CN104370977A - Preparation method of 2-O-(2, 3, 4, 6-tetra-O-acetyl-Beta-D-glucopyranosyl)-3-O-benzyl-5, 6-isopropylidene-ascorbic acid - Google Patents
Preparation method of 2-O-(2, 3, 4, 6-tetra-O-acetyl-Beta-D-glucopyranosyl)-3-O-benzyl-5, 6-isopropylidene-ascorbic acid Download PDFInfo
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Abstract
The invention relates to a preparation method of 2-O-(2, 3, 4, 6-tetra-O-acetyl-Beta-D-glucopyranosyl)-3-O-benzyl-5, 6-isopropylidene-ascorbic acid. The preparation method includes: under catalysis of p-toluenesulfonic acid and under the condition of ice bath, allowing vitamin C and acetone to react for 3-5h, and performing filtering, washing and drying to obtain white solid of 5, 6-O-isopropylidene-L-ascorbic acid; adding mixture of benzyl bromide, alkali and the white solid of the 5, 6-O-isopropylidene-L-ascorbic acid into solvent, performing heating to allow reflux reaction for 3-5h, and washing and purifying reaction liquid to obtain 3-O-benzyl-5, 6-O-isopropylidene-L-ascorbic acid; dissolving the 3-O-benzyl-5, 6-O-isopropylidene-L-ascorbic acid with dichloromethane, dropwise adding dissolved solution into sodium hydroxide solution containing phase-transfer catalysts such as 2, 3, 4, 6-tetra-O-acetyl-Alpha-glucopyranosyl bromide and quaternary ammonium salts, and allowing reaction to obtain a product. The preparation method has the advantages that raw materials are easy to obtain, reaction conditions are moderate, the synthetic process is easy to control, yield is high, and the method has important applicable value.
Description
Technical field
The present invention relates to a kind of preparation of vitamin C derivatives, particularly a kind of 2-O-(2,3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl) preparation method of-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid, belong to chemosynthesis technical field.
Background technology
Vitamins C, also known as the anti-hematic acid of L-, molecular formula is C
6h
8o
6though requirement is little, being maintain the necessary nutritive element of body, is maintain the necessary class low-molecular-weight organic compound of biological normal activities, in the process of growth protecting HUMAN HEALTH and animal, play irreplaceable effect.Vitamins C has many important functions and purposes: for health care, prevents the generation of various chronic infectious disease, vitamin C deficiency etc., builds up resistance, and promotes the healing of body wound, as ancillary drug in treatment and health care medicine; For beauty treatment, promote the synthesis of cell collagen albumen, decompose the melanochrome in skin, prevention pigmentation, prevents and treats the generation of freckle, chloasma, makes skin keep delicacy, whitening, health, is therefore widely used at cosmetic industry; Its reduced form and L mono-L-dehydroascorbic acid of oxidized form all have physiologically active, and cellular metabolism also applies this pair oxidation one restoring system that it is formed, and plays important physiological action simultaneously; For foodstuff additive, there is nutritional fortification, anti-metamorphic and fresh-keeping effect in food, therefore have the title of " food enrichment ".Though but the active high but extremely unstable in aqueous of vitamins C, oxygen simultaneously in air, heat, light, alkaline matter also can break its reducing power of ring, accelerate its degradation speed, it obviously reduces in the commercial value of cosmetic industry and effective rate of utilization, and people are finding the method that can improve Vitamin C Stability always.Research shows, vitamin C derivatives has good stability, 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid is the one of vitamin C derivatives, also be synthesize the important intermediate of the anti-hematic acid of 2-O-β-D-glucopyranosyl-L-, wherein, the anti-hematic acid of 2-O-β-D-glucopyranosyl-L-, be called for short AA-2 β G, the predecessor of the anti-hematic acid of a kind of novel stabilising, the growth of its energy check melanin cell, reduce melanic synthesis, tyrosine oxidase plays keying action in melanic catalysis and adjustment, AA-2 β G suppression its active in obviously especially in the vitamins C of equivalent, so it is at makeup, skin care aspect all plays very important effect.AA-2 β G is better than AA-2 α G in physiologically active, thus people expect that AA-2 β G has in makeup, medicine and food applies widely.In WO2003057707; the people such as Mitsuru Maeda propose 2-O-(2; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl) synthetic method of-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid: vitamins C and acetone reaction, and then and bromotoluene etherification reaction; last with 2; 3,4,6-tetra--O-ethanoyl-β-D-glucopyranosyl-2; 2; 2-trichloroethyl carbonate reaction obtains product 2-O-(2,3,4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid.In this preparation method 2,3,4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl-2,2,2-trichloroethyl carbonic ether trichloroethyl chloroformate and 2; 3,4,6-tetra--O-ethanoyl-β-D-Glucose reaction preparation; severe reaction conditions; trichloroethyl chloroformate is expensive, and building-up process uses phosgene, and toxicity is large; building-up process is complicated, and production cost is high.The present invention overcomes existing technical deficiency; improve for this synthetic method; thus be applied to research and development better; therefore; 2-O-(2,3,4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl) research of-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid new preparation process has very important significance.
Summary of the invention
The object of the invention is the deficiency in order to overcome above-mentioned technology; and a kind of 2-O-(2 is provided; 3,4,6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; this preparation method's raw material is easy to get, and selects quaternary ammonium salt to cook phase-transfer catalyst, and reaction conditions is gentle; reaction process is easy to control, and product stability is high.
The present invention is realized by following technical proposal:
A kind of preparation method of 2-O-(2,3,4,6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid, comprises step as follows:
(1) by vitamins C and acetone, under Catalyzed by p-Toluenesulfonic Acid, under condition of ice bath, react 3-5h, filter, washing, dry the anti-hematic acid white solid of 5,6-O-isopropylidene-L-;
(2) add in solvent by bromotoluene, alkali, the anti-hematic acid white solid mixing of 5,6-O-isopropylidene-L-, heating reflux reaction 3-5h, washs reaction solution, purifying obtains jonquilleous oily matter, i.e. the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-;
(3) the anti-hematic acid methylene dichloride of 3-O-benzyl-5,6-O-isopropylidene-L-is dissolved, be then added drop-wise to containing 2; in the sodium hydroxide solution of 3,4,6-tetra--O-ethanoyl-alpha-brominated glucose and quaternary ammonium salt-type phase transfer catalyst; reaction process temperature is at 30 ~ 100 DEG C; reaction times is 3 ~ 5h, is washed by reaction soln, purifies, obtain product 2-O-(2; 3; 4,6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid.
In above-mentioned preparation method, the amount of substance ratio of the vitamins C described in step (1), acetone, tosic acid is 1 ~ 5:1 ~ 20:0.1 ~ 5.0.In step (2), the amount of substance of bromotoluene, alkali, the anti-hematic acid of 5,6-O-isopropylidene-L-is than being 1:1 ~ 10:1 ~ 6; Described alkali is sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide.Described solvent is acetone or DMSO, and the volume ratio of bromotoluene and solvent is 1:1 ~ 20; Described washing, purify for washing, extraction, salt wash, distill, chromatography over CC.
In step (3), the amount of substance of the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-, 2,3,4,6-tetra--O-ethanoyl-alpha-brominated glucose, quaternary ammonium salt-type phase transfer catalyst is than being 1:1 ~ 5:1 ~ 10; The volume ratio of sodium hydroxide solution and methylene dichloride is 1:1 ~ 10.
Described quaternary ammonium salt-type phase transfer catalyst is any one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, Dodecyl trimethyl ammonium chloride.Described sodium hydroxide solution mass concentration is 1% ~ 20%.Described washing, purify for salt wash, extract, air distillation, chromatography over CC.
The invention has the beneficial effects as follows:
(1) the method raw material is easy to get, and methylene dichloride, quaternary ammonium salt are all the raw materials easily bought, and cost is also lower;
(2) utilize quaternary ammonium salt to make phase-transfer catalyst, at water react, reaction conditions is gentle, and reaction process is easy to control;
(3) reaction yield is high, and final step yield, up to 75%, has significant application value.
Embodiment
Below in conjunction with embodiment, the present invention will be further elaborated, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1
In the single port flask of 100mL, add 3.52g vitamins C, 2.76g tosic acid, 15mL acetone, under condition of ice bath, react 4h, vacuum filtration, uses ethyl acetate washing leaching cake, vacuum-drying, obtain 5,6-O-isopropylidene-L-anti-hematic acid white solid 4.08g, yield is 94.4%.
To mechanical stirrer is housed, reflux condensing tube, 5 are added in the there-necked flask of the 100mL of thermometer, the anti-hematic acid 2.16g of 6-O-isopropylidene-L-, sodium carbonate 1.06g, bromotoluene 1.20mL, acetone 20mL, 4h is reacted under reflux state, treat that above-mentioned solution is down to room temperature, reaction solution is washed, ethyl acetate (3 × 20mL) extracts, saturated nacl aqueous solution salt is washed, anhydrous magnesium sulfate drying, filter, normal pressure steams except ethyl acetate, column chromatography (sherwood oil: ethyl acetate=3:1) is purified and is obtained jonquilleous oily matter, obtain 3-O-benzyl-5, the anti-hematic acid 1.89g of 6-O-isopropylidene-L-, yield is 61.8%.
To mechanical stirrer is housed, reflux condensing tube, in the 100mL four-hole boiling flask of constant pressure funnel and thermometer, add 3.09g (7.5mmol) 2, 3, 4, 6-tetra--O-ethanoyl-alpha-brominated glucose, the sodium hydroxide solution of 10mL5wt%, 2.58g (8mmol) Tetrabutyl amonium bromide, by 1.84g (6mmol) 3-O-benzyl-5, 6-O-isopropylidene-L-anti-hematic acid 30mL methylene dichloride dissolves and is added drop-wise in above-mentioned solution, the temperature controlling in reaction process to react is 35 DEG C, reaction times is 4h, treat that above-mentioned reaction solution is down to room temperature, extract with methylene dichloride (3 × 20mL), anhydrous sodium sulfate drying, filter, normal pressure steams except methylene dichloride, column chromatography (sherwood oil: ethyl acetate=2:1) is purified, obtain product 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid 2.87g, yield is 75.5%.
ESI-MS：m/z Calcd C
30H
36O
15659.1946[M+Na]
+，found 659.1861[M+Na]
+
Embodiment 2
In the single port flask of 100mL, add 3.52g vitamins C, 2.76g tosic acid, 15mL acetone, under condition of ice bath, react 4h, vacuum filtration, uses ethyl acetate washing leaching cake, vacuum-drying, obtain 5,6-O-isopropylidene-L-anti-hematic acid white solid 4.08g, yield is 94.4%.
To mechanical stirrer is housed, reflux condensing tube, 5 are added in the there-necked flask of the 100mL of thermometer, the anti-hematic acid 2.16g of 6-O-isopropylidene-L-, salt of wormwood 1.40g, bromotoluene 1.20mL, acetone 20mL, carry out reaction 4h at reflux, treat that above-mentioned solution is down to room temperature, reaction solution is washed, ethyl acetate (3 × 20mL) extracts, saturated nacl aqueous solution salt is washed, anhydrous magnesium sulfate drying, filter, normal pressure steams except ethyl acetate, column chromatography (sherwood oil: ethyl acetate=3:1) is purified and is obtained jonquilleous oily matter, obtain 3-O-benzyl-5, the anti-hematic acid 1.43g of 6-O-isopropylidene-L-, yield is 46.7%.
To mechanical stirrer is housed, reflux condensing tube, 100mL constant pressure funnel, in the four-hole boiling flask of thermometer, add 4.94g (12mmol) 2, 3, 4, 6-tetra--O-ethanoyl-alpha-brominated glucose, the sodium hydroxide solution of 10mL5wt%, 2.58g (8mmol) Tetrabutyl amonium bromide, by 1.84g (6mmol) 3-O-benzyl-5, 6-O-isopropylidene-L-anti-hematic acid 30mL methylene dichloride dissolves and is added drop-wise in above-mentioned solution, the temperature controlling in reaction process to react is 35 DEG C, reaction times is 4h, treat that above-mentioned reaction solution is down to room temperature, extract with methylene dichloride (3 × 20mL), anhydrous sodium sulfate drying, filter, normal pressure steams except methylene dichloride, column chromatography (sherwood oil: ethyl acetate=2:1) is purified, obtain product 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid 2.56g, yield is 67.4%.
Embodiment 3
The preparation of the anti-hematic acid of 5,6-O-isopropylidene-L-and the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-is with embodiment 1.
To mechanical stirrer is housed, reflux condensing tube, 100mL constant pressure funnel, in the four-hole boiling flask of thermometer, add 3.09g (7.5mmol) 2, 3, 4, 6-tetra--O-ethanoyl-alpha-brominated glucose, the sodium hydroxide solution of 10mL5wt%, 1.82g (8mmol) benzyltriethylammoinium chloride, by 1.84g (6mmol) 3-O-benzyl-5, 6-O-isopropylidene-L-anti-hematic acid 30mL methylene dichloride dissolves and is added drop-wise in above-mentioned solution, the temperature controlling in reaction process to react is 35 DEG C, reaction times is 4h, treat that above-mentioned reaction solution is down to room temperature, extract with methylene dichloride (3 × 20mL), anhydrous sodium sulfate drying, filter, normal pressure steams except methylene dichloride, column chromatography (sherwood oil: ethyl acetate=2:1) is purified, obtain product 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid 2.61g, yield is 68.7%.
Embodiment 4
The preparation of the anti-hematic acid of 5,6-O-isopropylidene-L-and the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-is with embodiment 1.
To mechanical stirrer is housed, reflux condensing tube, 100mL constant pressure funnel, in the four-hole boiling flask of thermometer, add 3.09g (7.5mmol) 2, 3, 4, 6-tetra--O-ethanoyl-alpha-brominated glucose, the sodium hydroxide solution of 10mL5wt%, 2.58g (8mmol) Tetrabutyl amonium bromide, by 1.84g (6mmol) 3-O-benzyl-5, 6-O-isopropylidene-L-anti-hematic acid 30mL methylene dichloride dissolves and is added drop-wise in above-mentioned solution, the temperature controlling in reaction process to react is 25 DEG C, reaction times is 4h, extract with methylene dichloride (3 × 20mL), anhydrous sodium sulfate drying, filter, normal pressure steams except methylene dichloride, column chromatography (sherwood oil: ethyl acetate=2:1) is purified, obtain product 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid 2.14g, yield is 56.3%.
Embodiment 5
The preparation of the anti-hematic acid of 5,6-O-isopropylidene-L-and the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-is with embodiment 1.
To mechanical stirrer is housed, reflux condensing tube, 100mL constant pressure funnel, in the four-hole boiling flask of thermometer, add 3.09g (7.5mmol) 2, 3, 4, 6-tetra--O-ethanoyl-alpha-brominated glucose, the sodium hydroxide solution of 10mL5wt%, 2.58g (8mmol) Tetrabutyl amonium bromide, by 1.84g (6mmol) 3-O-benzyl-5, 6-O-isopropylidene-L-anti-hematic acid 30mL methylene dichloride dissolves and is added drop-wise in above-mentioned solution, be 55 DEG C at oil bath temperature to react, reaction times is 4h, treat that above-mentioned reaction solution is down to room temperature, extract with methylene dichloride (3 × 20mL), anhydrous sodium sulfate drying, filter, normal pressure steams except methylene dichloride, column chromatography (sherwood oil: ethyl acetate=2:1) is purified, obtain product 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid 1.68g, yield is 44.2%.
Embodiment 6
The preparation of the anti-hematic acid of 5,6-O-isopropylidene-L-and the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-is with embodiment 1.
To mechanical stirrer is housed, reflux condensing tube, 100mL constant pressure funnel, in the four-hole boiling flask of thermometer, add 3.09g (7.5mmol) 2, 3, 4, 6-tetra--O-ethanoyl-alpha-brominated glucose, the sodium hydroxide solution of 10mL10wt%, 2.58g (8mmol) Tetrabutyl amonium bromide, by 1.84g (6mmol) 3-O-benzyl-5, 6-O-isopropylidene-L-anti-hematic acid 30mL methylene dichloride dissolves and is added drop-wise in above-mentioned solution, the temperature controlling in reaction process to react is 35 DEG C, reaction times is 4h, treat that above-mentioned reaction solution is down to room temperature, extract with methylene dichloride (3 × 20mL), anhydrous sodium sulfate drying, filter, normal pressure steams except methylene dichloride, column chromatography (sherwood oil: ethyl acetate=2:1) is purified, obtain product 2-O-(2, 3, 4, 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5, 6-O-isopropylidene-anti-hematic acid 2.08, yield is 54.7%.
Claims (10)
1. the preparation method of 2-O-(2,3,4,6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid, is characterized in that, comprise step as follows:
(1) by vitamins C and acetone, under Catalyzed by p-Toluenesulfonic Acid, under condition of ice bath, react 3-5h, filter, washing, dry the anti-hematic acid white solid of 5,6-O-isopropylidene-L-;
(2) add in solvent by bromotoluene, alkali, the anti-hematic acid white solid mixing of 5,6-O-isopropylidene-L-, heating reflux reaction 3-5h, washs reaction solution, purifying obtains jonquilleous oily matter, i.e. the anti-hematic acid of 3-O-benzyl-5,6-O-isopropylidene-L-;
(3) the anti-hematic acid methylene dichloride of 3-O-benzyl-5,6-O-isopropylidene-L-is dissolved, be then added drop-wise to containing 2; in the sodium hydroxide solution of 3,4,6-tetra--O-ethanoyl-alpha-brominated glucose and quaternary ammonium salt-type phase transfer catalyst; reaction process temperature is at 30 ~ 100 DEG C; reaction times is 3 ~ 5h, is washed by reaction soln, purifies, obtain product 2-O-(2; 3; 4,6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5,6-O-isopropylidene-anti-hematic acid.
2. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the amount of substance ratio of the vitamins C described in step (1), acetone, tosic acid is 1 ~ 5:1 ~ 20:0.1 ~ 5.0.
3. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, in step (2), the amount of substance of bromotoluene, alkali, the anti-hematic acid of 5,6-O-isopropylidene-L-is than being 1:1 ~ 10:1 ~ 6.
4. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the alkali described in step (2) is sodium carbonate, salt of wormwood, sodium hydroxide or potassium hydroxide.
5. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the solvent described in step (2) is acetone or DMSO, and the volume ratio of bromotoluene and solvent is 1:1 ~ 20.
6. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the washing described in step (2), purify for washing, extraction, salt wash, distill, chromatography over CC.
7. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that; 3-O-benzyl-5 in step (3); the anti-hematic acid of 6-O-isopropylidene-L-, 2; 3; the amount of substance of 4,6-tetra--O-ethanoyl-alpha-brominated glucose, quaternary ammonium salt-type phase transfer catalyst is than being 1:1 ~ 5:1 ~ 10, and the volume ratio of sodium hydroxide solution and methylene dichloride is 1:1 ~ 10.
8. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the quaternary ammonium salt-type phase transfer catalyst described in step (3) is any one in benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, Dodecyl trimethyl ammonium chloride.
9. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the sodium hydroxide solution mass concentration described in step (3) is 1% ~ 20%.
10. a kind of 2-O-(2 according to claim 1; 3; 4; 6-tetra--O-ethanoyl-β-D-glucopyranosyl)-3-O-benzyl-5; the preparation method of 6-O-isopropylidene-anti-hematic acid; it is characterized in that, the washing described in step (3), purify for salt wash, extract, air distillation, chromatography over CC.
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| CN105367524A (en) * | 2015-06-19 | 2016-03-02 | 上海珈叶实业有限公司 | Preparation method of 3-O-alkyl ascorbic acid |
| CN110183432A (en) * | 2019-06-28 | 2019-08-30 | 珠海市柏瑞医药科技有限公司 | A kind of preparation process of 5,6-O- isopropylidene-L-AA |
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| WO2003057707A1 (en) * | 2001-12-28 | 2003-07-17 | Suntory Limited | 2-o-( -d-glucopyranosyl)ascorbic acid, process for its production, and foods and cosmetics containing compositions comprising it |
| TWI329024B (en) * | 2003-06-26 | 2010-08-21 | Suntory Holdings Ltd | Composition for skin, kit for skin and skin permeation enhancer |
| CN102477051A (en) * | 2010-11-30 | 2012-05-30 | 重庆礼邦药物开发有限公司 | Technology for preparing key intermediate of telbivudine |
| CN103588759B (en) * | 2013-11-20 | 2016-08-17 | 北京桑普生物化学技术有限公司 | The preparation technology of 5,6-O-isopropylidene-L-AA |
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| CN105367524A (en) * | 2015-06-19 | 2016-03-02 | 上海珈叶实业有限公司 | Preparation method of 3-O-alkyl ascorbic acid |
| CN110183432A (en) * | 2019-06-28 | 2019-08-30 | 珠海市柏瑞医药科技有限公司 | A kind of preparation process of 5,6-O- isopropylidene-L-AA |
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