CN100579973C - Process for producing glucal - Google Patents
Process for producing glucal Download PDFInfo
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- CN100579973C CN100579973C CN200710048471A CN200710048471A CN100579973C CN 100579973 C CN100579973 C CN 100579973C CN 200710048471 A CN200710048471 A CN 200710048471A CN 200710048471 A CN200710048471 A CN 200710048471A CN 100579973 C CN100579973 C CN 100579973C
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Abstract
The invention relates to the technical field of organic chemistry, in particular to a preparation method of glucal. 1-acetyl glucopyranosyl bromide is added in phosphate buffer solution which contains zinc powder and copper sulfate or the zinc powder and the 1-acetyl glucopyranosyl bromide are added in sodium dihydrogen phosphate water solution, stirring reaction is carried out for 0.5 to 8 hours under the room temperature, then NaOH or KOH is added, the stirring reaction is carried out again for 0.5 to 3 hours under the room temperature, after that, the glucal can be generated. The synthetic method of glucal is also called as a one-pot synthetic method of the glucal and has the advantages of simple operation, shortened process flow, high yield, short reaction time, low cost, less three wastes, small environmental pollution and easy industrialization.
Description
Technical field
The present invention relates to technical field of organic chemistry, be specifically related to a kind of preparation method of glucal.
Background technology
In organic synthesis and medicine were synthetic, glucal and acetylated glucal were unusual important material.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.Preparation acetylated glucal and other glycal compound, one of its main method are to obtain target product from one substituent, as: (1) Tetrahedron Letters2001,42 (42), 7371-7374
And for example: (2) Journal of the American Chemical Society 2005,127 (30), 10747-10752
Also as: (3) Synlett 2005,4,587-590
(4) J.Org.Chem.1999 for another example, 64,3987-3995
(5)Tetrahedron?Letters?2006，47(34)，6117-6120
(6)Journal?of?the?American?Chemical?Society?1995，117(46)，11455-70
The preparation of acetylated glucal has also been described among the patent CN1803818A in addition:
Above-mentioned several synthetic method all can obtain product, and raw material is expensive, productive rate is not high, solvent has different shortcomings such as toxicity, complex operation and intermediate product need separate but exist.
Summary of the invention
The objective of the invention is provides the method for the synthetic glucal that a kind of raw material is cheap, productive rate is high, simple and effective for the not high shortcoming of cost height, complex operation and productive rate among the preparation method who solves glucal.
The present invention realizes in the following way:
(wherein the weight ratio of Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC and water is 11: 14: 100) adds 1-bromo acetyl glucosamine or add zinc powder and 1-bromo acetyl glucosamine in the bulking value specific concentration is the biphosphate sodium water solution of 20% (g/mL) in containing the phosphate buffered saline buffer that weight ratio is 10: 1 zinc powder and copper sulfate, the weight ratio of 1-bromo acetyl glucosamine and zinc powder is 1: 1, the restir reaction is 0.5-8 hour under the room temperature, generates the D-acetylated glucal; In the D-acetylated glucal reaction solution that generates, add NaOH or KOH then, the weight ratio of NaOH or KOH and 1-bromo acetyl glucosamine is 1: 1, under the room temperature stirring reaction 0.5-3 hour, can generate glucal.
The reaction process that the present invention prepares glucal is as follows respectively:
Or
The method of the synthetic glucal of the present invention is called the method for the synthetic glucal of one kettle way again, and its advantage is: simple to operate, shortened technical process, and the productive rate height, the reaction times is short, cost is low, the three wastes are few, and environmental pollution is little, is easy to industrialization.
Embodiment
In order further to understand summary of the invention of the present invention, characteristics and effect, enumerate following examples:
Example 1: in the 100mL round-bottomed flask, add 40mL phosphate buffered saline buffer (wherein the weight ratio of Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC and water is 11: 14: 100), add the 2.1g zinc powder again, 0.21g copper sulfate, stir, add 2.1g 1-bromo acetyl glucosamine then, stirring reaction is 8 hours under the room temperature, after the TLC detection reaction is complete, add 2.1g NaOH in the above-mentioned reaction solution, stirring reaction is 3 hours under the room temperature.Through the silicagel column purifying, get pure glucal 0.717g, productive rate is 96%.
Example 2: in the 100mL round-bottomed flask, add 20mL phosphate buffered saline buffer (wherein the weight ratio of Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC and water is 11: 14: 100), add the 1.0g zinc powder again, 0.1g copper sulfate, stir, add 1.0g 1-bromo acetyl glucosamine then, stirring reaction is 5 hours under the room temperature, after the TLC detection reaction is complete, add 1.0g KOH in the above-mentioned reaction solution, stirring reaction is 1.5 hours under the room temperature.Through the silicagel column purifying, get pure glucal 0.334g, productive rate is 94%.
Example 3: in the 50mL round-bottomed flask, add 2.0g SODIUM PHOSPHATE, MONOBASIC, 10mL water, add the 1.0g zinc powder again, stir, add 1.0g 1-bromo acetyl glucosamine then, stirring reaction is 0.5 hour under the room temperature, after the TLC detection reaction is complete, add 1.0g KOH in the above-mentioned reaction solution, stirring reaction is 0.5 hour under the room temperature.Through the silicagel column purifying, get pure glucal 0.312g, productive rate is 88%.
Claims (4)
1. the preparation method of a glucal, it is characterized in that: in the phosphate buffered saline buffer of zincilate and copper sulfate, add 1-bromo acetyl glucosamine or in the biphosphate sodium water solution, add zinc powder and 1-bromo acetyl glucosamine, under the room temperature after stirring reaction 0.5-8 hour, add NaOH or KOH, the restir reaction is 0.5-3 hour under the room temperature, can generate glucal; Wherein, phosphate buffered saline buffer is that 11: 14: 100 ratio is formed by Sodium phosphate dibasic, SODIUM PHOSPHATE, MONOBASIC and water by weight.
2. the preparation method of glucal according to claim 1, it is characterized in that: the weight ratio of described zinc powder and copper sulfate is 10: 1; The bulking value specific concentration of biphosphate sodium water solution is 20g/100mL; The 1-bromo acetyl glucosamine that adds and the weight ratio of zinc powder are 1: 1; The NaOH that adds or the weight ratio of KOH and 1-bromo acetyl glucosamine are 1: 1.
3, the preparation method of glucal according to claim 1 is characterized in that: before adding NaOH or KOH, after stirring reaction 0.5-8 hour, the intermediate product that is generated is the D-acetylated glucal under the room temperature.
4, the preparation method of the described glucal of claim 1, its reaction process is as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710048471A CN100579973C (en) | 2007-02-13 | 2007-02-13 | Process for producing glucal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710048471A CN100579973C (en) | 2007-02-13 | 2007-02-13 | Process for producing glucal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101245057A CN101245057A (en) | 2008-08-20 |
| CN100579973C true CN100579973C (en) | 2010-01-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200710048471A Expired - Fee Related CN100579973C (en) | 2007-02-13 | 2007-02-13 | Process for producing glucal |
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| CN (1) | CN100579973C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101747304B (en) * | 2008-11-28 | 2012-01-04 | 中国科学院成都生物研究所 | Method for preparing glycal |
| CN103142627B (en) * | 2010-07-21 | 2014-08-20 | 苏州天人合生物技术有限公司 | Application of triacetyl glucal in preparation of antiviral drug |
| CN102397270B (en) * | 2010-09-17 | 2014-02-05 | 苏州天人合生物技术有限公司 | Application of glucal and glucal derivative in preparation of drugs |
| CN102453686B (en) * | 2010-10-27 | 2013-12-18 | 中国科学院植物研究所 | Method for inhibiting generation of aflatoxin by using D-glucal |
| CN102702276B (en) * | 2012-06-08 | 2015-07-08 | 济南圣泉唐和唐生物科技有限公司 | Postprocessing method for glycal reaction solution |
| CN103288789B (en) * | 2013-06-04 | 2016-01-20 | 华东师范大学 | A kind of preparation method of full acidylate thin malt sugar |
| CN114456217A (en) * | 2022-03-02 | 2022-05-10 | 江西科技师范大学 | Synthetic method of glycal compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800193A (en) * | 2005-12-07 | 2006-07-12 | 江苏汉发贸易发展有限公司 | 2-deoxidized glucose preparation method |
| CN1803818A (en) * | 2005-12-30 | 2006-07-19 | 江苏汉发贸易发展有限公司 | Method for preparing acetylated glucal |
-
2007
- 2007-02-13 CN CN200710048471A patent/CN100579973C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1800193A (en) * | 2005-12-07 | 2006-07-12 | 江苏汉发贸易发展有限公司 | 2-deoxidized glucose preparation method |
| CN1803818A (en) * | 2005-12-30 | 2006-07-19 | 江苏汉发贸易发展有限公司 | Method for preparing acetylated glucal |
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| CN101245057A (en) | 2008-08-20 |
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Granted publication date: 20100113 Termination date: 20190213 |