CN1290705A - Synthesizing method of 1-hydroxy monosaccharide benzoylate - Google Patents
Synthesizing method of 1-hydroxy monosaccharide benzoylate Download PDFInfo
- Publication number
- CN1290705A CN1290705A CN 99119756 CN99119756A CN1290705A CN 1290705 A CN1290705 A CN 1290705A CN 99119756 CN99119756 CN 99119756 CN 99119756 A CN99119756 A CN 99119756A CN 1290705 A CN1290705 A CN 1290705A
- Authority
- CN
- China
- Prior art keywords
- benzoyl
- monose
- ethanoyl
- hydroxyl
- benzoylated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Saccharide Compounds (AREA)
Abstract
Monosaccharide benzoylate is acetylated in an acetic anhydride-sulfuric acid or an acetic anhydride-acetic acid-sulfuric acid system into monosaccharide with acetyl radical in the first place and benzoyl radicals in other places, which is made to react with equimolar ammonium carbonate in dimethyl formamide solvent at 30 deg.C for 20 hr to prepare monosaccharide with hydroxyl radical in the first place and benzoyl radicals in other places of the present invention. It is much easier to eliminate acetyl radical in the first place than to eliminate benzoyl radical in the first place, to the process of the present invlention can obtain monosaccharide with hydroxyl radical in the first place and benzoyl radicals in other places at high yield easily.
Description
The invention belongs to the preparing technical field of bioactive oligosaccharides; particularly relate to and can be used for synthetic complex oligosaccharide, as the important intermediate-1 of plant ego defense system activating agent grape six sugar and seven sugar and lentinan core fragment oligosaccharides be hydroxyl, other is synthetic method of the monose of benzoyl.
Oligosaccharides, polysaccharide and glycoconjugate (glycoprotein, glycolipid) is important information substance in the organism, participates in the contact process of all cells, the communication of the oligosaccharides of cell surface between cell, identification and interaction, the embryo is taken place, and shifts, in the signal transmission, cell movement with stick, and the interaction aspect of cause of disease and host cell plays an important role.Up-to-date studies show that, oligosaccharides not only with they conjugate in action, a lot of oligosaccharides itself just have the important physical function, the oligosaccharides that has can excite the immunity system of plant, the oligosaccharides that has can be induced the nitrogen fixation of root nodule bacterium; The oligosaccharides that has can combine with the glycoprotein on the microorganism of invading and stop the invasion and attack of these microorganisms to the human normal cell, some oligosaccharides then have the function of heparin (haparin), the medicine of the anti-curing cancers that blood group decision family oligosaccharides gets a good chance of especially.Oligosaccharides is in agricultural, and the pharmaceutical sector aspect has wide practical use.And oligosaccharides and polysaccharide are removed disease directly as drug use, improve health, and will cause the renewal of disease preventing and treating idea, also are that of life science makes progress greatly.Emerging " sugared engineering " (based on drug development of carbohydrate) is in flourish ground zero, according to " biotechnology news " (Biotech News) 1995,14 (4), 7 the report, the market share of carbohydrate medicine will from 1993 13% increase to 2000 24%.
Can adopt several different methods to the synthetic of oligosaccharides, but the first-elected Schmidt method of most important method.This just need at first prepare 1 for hydroxyl, other has the sugar of various protecting groups.Preparing 1 is hydroxyl, other existing many effective meanss of monose for Bian Ji protection or ethanoyl protection.1 of existing preparation is that hydroxyl, other method for the monose of benzoyl then exist yield low, the problem of separation difficulty [Carbohydrate Research.156 (1986) 241-246; 191 (1989) 150-153].This just needs a kind of yield height of development, and easy to operate, raw material is cheap, can prepare the method for this compounds in a large number.
The objective of the invention is to through 1 for ethanoyl, other is intermediate for the monose of benzoyl, provides a kind of step simple, 1 of time saving and energy saving preparation is a hydroxyl, other is synthetic method of the monose of benzoyl.
The object of the present invention is achieved like this: with complete benzoylated monose is raw material, through acetolysls make its almost be converted into quantitatively 1 for ethanoyl, other is the monose of benzoyl.Owing to remove the existing multiple high-efficiency method of 1 ethanoyl, therefore can obtain with high yield, easily 1 for hydroxyl, other is the monose of benzoyl.Through 1 for ethanoyl, other is that intermediate is a key of the present invention for the sugar of benzoyl.
Synthetic method of the present invention is: complete benzoylated monose; acetolysls in acetic anhydride-sulfuric acid or acetic anhydride-acetic acid-vitriolic system; react after 2-20 hour, with ordinary method processing reaction liquid, almost obtain quantitatively 1 for ethanoyl, other is the monose of benzoyl.Its purity can be directly used in next step reaction greater than 90%; With resulting 1 for ethanoyl, other is dissolved in the dimethyl formamide solution for the monose of benzoyl; the volatile salt that adds equimolar porphyrize; after reacting 20 hours under 30 ℃; add the methylene dichloride dilution; water flush away dimethyl formamide, organic phase is drained under vacuum, and crude product is refining with silica gel column chromatography; obtain the monose compound that the inventive method is prepared, productive rate is at 70-90%.
Described complete benzoylated monose is complete benzoylated glucose, complete benzoylated semi-lactosi, complete benzoylated seminose; complete benzoylated rhamnosyl, complete benzoylated Fucose, complete benzoylated wood sugar; complete benzoylated pectinose, complete benzoylated lyxose.
Described 1 is ethanoyl; other is ethanoyl for the monose of benzoyl is 1; other is the glucose of benzoyl; 1 is ethanoyl; other is the semi-lactosi of benzoyl; 1 is ethanoyl; other is the seminose of benzoyl; 1 is ethanoyl; other is the rhamnosyl of benzoyl; 1 is ethanoyl; other is the Fucose of benzoyl; 1 is ethanoyl; other is the wood sugar of benzoyl; 1 is ethanoyl; other is the pectinose of benzoyl, and 1 is ethanoyl; other is the lyxose of benzoyl.
Described 1 for hydroxyl, other for the monose of benzoyl be 1 be hydroxyl, other is the glucose of benzoyl; 1 is hydroxyl, other is the semi-lactosi of benzoyl; 1 is hydroxyl, other is the seminose of benzoyl; 1 is hydroxyl, other is the rhamnosyl of benzoyl; 1 is hydroxyl, other is the Fucose of benzoyl; 1 is hydroxyl, other is the wood sugar of benzoyl; 1 is hydroxyl, other is the pectinose of benzoyl, and 1 is hydroxyl, other is the lyxose of benzoyl.
With following is example
The a-methylene dichloride; acetic anhydride/acetic acid/sulfuric acid; room temperature; 2-20 hour b-dimethyl formamide; volatile salt; 30 degrees centigrade, (being glucose among the figure) sugared 2---1 position of 20 hours full benzoylizations of 1---is an ethanoyl, other is for the monose of benzoyl (being glucose among the figure) 3---1 position is a hydroxyl, other is the monose of benzoyl (being glucose among the figure).
With glucose, semi-lactosi, seminose, rhamnosyl, Fucose, wood sugar, pectinose, lyxose are raw material, their the full benzoylation sugar of method preparation of pressing (Methods in Carbohydrate Chemistry II) is as raw material.
The present invention can simplify greatly 1 for hydroxyl, other is synthetic for the monose of benzoyl.
The present invention can prepare the used important intermediate-1 of synthetic complex oligosaccharide for hydroxyl, other is the monose of benzoyl; make Schmidt reagent by these intermediates and can be used for that the synthetic of bioactive disaccharide and oligosaccharides arranged, these sugar can be used for the pharmaceutical activity experiment.
Below in conjunction with embodiment the present invention is described in detail.Embodiment 1:1 position is hydroxyl, other preparation for the glucose of benzoyl
Complete benzoylated glucose (1; 30 grams; 42.86 mmole) be dissolved in 50 milliliters of methylene dichloride; in this solution, add 30 milliliters of acetic anhydride; 30 milliliters of acetic acid and 15 milliliters of sulfuric acid; reaction added 200 milliliters of methylene dichloride after 2 hours under the room temperature, under agitation adds less water then excessive acetic anhydride is decomposed.Add a large amount of water washings, aqueous phase discarded after the layering is gone the pickling in the organic phase with saturated sodium hydrogen carbonate solution then.Organic phase with anhydrous sodium sulfate drying after, under vacuum, drain, obtain product 2, its purity can be directly used in next step reaction greater than 90%.Products therefrom 2 is dissolved in 150 milliliters of dimethyl formamide solutions, the volatile salt that adds 15 gram porphyrizes is after reacting 220 hours under the 30 degree temperature, add 200 milliliters of methylene dichloride, wash solution with water, aqueous phase discarded, organic phase is drained under vacuum, crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/4), obtain the monose compound 3 (21 gram) that the inventive method is prepared, overall yield 82%
Embodiment 2:1 position is hydroxyl, other preparation for the semi-lactosi of benzoyl
Complete benzoylated semi-lactosi (4; 20 grams; 28.57 mmole) be dissolved in 40 milliliters of methylene dichloride; in this solution, add 20 milliliters of acetic anhydride and 10 milliliters of sulfuric acid; reaction is after 6 hours under the room temperature; add 150 milliliters of methylene dichloride, under agitation add less water then excessive acetic anhydride is decomposed.Add a large amount of water washings, aqueous phase discarded after the layering is gone the pickling in the organic phase with saturated sodium hydrogen carbonate solution then.Organic phase with anhydrous sodium sulfate drying after, under vacuum, drain, obtain product 5, its purity can be directly used in next step reaction greater than 90%.Products therefrom 5 is dissolved in 120 milliliters of dimethyl formamide solutions, the volatile salt that adds 10 gram porphyrizes is after reacting 20 hours under the 30 degree temperature, add 150 milliliters of methylene dichloride, wash solution with water, aqueous phase discarded, organic phase is drained under vacuum, crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/4), obtain the monose compound 6 (13.6 gram) that the inventive method is prepared, overall yield 80%
Embodiment 3:1 position is hydroxyl, other preparation for the seminose of benzoyl
Complete benzoylated seminose (7; 34 grams; 48.67 mmole) be dissolved in 60 milliliters of methylene dichloride; in this solution, add 35 milliliters of acetic anhydride; 35 milliliters of acetic acid and 17 milliliters of sulfuric acid; reaction added 200 milliliters of methylene dichloride after 10 hours under the room temperature, under agitation adds less water then excessive acetic anhydride is decomposed.Add a large amount of water washings, aqueous phase discarded after the layering is gone the pickling in the organic phase with saturated sodium hydrogen carbonate solution then.Organic phase with anhydrous sodium sulfate drying after, under vacuum, drain, obtain product 8, its purity can be directly used in next step reaction greater than 95%.Products therefrom 8 is dissolved in 150 milliliters of dimethyl formamide solutions, the volatile salt that adds 17 gram porphyrizes is after reacting 20 hours under the 30 degree temperature, add 200 milliliters of methylene dichloride, wash solution with water, aqueous phase discarded, organic phase is drained under vacuum, crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/4), obtain the monose compound 9 (26 gram) that the inventive method is prepared, overall yield 90%
Embodiment 4:1 position is hydroxyl, other preparation for the pectinose of benzoyl
Complete benzoylated pectinose (10; 16 grams; 28.27 mmole) be dissolved in 30 milliliters of methylene dichloride; in this solution, add 17 milliliters of acetic anhydride; 17 milliliters of acetic acid and 8 milliliters of sulfuric acid; reaction added 130 milliliters of methylene dichloride after 20 hours under the room temperature, under agitation adds less water then excessive acetic anhydride is decomposed.Add a large amount of water washings, aqueous phase discarded after the layering is gone the pickling in the organic phase with saturated sodium hydrogen carbonate solution then.Organic phase with anhydrous sodium sulfate drying after, under vacuum, drain, obtain product 11, its purity can be directly used in next step reaction greater than 90%.Products therefrom 11 is dissolved in 100 milliliters of dimethyl formamide solutions, the volatile salt that adds 7 gram porphyrizes is after reacting 20 hours under the 30 degree temperature, add 130 milliliters of methylene dichloride, wash solution with water, aqueous phase discarded, organic phase is drained in vacuum, crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/4), obtain the monose compound 12 (9.1 gram) that the inventive method is prepared, overall yield 70%
Embodiment 5:1 position is hydroxyl, other preparation for the wood sugar of benzoyl
Complete benzoylated wood sugar (13,11 grams, 19.43 mmoles) is dissolved in 20 milliliters of methylene dichloride; in this solution, add 12 milliliters of acetic anhydride and 6 milliliters of sulfuric acid; reaction added 100 milliliters of methylene dichloride after 5 hours under the room temperature, under agitation adds less water then excessive acetic anhydride is decomposed.Add a large amount of water washings, aqueous phase discarded after the layering is gone the pickling in the organic phase with saturated sodium hydrogen carbonate solution then.Organic phase with anhydrous sodium sulfate drying after, under vacuum, drain, obtain product 14, its purity can be directly used in next step reaction greater than 90%.Products therefrom 14 is dissolved in 80 milliliters of dimethyl formamide solutions, the volatile salt that adds 5 gram porphyrizes is after reacting 20 hours under the 30 degree temperature, add 110 milliliters of methylene dichloride, wash solution with water, aqueous phase discarded, organic phase is drained in vacuum, crude product is refining with silica gel column chromatography, as leacheate drip washing, collects respective components with ethyl acetate/petroleum ether (1/4), obtain the monose compound 15 (6.5 gram) that the inventive method is prepared, overall yield 72%
Claims (4)
- One kind with 1 be ethanoyl, other is that the monose of benzoyl is that 1 of intermediate preparation is a hydroxyl, other is the synthetic method of the monose of benzoyl, it is characterized in that:(1) complete benzoylated monose, acetolysls in acetic anhydride-sulfuric acid or acetic anhydride-acetic acid-vitriolic system reacted after 2-20 hour, with ordinary method processing reaction liquid, almost obtain quantitatively 1 for ethanoyl, other is the monose of benzoyl.Its purity can be directly used in next step reaction greater than 90%;(2) with resulting 1 for ethanoyl, other is dissolved in the dimethyl formamide solution for the monose of benzoyl; the volatile salt that adds equimolar porphyrize; after reacting 20 hours under 30 ℃; add the methylene dichloride dilution; water flush away dimethyl formamide, organic phase is drained under vacuum, and crude product is refining with silica gel column chromatography; obtain the monose compound that the inventive method is prepared, productive rate is at 70-90%.
- 2. as claimed in claim 1 a kind of with 1 be ethanoyl, other is that the monose of benzoyl is that 1 of intermediate preparation is a hydroxyl, other is the synthetic method of the monose of benzoyl; it is characterized in that described complete benzoylated monose is complete benzoylated glucose; complete benzoylated semi-lactosi; complete benzoylated seminose; complete benzoylated rhamnosyl; complete benzoylated Fucose; complete benzoylated wood sugar; complete benzoylated pectinose, complete benzoylated lyxose.
- 3. as claimed in claim 1 a kind of be ethanoyl with 1; other is that 1 of intermediate preparation is hydroxyl for the monose of benzoyl; other is the synthetic method of the monose of benzoyl; it is characterized in that described 1 is ethanoyl; other is ethanoyl for the monose of benzoyl is 1; other is the glucose of benzoyl; 1 is ethanoyl; other is the semi-lactosi of benzoyl; 1 is ethanoyl; other is the seminose of benzoyl; 1 is ethanoyl; other is the rhamnosyl of benzoyl; 1 is ethanoyl; other is the Fucose of benzoyl; 1 is ethanoyl; other is the wood sugar of benzoyl; 1 is ethanoyl; other is the pectinose of benzoyl, and 1 is ethanoyl; other is the lyxose of benzoyl.
- 4. as claimed in claim 1 a kind of be ethanoyl with 1; other is that 1 of intermediate preparation is hydroxyl for the monose of benzoyl; other is the synthetic method of the monose of benzoyl; it is characterized in that described 1 is hydroxyl; other is hydroxyl for the monose of benzoyl is 1; other is the glucose of benzoyl; 1 is hydroxyl; other is the semi-lactosi of benzoyl; 1 is hydroxyl; other is the seminose of benzoyl; 1 is hydroxyl; other is the rhamnosyl of benzoyl; 1 is hydroxyl; other is the Fucose of benzoyl; 1 is hydroxyl; other is the wood sugar of benzoyl; 1 is hydroxyl; other is the pectinose of benzoyl, and 1 is hydroxyl; other is the lyxose of benzoyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119756 CN1290705A (en) | 1999-09-30 | 1999-09-30 | Synthesizing method of 1-hydroxy monosaccharide benzoylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99119756 CN1290705A (en) | 1999-09-30 | 1999-09-30 | Synthesizing method of 1-hydroxy monosaccharide benzoylate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1290705A true CN1290705A (en) | 2001-04-11 |
Family
ID=5281082
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99119756 Pending CN1290705A (en) | 1999-09-30 | 1999-09-30 | Synthesizing method of 1-hydroxy monosaccharide benzoylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1290705A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432089C (en) * | 2005-05-13 | 2008-11-12 | 湖南中烟工业有限责任公司 | Process of synthesizing 2,3,4,6-tetraacyl pyrane glucose |
| CN108314696A (en) * | 2018-03-16 | 2018-07-24 | 上药康丽（常州）药业有限公司 | 2- hydroxyls -1,3, the utilization method of tri--O- benzoyls-α of 5--D-RIBOSE crystalline mother solution |
| CN114560897A (en) * | 2022-04-06 | 2022-05-31 | 江西艾立斯特生物科技有限公司 | Post-treatment method for preparing all-benzoylated glucose |
-
1999
- 1999-09-30 CN CN 99119756 patent/CN1290705A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432089C (en) * | 2005-05-13 | 2008-11-12 | 湖南中烟工业有限责任公司 | Process of synthesizing 2,3,4,6-tetraacyl pyrane glucose |
| CN108314696A (en) * | 2018-03-16 | 2018-07-24 | 上药康丽（常州）药业有限公司 | 2- hydroxyls -1,3, the utilization method of tri--O- benzoyls-α of 5--D-RIBOSE crystalline mother solution |
| CN108314696B (en) * | 2018-03-16 | 2021-07-13 | 上药康丽（常州）药业有限公司 | Utilization method of 2-hydroxy-1, 3, 5-tri-O-benzoyl-alpha-D-ribofuranose crystallization mother liquor |
| CN114560897A (en) * | 2022-04-06 | 2022-05-31 | 江西艾立斯特生物科技有限公司 | Post-treatment method for preparing all-benzoylated glucose |
| CN114560897B (en) * | 2022-04-06 | 2024-02-27 | 江西艾立斯特生物科技有限公司 | Post-treatment method for preparing fully-benzoylated glucose |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101206288B1 (en) | Ascorbic acid derivates, their preparation methods, intermediates and uses in cosmetics | |
| CN103360439B (en) | Prepare new intermediate of heparin pentasaccharides and preparation method thereof | |
| CN106432538A (en) | Method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides | |
| Wang et al. | Assembly of a β-(1→ 3)-glucan laminarihexaose on ionic liquid support | |
| CN112538099B (en) | Preparation method and application of 1-thioglucose and glucose 1-thiol protected by total acyl | |
| CN1290705A (en) | Synthesizing method of 1-hydroxy monosaccharide benzoylate | |
| Reeves et al. | A Glycerol Galactofuranoside from the Lipid of an Anaerobe | |
| CN1138783C (en) | Synthesis of 1-hydroxy, 6 or 5-acetyl monosaccharide benzoylate | |
| JP2587268B2 (en) | Method for producing low-viscosity hyaluronic acid or salt thereof | |
| CN1054607C (en) | Zone selection using saccharous ortho-ester as key intemediate and method for stereospecific synthesis of oligose | |
| CN1554267A (en) | Method for preparing water soluble chitosan | |
| CN1680571A (en) | Preparation of maltotriose | |
| CN114736316B (en) | Green preparation method and application of acetylated hyaluronate | |
| CN1072677C (en) | Method for synthesizing disaccharide and trisaccharide ortho-esters | |
| JP3650409B2 (en) | Process for producing low molecular weight branched β-1,3-glucan and branched laminary oligosaccharide | |
| CN101235058A (en) | Method for synthesizing N-acetaminoglucose | |
| JP3713065B2 (en) | Disaccharide monomer, oligomer thereof and method for producing oligomer | |
| JP3939592B2 (en) | Method for producing oligosaccharide (salt) | |
| KR20020009735A (en) | Method of making useing agar oligosaccharide for edible acetic acid | |
| CN1129600C (en) | Synthesis of lentinan core fragment trisaccharide, tetrasaccharide, hexasaccharide and heptasaccharide | |
| US20040260077A1 (en) | Method for preparaing water-soluble free amine chitosan | |
| CN114736315B (en) | Method for synthesizing heptasaccharide of lentinan core fragment beta- (1 → 6) branched chain beta- (1 → 3) main chain | |
| JP3037445B2 (en) | Production method of retinyl glucoside | |
| CN105037455B (en) | The synthetic method of alkyl β D glucopyranosides | |
| JPH0560474B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| AD01 | Patent right deemed abandoned | ||
| C20 | Patent right or utility model deemed to be abandoned or is abandoned |