CN102040636B - Synthesizing beta-arbutin by adopting alpha-D-glucose pentaacetate - Google Patents
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- BJRNKVDFDLYUGJ-RMPHRYRLSA-N hydroquinone O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-RMPHRYRLSA-N 0.000 title claims abstract description 53
- UAOKXEHOENRFMP-UHFFFAOYSA-N (2,3,4,5-tetraacetyloxy-6-oxohexyl) acetate Chemical compound CC(=O)OCC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C=O UAOKXEHOENRFMP-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 title abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000006227 byproduct Substances 0.000 claims abstract description 8
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 24
- 229960000271 arbutin Drugs 0.000 description 11
- BJRNKVDFDLYUGJ-UHFFFAOYSA-N p-hydroxyphenyl beta-D-alloside Natural products OC1C(O)C(O)C(CO)OC1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-UHFFFAOYSA-N 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LPTITAGPBXDDGR-UHFFFAOYSA-N Penta-Ac-Mannose Natural products CC(=O)OCC1OC(OC(C)=O)C(OC(C)=O)C(OC(C)=O)C1OC(C)=O LPTITAGPBXDDGR-UHFFFAOYSA-N 0.000 description 3
- LPTITAGPBXDDGR-IBEHDNSVSA-N beta-d-glucose pentaacetate Chemical compound CC(=O)OC[C@H]1O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)[C@@H]1OC(C)=O LPTITAGPBXDDGR-IBEHDNSVSA-N 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229930182470 glycoside Natural products 0.000 description 3
- 150000002338 glycosides Chemical class 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- -1 acyl glucosides Chemical class 0.000 description 2
- BJRNKVDFDLYUGJ-ZIQFBCGOSA-N alpha-Arbutin Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-ZIQFBCGOSA-N 0.000 description 2
- 229940033280 alpha-arbutin Drugs 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000012871 Arctostaphylos uva ursi Nutrition 0.000 description 1
- 241001656831 Arctous alpina Species 0.000 description 1
- 240000004972 Bergenia crassifolia Species 0.000 description 1
- 235000014785 Bergenia crassifolia Nutrition 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 235000016357 Mirtillo rosso Nutrition 0.000 description 1
- 240000001987 Pyrus communis Species 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 235000003095 Vaccinium corymbosum Nutrition 0.000 description 1
- 244000003892 Vaccinium erythrocarpum Species 0.000 description 1
- 240000001717 Vaccinium macrocarpon Species 0.000 description 1
- 235000012545 Vaccinium macrocarpon Nutrition 0.000 description 1
- 235000017537 Vaccinium myrtillus Nutrition 0.000 description 1
- 235000002118 Vaccinium oxycoccus Nutrition 0.000 description 1
- 244000077233 Vaccinium uliginosum Species 0.000 description 1
- 244000077923 Vaccinium vitis idaea Species 0.000 description 1
- 235000017606 Vaccinium vitis idaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000021014 blueberries Nutrition 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 235000004634 cranberry Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000007854 depigmenting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 150000008495 β-glucosides Chemical class 0.000 description 1
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- Saccharide Compounds (AREA)
Abstract
The invention takes alpha-D-glucose pentaacetate as the raw material to synthesize a key intermediate 4-hydroxyphenyl-beta-glucoside tetraacetate or 4-acetyloxyphenyl-beta-glucoside tetraacetate, thus synthesizing beta-arbutin. The invention develops a new method and new process for synthesizing beta-arbutin by adopting the raw materials or by-products such as alpha-D-glucose pentaacetate and the like.
Description
Technical field
The invention belongs to the exploitation of synthetic β-arbutin technique Raw, relating to take the alpha-D-glucose pentaacetate as raw material and to replace the synthetic β-arbutin of β-D-Glucose pentaacetate, is the by product of synthetic β-D-Glucose pentaacetate as the alpha-D-glucose pentaacetate of new raw material.
Background technology
Arbutin (Arbutin) chemistry 4-hydroxy phenyl-β by name-D-glucopyranoside is to separate the natural active matter that obtains from plant.As far back as nineteen thirty report is just arranged, contain arbutin in the leaf of Rhizoma Seu Herba Bergeniae (Bergenia Crassifolia), in succession in the leaf of bird meal tree (Blueberry), cowberry (Cranberry), black bearberry (Bearberry) and pear tree, find arbutin later on.
The for a long time chemosynthesis of many scholar's research arbutin.1980 mid-nineties 90s were emerged in large numbers a large amount of relevant patents, and generation nineteen ninety rises, and arbutin begins for makeup.Nowadays, arbutin occupies critical role as the skin-whitening agents of makeup in makeup whitening function additive.
Early stage employing glucose is starting raw material, obtain β-D-Glucose pentaacetate (hereinafter to be referred as β-five acetyl sugar) through acetylize, and then through the synthetic arbutin of bromo sugar, this method raw material is expensive, intermediate is unstable, is worthless as production technique.
Helferich in 1938 and Reischel report are with 4-MeC
6H
4SO
3H is catalyzer, with 4-HOC
6H
4The condensation of OBz and β-five acetyl sugar gets β-benzyl oxy phenyl tetrem acyl glucosides.The latter is through being hydrolyzed to get arbutin.
Owing to be subjected to the impact of the 2-acetoxyl group anchimeric assistance of β-five acetyl sugar, the chemical activity of β-five acetyl sugar is better than alpha-D-glucose pentaacetate (hereinafter to be referred as α-five acetyl sugar), so usually all adopt directly synthesis of glycoside of β-five acetyl sugar.Its industrial production adopts 3 step synthesis techniques: 1) glucose gets β-five acetyl sugar with the acetic anhydride acetylize; 2) latter and Resorcinol react to get 4-hydroxy phenyl-beta-glucoside tetraacetate, for convenient crystallization and the purifying of obtaining, through the acetic anhydride acetylize, obtain key intermediate 4-acetoxyl group phenyl-beta-glucoside tetraacetate; 3) latter's ammonia solves product β-arbutin.This has become classical production technique.
The crucial part of this technique is: 1) beta configuration of the intermediate β-five acetyl sugar of arbutin is essential, and its purity and quality are very important, are the key factors that second step becomes the glycosides quality; 2) acetic anhydride of 6～9 times of the synthetic needs of β-five acetyl sugar, the consumption of acetic anhydride is the key of raw materials cost.Wherein, the synthetic employing sodium acetate of β-five acetyl sugar is catalyzer, under such condition, obtains β-five acetyl sugar crude product, and after making with extra care, the β of gained-five acetyl sugar yield is 65%,, by product is α-five acetyl sugar, about 25%.
Above-mentioned present situation and the analysis showed that, research and development more be easy to get, more cheap raw material is for the synthesis of key intermediate 4-hydroxy phenyl-beta-glucoside tetraacetate or 4-acetoxyl group phenyl-beta-glucoside tetraacetate.Exploitation is very useful with novel method and the novel process that such new raw material synthesizes beta-glucoside, meets simultaneously the low-carbon (LC) advocated in the world and the policy of cleaner production, and very large economic and social benefit is arranged.
Summary of the invention
The present invention with the synthetic key intermediate 4-hydroxy phenyl of α-five acetyl sugar-beta-glucoside tetraacetate or 4-acetoxyl group phenyl-beta-glucoside tetraacetate, thereby synthesizes β-arbutin by the careful above-mentioned key issue of having researched and solved.Exploitation is with the sugared such new raw material of α-five acetyl or utilize such by product to synthesize novel method and the novel process of β-arbutin.
For a long time, many documents are paid close attention to the desired α of various catalyzer acquisition-or the glucide of beta configuration.Usually with various acid as catalyst acquisition α-or the glucosides of beta configuration.Sometimes in specifying configuration, judge by accident.Kurosu etc. obtain alpha-arbutin with microbial fermentation processes, and its proton nmr spectra and the spectrum of β-arbutin are contrasted, and clearly illustrate that, can use
1The coupling constant of 1-H is judged the α of arbutin-or beta configuration among the HNMR, i.e. the J=3.7Hz of alpha-arbutin 1-H, and J=7Hz～9Hz of β-arbutin 1-H.β-the arbutin that obtains in the production, its proton nmr spectra is consistent with the above results.
Owing to be subjected to the impact of the 2-acetoxyl group anchimeric assistance of β-five acetyl sugar, the chemical activity of β-five acetyl sugar is better than α-five acetyl sugar, so existing production technique all adopts directly synthesis of glycoside of β-five acetyl sugar usually.The acetic anhydride that the synthetic needs of β-five acetyl sugar are 6～9 times, the consumption of acetic anhydride is the key of raw materials cost.Wherein, the synthetic employing sodium acetate of β-five acetyl sugar is catalyzer, under such condition, obtains β-five acetyl sugar crude product, and after making with extra care, the β of gained-five acetyl sugar yield is 65%,, by product is α-five acetyl sugar, about 25%.The latter waits to locate as refuse, has greatly increased raw-material consumption and production cost.
Synthesizing of β-arbutin all has the lot of documents report both at home and abroad, and these reports show that synthetic many employing glucose of β-arbutin are starting raw material, and it is sugared to obtain β-five acetyl through acetylize, and then reaction obtains β-arbutin.But synthetic β-arbutin has no bibliographical information take α-five acetyl sugar as starting raw material.
The present invention adopts the synthetic β-arbutin of α-five acetyl sugar.α-five acetyl sugar can be the by product of producing β-five acetyl sugar, and also can adopt glucose is starting raw material, obtains through acetylize.Catalyzer is the various inorganic or organic Lewis acids (Lewis acid) such as zinc chloride, and suitable solvent comprises the organic solvent of various nonpolar, the polarity such as toluene, or their mixed solvent.Should be appreciated that simultaneously those specific descriptions that the present invention is not limited to exemplify.
What have feature of the present invention synthesizes key intermediate 4-hydroxy phenyl-beta-glucoside tetraacetate or 4-acetoxyl group phenyl-beta-glucoside tetraacetate with α-five acetyl sugar, thus synthetic β-arbutin, and its synthetic route is as follows.
α-five acetyl sugar (1) derive from β-arbutin produce in the by product of synthetic β-five acetyl sugar, or be starting raw material with glucose, obtain through acetylize.Two kinds of approach resulting α-five acetyl sugar (1) have identical physico-chemical property, 111～112 ℃ of fusing points, [α]
D 20+ 102 (C=1, CHCl
3).α-five acetyl the sugar (1) of two kinds of approach acquisitions is respectively applied to then synthetic β-arbutin (3) of synthetic key intermediate (2), obtains same result.
According to the present invention, with reactions such as solvent such as toluene, hexane, other solvents or mixed solvent, α-five acetyl sugar (1), Resorcinol, catalyzer zinc chloride or tosic acid, temperature is 30～160 ℃, reaction 1～6h, obtain 4-hydroxy phenyl-beta-glucoside tetraacetate, or the adding acetic anhydride obtains 4-acetoxyl group phenyl-beta-glucoside (2) after condensation reaction is finished.Obtain β-arbutin crude product with conventional ammonia solution, the crystal makes β-arbutin (3).
By then synthetic (3), synthetic (2) of α-five acetyl sugar (1), the fusing point of gained compound (2) and (3) with
1The physico-chemical properties such as HMR are with consistent shown in the document, and are consistent with the result who synthesizes β-arbutin gained take β-five acetyl sugar as raw material of routine.(2) 145～146 ℃ of fusing points,
1HMR (400MHz, CDCl
3): δ 7.00 (4H, s, Ph), 5.23-5.27 (1H, m), 5.14-5.18 (1H, m), 5.03-5.04 (1H, m), 4.27-4.30 (1H, m), 4.15-4.18 (1H, m), 3.83-3.85 (1H, m), 2.28 (3H, s, PhOCOCH
3), 2.04-2.07 (12H, m, COCH
3).(3) 199～200 ℃ of fusing points,
1HMR (400MHz, DMSO-d
6): δ 9.61 (1H, S, Ar-OH), 6.87 (2H, d, ArH), 6.67 (2H, d, ArH), 5.25 (1H, d, 2-OH), 5.05 (1H, d, 3-OH), 4.99 (1H, d, 4-OH), 4.65 (1H, d, J=7.4,1-H), 4.56 (1H, t, 6-OH), 3.69 (1H, m, 6-CH), (3.46 1H, m, 6-CH), 3.24 (1H, m, 3-H), (3.19 1H, m, 5-H), 3.15 (1H, m, 4-H).
Embodiment
Following examples are to illustrate and unrestricted the present invention.
The synthetic 4-acetoxyl group phenyl of embodiment 1 usefulness α-five acetyl sugar (1)-beta-glucoside tetraacetate (2)
In reaction flask, add toluene 45ml, β-five acetyl sugar (1) 18.8g (0.048mol), Resorcinol 5.5g (0.05mol), zinc chloride 1.8g (0.013mol), reacting by heating 4h.Add acetic anhydride 9.5g (0.093mol), continue reaction 1h, cooling wait solid is fully separated out.Tell organic layer.With 30ml ethyl alcohol recrystallization solid, drying, get 4-acetoxyl group phenyl-beta-glucoside tetraacetate (2) 6.9g, 145～146 ℃ of fusing points,
1HMR (400MHz, CDCl
3): δ 7.00 (4H, s, Ph), 5.23-5.27 (1H, m), 5.14-5.18 (1H, m), 5.03-5.04 (1H, m), 4.27-4.30 (1H, m), 4.15-4.18 (1H, m), 3.83-3.85 (1H, m), 2.28 (3H, s, PhOCOCH
3), 2.04-2.07 (12H, m, COCH
3).
Embodiment 2 usefulness 4-acetoxyl group phenyl-beta-glucoside tetraacetates (2) synthesize β-arbutin (3)
Add methyl alcohol 25ml and (2) 6.9g in reaction flask, be cooled to 5 ℃, pass into ammonia, holding temperature is reacted 3h below 10 ℃, and placement is spent the night.Concentrating under reduced pressure adds chloroform 90ml, stirs, and β-arbutin is fully separated out, and the water recrystallization gets product 2.7g.199～200 ℃ of fusing points,
1HMR (400MHz, DMSO-d
6): δ 9.61 (1H, S, Ar-OH), 6.87 (2H, d, ArH), 6.67 (2H, d, ArH), 5.25 (1H, d, 2-OH), 5.05 (1H, d, 3-OH), 4.99 (1H, d, 4-OH), 4.65 (1H, d, J=7.4,1-H), 4.56 (1H, t, 6-OH), 3.69 (1H, m, 6-CH), (3.46 1H, m, 6-CH), 3.24 (1H, m, 3-H), 3.19 (1H, m, 5-H), 3.15 (1H, m, 4-H), [α]
D 25=-64 ° of (C=3.0, H
2O).
Claims (3)
1. the method for a synthetic β-arbutin is characterized in that, may further comprise the steps:
Steps A: take the alpha-D-glucose pentaacetate as raw material, at toluene or/and hexane is that solvent and zinc chloride or tosic acid are under the catalyzer condition, with the Resorcinol condensation reaction, synthetic 4-hydroxy phenyl-beta-glucoside tetraacetate, described temperature of reaction is 30～160 ℃, and the described reaction times is 1～6 hour;
Step B: described 4-hydroxy phenyl-beta-glucoside tetraacetate prepares β-arbutin through conventional ammonia solution.
2. the method for described synthetic β-arbutin according to claim 1; it is characterized in that; the described 4-hydroxy phenyl of step B-beta-glucoside tetraacetate obtains 4-acetoxyl group phenyl-beta-glucoside tetraacetate through acetylize, and described 4-acetoxyl group phenyl-beta-glucoside tetraacetate prepares β-arbutin through conventional ammonia solution again.
3. the method for described synthetic β-arbutin according to claim 1 and 2 is characterized in that, the described alpha-D-glucose pentaacetate of steps A for the by product of producing β-five acetyl sugar and/or glucose through acetylizad product.
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| CN104098622B (en) * | 2013-04-09 | 2023-11-03 | 中国医学科学院药物研究所 | β-Arbutin crystal type IV substance and its preparation method and its composition and use |
| CN104098621B (en) * | 2013-04-09 | 2023-05-09 | 中国医学科学院药物研究所 | Beta-arbutin crystal III substance, preparation method, composition and application thereof |
| CN105968149A (en) * | 2016-05-06 | 2016-09-28 | 江西金顿香料有限公司 | Preparation method of beta-arbutin |
| CN107216359A (en) * | 2017-07-24 | 2017-09-29 | 湖北阿泰克生物科技股份有限公司 | A kind of synthetic method of β ursin |
| CN112358514B (en) * | 2020-10-19 | 2023-01-31 | 浙江拓普药业股份有限公司 | Synthesis process of arbutin |
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| CN1724551A (en) * | 2005-07-21 | 2006-01-25 | 华东理工大学 | A kind of preparation method of α-arbutin |
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| CN1724551A (en) * | 2005-07-21 | 2006-01-25 | 华东理工大学 | A kind of preparation method of α-arbutin |
Non-Patent Citations (3)
| Title |
|---|
| Ivica C. 等.Simple and efficient synthesis of arbutin.《ARKIVOC》.2008,(第2期), * |
| 刘锋 等.熊果苷合成研究进展.《日用化学工业》.2004,第34卷(第4期), * |
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