CN101328160B - Preparation of xylose glycal - Google Patents
Preparation of xylose glycal Download PDFInfo
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- CN101328160B CN101328160B CN2007100493371A CN200710049337A CN101328160B CN 101328160 B CN101328160 B CN 101328160B CN 2007100493371 A CN2007100493371 A CN 2007100493371A CN 200710049337 A CN200710049337 A CN 200710049337A CN 101328160 B CN101328160 B CN 101328160B
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- glycal
- xylose
- acetylize
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Abstract
The invention relates to the organic chemistry technical field, in particular to a method for preparing xylose glycal, comprising the following steps that: firstly, 1-brominated glucose is added into a solution containing zinc powder, sodium dihydrogen phosphate, ethyl acetate, sulphuric acid and water to react to produce acetylated xylose glycal; and secondly, the produced acetylated xylose glycal is dissolved into methanol, and the mixed solution is added with alkali to react so that the xylose glycal is produced. The method has the advantages of simple operation, short reaction time, low cost, few three wastes, little environmental protection, easy industrialization, etc.
Description
Technical field
The invention belongs to technical field of organic chemistry, be specifically related to a kind of preparation method of xylose glycal.
Background technology
In organic cpds and medicine synthetic, wood sugar pyrans glycal and acetylated glucal are important synthesis materials, but the price on the market is high, this with regard to limitations greatly its in breadboard application.At present, the preparation method of acetylated glucal is had a lot, can retrieve more than tens kinds, and new technology report is constantly arranged.But the report to preparation acetylize xylose glycal is less, and its main method is to obtain target compound from one substituent, as: (1) J.Org.Chem.1995,60,7055-7057
(2)Synthesis?2006，6，946-948
(3)Synthesis1989，10，758-759
(4)TetrahedronLetters2001，42，7371-7374
Above-mentioned several kinds of compound methods all can obtain product, and reagent is expensive, productive rate is not high and different shortcomings such as complex operation but exist.
Summary of the invention
The objective of the invention is, complex operation high and the not high shortcoming of productive rate, a kind of method of synthetic xylose glycal simple and effective, with low cost is provided for cost among the preparation method who solves existing xylose glycal.
The reaction process that the present invention prepares xylose glycal is following: at first in the reaction system that contains zinc powder, saturated sodium dihydrogen phosphate, ETHYLE ACETATE, add 1-bromo acetylize wood sugar; Stir after 10 minutes; The acid (sulfuric acid or phosphoric acid) that adds catalytic amount, stirring reaction generated the acetylize xylose glycal in 2-5 hours under the room temperature.
Wherein the mass ratio of bromo acetylize wood sugar and zinc powder is 1: 3, and the quality of bromo acetylize wood sugar and the volume of sodium dihydrogen phosphate, the volume of ETHYLE ACETATE, vitriolic volume ratio are 1: 5: 20: 1.
Then the acetylize xylose glycal that generates is dissolved in the solvent, adds alkali, reaction generated xylose glycal in 10-30 minute under the room temperature.
The alkali that wherein adopts is K
2CO
3, Na
2CO
3, one or more the miscellany in the triethylamine, diethylamine, ammoniacal liquor, sodium methylate, Pottasium Hydroxide, sodium hydroxide; The solvent that adopts is methyl alcohol, ethanol, propyl alcohol, Virahol, water, CH
2Cl
2, acetone, THF one or more miscellany; The wherein volume of the quality of acetylize xylose glycal, methyl alcohol, K
2CO
3Mass ratio be 1: 10-30: 0.1-0.5 is preferably 1: 20: 0.2; The mass ratio of the quality of acetylize xylose glycal, the volume of methyl alcohol, KOH is 1: 10-30: 0.05-0.5 is preferably 1: 20: 0.1.
Advantage of the present invention is: simple to operate, the reaction times is short, cost is low, the three wastes are few, environmental pollution is little, is easy to industriallization.
Embodiment
In order further to understand summary of the invention of the present invention, characteristics and effect, enumerate following examples:
Instance 1: in the 100mL round-bottomed flask, add 5mL SODIUM PHOSPHATE, MONOBASIC saturated solution, 1500mg zinc powder, 5mL ETHYLE ACETATE and 500mg acetylize bromo wood sugar successively; Stir after 10 minutes; Drip 0.25mL concentration again and be 98% the vitriol oil, stirring reaction is 2.5 hours under the room temperature.After the TLC detection reaction is complete, in reaction solution, add the methylene dichloride dilution, filter, filtrate water washing 2 times, organic phase is used anhydrous magnesium sulfate drying, and concentrating under reduced pressure through the silicagel column purifying, gets pure acetylize xylose glycal 224mg, productive rate 76%.
Get the acetylize xylose glycal 100mg of generation, use the 2.0mL dissolve with methanol, add 10mg KOH in the reaction solution, stirred 10 minutes under the room temperature.After the TLC detection reaction was complete, pressure reducing and steaming methyl alcohol through the silicagel column purifying, got xylose glycal 53mg, productive rate 91%.
Instance 2: in the 100mL round-bottomed flask, add 5mL SODIUM PHOSPHATE, MONOBASIC saturated solution, 1500mg zinc powder, 5mL ETHYLE ACETATE and 500mg acetylize bromo wood sugar successively; Stir after 10 minutes; Drip 0.25mL concentration again and be 98% the vitriol oil, stirring reaction is 2.5 hours under the room temperature.After the TLC detection reaction is complete, in reaction solution, add the methylene dichloride dilution, filter, filtrate water washing 2 times, organic phase is used anhydrous magnesium sulfate drying, and concentrating under reduced pressure through the silicagel column purifying, gets pure acetylize xylose glycal 230mg, productive rate 78%.
Get the acetylize xylose glycal 100mg of generation, use the 2.0mL dissolve with methanol, add 20mg K in the reaction solution
2CO
3, stirred 10 minutes under the room temperature.After the TLC detection reaction was complete, pressure reducing and steaming methyl alcohol through the silicagel column purifying, got xylose glycal 55mg, productive rate 95%.
Instance 3: in the 100mL round-bottomed flask, add 5mL SODIUM PHOSPHATE, MONOBASIC saturated solution, 1500mg zinc powder, 5mL ETHYLE ACETATE and 500mg acetylize bromo wood sugar successively, stir after 10 minutes, drip 0.5mL phosphoric acid again, stirring reaction is 5 hours under the room temperature.After the TLC detection reaction is complete, in reaction solution, add the methylene dichloride dilution, filter, filtrate water washing 2 times, organic phase is used anhydrous magnesium sulfate drying, and concentrating under reduced pressure through the silicagel column purifying, gets pure acetylize xylose glycal 215mg, productive rate 73%.
Get the acetylize xylose glycal 100mg of generation, use the 2.0mL dissolve with methanol, add 20mg NaOH, stirring at room 10 minutes in the reaction solution.After the TLC detection reaction was complete, pressure reducing and steaming methyl alcohol through the silicagel column purifying, got xylose glycal 56mg, productive rate 96%.
Claims (3)
1. the preparation method of an xylose glycal is characterized in that: comprise the steps:
A. bromo acetylize wood sugar is added and contain in the system of saturated sodium dihydrogen phosphate, zinc powder, ETHYLE ACETATE, stir after 10 minutes, add the vitriol oil or phosphoric acid again, reaction obtains the acetylize xylose glycal;
B. the acetylize xylose glycal that steps A is generated is dissolved in the solvent, adds alkali, and reaction generates xylose glycal.
2. the preparation method of xylose glycal according to claim 1, it is characterized in that: the mass ratio of bromo acetylize wood sugar and zinc powder is 1: 3 in the steps A, room temperature reaction 2-5 hour.
3. the preparation method of xylose glycal according to claim 1 is characterized in that: the alkali that step B adopts is K
2CO
3, Na
2CO
3, one or more the miscellany in the triethylamine, diethylamine, ammoniacal liquor, sodium methylate, Pottasium Hydroxide, sodium hydroxide; The solvent that adopts is methyl alcohol, ethanol, propyl alcohol, Virahol, water, CH
2Cl
2, acetone, THF one or more miscellany; Reaction is 10-30 minute under the room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100493371A CN101328160B (en) | 2007-06-20 | 2007-06-20 | Preparation of xylose glycal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100493371A CN101328160B (en) | 2007-06-20 | 2007-06-20 | Preparation of xylose glycal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101328160A CN101328160A (en) | 2008-12-24 |
| CN101328160B true CN101328160B (en) | 2012-04-11 |
Family
ID=40204204
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100493371A Expired - Fee Related CN101328160B (en) | 2007-06-20 | 2007-06-20 | Preparation of xylose glycal |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114456217A (en) * | 2022-03-02 | 2022-05-10 | 江西科技师范大学 | Synthetic method of glycal compound |
-
2007
- 2007-06-20 CN CN2007100493371A patent/CN101328160B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Cullen L. et al..A Rapid Synthesis of Pyranoid Glycals from Glycosyl Bromides.J. Org. Chem.60 21.1995,60(21),7055-7057. |
| Cullen L. et al..A Rapid Synthesis of Pyranoid Glycals from Glycosyl Bromides.J. Org. Chem.60 21.1995,60(21),7055-7057. * |
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| CN101328160A (en) | 2008-12-24 |
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