the present invention, and the time, feedstock conversion was incomplete too in short-term, and the time, by product obviously increased when oversize.Reaction times was advisable with 0.5-5.0 hour, and was good with 1.0-2.5 hour.
The chemical equation of chemosynthesis rhodioside of the present invention is as follows, and wherein, structural formula I is a rhodioside, and structure I I is a pentacetyl-beta-D-glucose, and structure III is a p-hydroxyphenylethanol, and structural formula IV is a tetracetyl rhodiola glycoside:
Beneficial effect of the present invention is: compare with traditional synthetic method, need not in advance pentacetyl-beta-D-glucose to be converted into highly active tetrem acyl-D-glucose-1-bromo sugar or tetra-acetylated-alpha-D-glucose base tribromo-acetyl imines ester, phenolic hydroxyl group in the p-hydroxyphenylethanol does not also need protection and direct glucosides generation glucosides, has therefore shortened reactions steps; As long as catalyzer SnCl in the condensation reaction
4, BF
3So cheap Lewis acid, and need not to use expensive silver carbonate, preparation cost obviously descends.So this synthetic method can become the method that is suitable for the suitability for industrialized production rhodioside.
Embodiment
Embodiment 1
(2.93g adds 4A molecular sieve 2 grams in methylene dichloride 7.5mmol) (30ml) solution, stirred 1 hour under nitrogen protection at pentacetyl-beta-D-glucose.Then, (0.585ml 5.0mmol), adds p-hydroxyphenylethanol (0.69g, methylene dichloride 5mmol) (20ml) suspension, stirring at room reaction 2 hours immediately after adding to add tin tetrachloride.Reaction finishes after placing, and topples over organic layer, and organic layer is poured out in minute hypsokinesis of adding ethyl acetate stirred for several in the solids again, repeats once again.After organic phase merges, under agitation pour in the saturated sodium bicarbonate (75ml), tell organic layer after, water layer dichloromethane extraction (3 * 15ml), wash with water after organic layer merges (2 * 30ml), on diatomite, filter then, and remove solvent under reduced pressure and get soup compound.(sherwood oil: methylene dichloride) separate, the pressure reducing and steaming solvent gets white solid tetracetyl rhodiola glycoside 1.06 grams to this soup compound with silica gel column chromatography.
1H?NMR(400MHz，CDCl
3)δ7.03(d，J＝8.4Hz，2H)，6.74(d，J＝8.4Hz，2H)，5.64(s，1H)，5.17(t，J＝9.2Hz，1H)，5.07(dd，J＝10.0Hz，9.2Hz，1H)，4.98(dd，J＝10.0Hz，9.6Hz，1H)，4.47(d，J＝8.4Hz，1H)，4.25(dd，J＝12.4Hz，4.4Hz，1H)，4.14-4.06(m，2H)，3.68-3.60(m，2H)，2.81-2.77(m，2H)，2.08(s，3H)，2.01(s，3H)，1.99(s，3H)，1.91(s，3H)。
Above-mentioned tetracetyl rhodiola glycoside be dissolved in contain sodium methylate (0.27 the gram; 5.0mmol) anhydrous methanol (12.5ml) in; stirring at room reaction 24 hours; after question response finishes, add the acidic resins neutralization, then the elimination resin; filtrate is through concentrating under reduced pressure; and purify to such an extent that rhodioside 0.67 restrains with the silicagel column separation, and overall yield 45%, fusing point is 160-162 ℃.
1H?NMR(500MHz，D
2O)7.12(d，J＝8.5Hz，2H)，6.76(d，J＝8.5Hz，2H)，4.35(d，J＝8.0Hz，1H)，4.10-3.90(m，1H)，3.81-3.70(m，2H)，3.61(dd，J＝12.5Hz，5.5Hz，1H)，3.38-3.25(m，3H)，3.14(dd，J＝9.0Hz，8.0Hz，1H)，2.78(t，J＝7.0Hz，2H).
Embodiment 2
(2.96g adds 4A molecular sieve 2 grams to five acetyl β-D-glucose in methylene dichloride 7.5mmol) (30ml) solution, stirred 1 hour under nitrogen protection.Then, (0.63ml 5.0mmol), adds p-hydroxyphenylethanol (0.69g, methylene dichloride 5mmol) (20ml) suspension, stirring at room reaction 5 hours immediately after adding to add boron trifluoride ether solution.Obtain tetracetyl rhodiola glycoside 0.30 gram.
Above-mentioned tetracetyl rhodiola glycoside be dissolved in contain sodium methylate (0.07 gram, in anhydrous methanol 1.3mmol) (12.5ml), stirring at room reaction 12 hours.After question response finishes, add the acidic resins neutralization, elimination resin then, filtrate is through concentrating under reduced pressure, and with silicagel column separate purify rhodioside 0.17 gram, overall yield 11%.
Embodiment 3
(3.90g adds 4A molecular sieve 2 grams to five acetyl β-D-glucose in methylene dichloride 1.0mmol) (30ml) solution, stirred 1 hour under nitrogen protection.Then, (0.88ml 7.5mmol), adds p-hydroxyphenylethanol (0.69g, methylene dichloride 5mmol) (20ml) suspension, stirring at room reaction 2 hours immediately after adding to add tin tetrachloride.Obtain tetracetyl rhodiola glycoside 0.56 gram.
Above-mentioned tetracetyl rhodiola glycoside be dissolved in contain sodium methylate (0.14 gram, in anhydrous methanol 2.5mmol) (12.5ml), stirring at room reaction 24 hours.After question response finishes, add the acidic resins neutralization, elimination resin then, filtrate is through concentrating under reduced pressure, and with silicagel column separate purify rhodioside 0.33 gram, overall yield 22%.
Embodiment 4
(2.96g adds 4A molecular sieve 6 grams to five acetyl β-D-glucose in ethylene dichloride 7.5mmol) (30ml) solution, stirred 1 hour under nitrogen protection.Then, (0.585ml, 5.0mmol), (0.69g, ethylene dichloride 5mmol) (20ml) suspension was 35 ℃ of stirring reactions 4 hours to add p-hydroxyphenylethanol after adding immediately to add tin tetrachloride.Obtain tetracetyl rhodiola glycoside 0.42 gram.
Above-mentioned tetracetyl rhodiola glycoside be dissolved in contain sodium methylate (0.27 gram, in anhydrous methanol 5.0mmol) (12.5ml), stirring at room reaction 12 hours.After question response finishes, add the acidic resins neutralization, elimination resin then, filtrate is through concentrating under reduced pressure, and with silicagel column separate purify rhodioside 0.25 gram, overall yield 17%.
Embodiment 5
(2.96g adds 4A molecular sieve 2 grams to five acetyl β-D-glucose in methylene dichloride 7.5mmol) (30ml) and ether (15ml) solution, stirred 1 hour under nitrogen protection.Then, be cooled to 10 ℃ and add tin tetrachloride (0.585ml, 5.0mmol), (0.69g, methylene dichloride 5mmol) (20ml) suspension was 10 ℃ of stirring reactions 5 hours to add p-hydroxyphenylethanol after adding immediately.Obtain tetracetyl rhodiola glycoside 0.22 gram.
Above-mentioned tetracetyl rhodiola glycoside be dissolved in contain sodium methylate (0.14 gram, in anhydrous methanol 2.5mmol) (12.5ml), stirring at room reaction 12 hours.After question response finishes, add the acidic resins neutralization, elimination resin then, filtrate is through concentrating under reduced pressure, and with silicagel column separate purify rhodioside 0.14 gram, overall yield 9%.
Embodiment 6
(3.90g adds 4A molecular sieve 4 grams to five acetyl β-D-glucose in methylene dichloride 1.0mmol) (30ml) solution, stirred 1 hour under nitrogen protection.Then, (1.17ml 1.0mmol), adds p-hydroxyphenylethanol (0.69g, methylene dichloride 5mmol) (20ml) suspension, stirring at room reaction 0.5 hour immediately after adding to add tin tetrachloride.Obtain tetracetyl rhodiola glycoside 0.63 gram.
Above-mentioned tetracetyl rhodiola glycoside be dissolved in contain sodium methylate (0.27 gram, in anhydrous methanol 5.0mmol) (12.5ml), stirring at room reaction 24 hours.After question response finishes, add the acidic resins neutralization, elimination resin then, filtrate is through concentrating under reduced pressure, and with silicagel column separate purify rhodioside 0.39 gram, overall yield 26%.
Claims (9)
1. the method for a chemosynthesis rhodioside, its step is as follows:
1) in the presence of molecular sieve, by Louis acid catalysis, with pentacetyl-beta-D-glucose and p-hydroxyphenylethanol in organic solvent, under 10-35 ℃ of temperature glycosylation reaction 0.5-5.0 hour, generate tetrem acyl rhodioside, the volumetric molar concentration of p-hydroxyphenylethanol is 0.1-1.0M, the equivalence ratio of pentacetyl-beta-D-glucose and p-hydroxyphenylethanol is 1.0-5.0, the molecular sieve consumption is 0.5-3.0 a times of pentacetyl-beta-D-glucose weight, the equivalence ratio of Lewis acid and pentacetyl-beta-D-glucose is 0.5-3.0, and said Lewis acid is tin tetrachloride or boron trifluoride;
2) the tetrem acyl rhodioside that step 1) is obtained joins NaOCH
3Methanol solution in, the volumetric molar concentration of tetrem acyl rhodioside is 0.05-0.5M, NaOCH
3Volumetric molar concentration be 0.1-0.5M, under the room temperature reaction at least 12 hours, deacetylate obtains rhodioside.
2. the method for chemosynthesis rhodioside according to claim 1, the equivalence ratio that it is characterized in that pentacetyl-beta-D-glucose and p-hydroxyphenylethanol is 1.5-2.5.
3. the method for chemosynthesis rhodioside according to claim 1 is characterized in that said molecular sieve is the 4A molecular sieve.
4. the method for chemosynthesis rhodioside according to claim 1 is characterized in that the molecular sieve consumption is 1.0-2.0 a times of pentacetyl-beta-D-glucose weight.
5. the method for chemosynthesis rhodioside according to claim 1, the equivalence ratio that it is characterized in that Lewis acid and pentacetyl-beta-D-glucose is 1.0-2.0.
6. the method for chemosynthesis rhodioside according to claim 1, it is characterized in that said organic solvent is methylene dichloride or ethylene dichloride, or the mixed solvent of methylene dichloride and ether or tetrahydrofuran (THF), or the mixed solvent of ethylene dichloride and ether or tetrahydrofuran (THF).
7. the method for chemosynthesis rhodioside according to claim 1, the volumetric molar concentration that it is characterized in that p-hydroxyphenylethanol is 0.2-0.4M.
8. the method for chemosynthesis rhodioside according to claim 1 is characterized in that the glycosylation reaction temperature is 15-30 ℃.
9. the method for chemosynthesis rhodioside according to claim 1 is characterized in that the glycosylation reaction time is 1.0-2.5 hour.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304157B (en) * | 2011-07-01 | 2014-06-18 | 北京大学 | Salidroside chemical synthesis method for industrialization |
| CN102286036A (en) * | 2011-08-28 | 2011-12-21 | 武汉信嘉和诚药物化学有限公司 | Synthesis method of rhodioside |
| CN104045669B (en) * | 2014-06-05 | 2016-08-24 | 辽宁大学 | A kind of separation method of the chemosynthesis rhodioside of applicable industrialized production |
| CN105294787B (en) * | 2014-07-16 | 2018-11-27 | 宜昌人福药业有限责任公司 | A kind of synthetic method and its midbody compound of rhodioside |
| CN104542036A (en) * | 2015-01-06 | 2015-04-29 | 湖南中医药大学 | Cultivation method of vegetable containing salidroside and application |
| CN104585374A (en) * | 2015-01-06 | 2015-05-06 | 湖南中医药大学 | Preparation method and application of tea containing salidroside |
| CN104592321B (en) * | 2015-01-09 | 2017-09-19 | 武汉信嘉和诚药物化学有限公司 | The process for catalytic synthesis of rhodioside |
| CN106674300B (en) * | 2016-12-05 | 2019-07-16 | 湖南大学 | A kind of preparation method of natural products rhodioside |
| CN109422784B (en) * | 2017-09-04 | 2022-02-08 | 福建中医药大学 | Salidroside derivative and preparation method and application thereof |
| CN107936065A (en) * | 2017-12-12 | 2018-04-20 | 浙江农林大学 | A kind of application of rhodioside of method and synthesis based on Microwave-assisted synthesis rhodioside on anti-senile preparation |
| WO2021139621A1 (en) * | 2020-01-09 | 2021-07-15 | 上海和黄药业有限公司 | Method for preparing glycoside compound |
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