CN102702276A - Postprocessing method for glycal reaction solution - Google Patents
Postprocessing method for glycal reaction solution Download PDFInfo
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- CN102702276A CN102702276A CN2012101865103A CN201210186510A CN102702276A CN 102702276 A CN102702276 A CN 102702276A CN 2012101865103 A CN2012101865103 A CN 2012101865103A CN 201210186510 A CN201210186510 A CN 201210186510A CN 102702276 A CN102702276 A CN 102702276A
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Abstract
The invention relates to the technical field of glycal, in particular to a postprocessing method for a glycal reaction solution. The glycal reaction solution is washed with acid within one hour until the aqueous phase PH is acidic or neutral, then the glycal reaction solution is washed until the aqueous phase PH is neutral or alkaline, organic phases are separated, and the purified glycal is obtained after drying. According to the postprocessing method for the glycal reaction solution disclosed by the invention, time, labor and cost are saved, waste eluent which can not be processed can not be largely produced, the yield and the purity of the obtained glycal are high, and the method can be used for production on a large scale.
Description
Technical field
The present invention relates to the glycal technical field, particularly a kind of post-treating method of glycal reaction solution.
Background technology
Saccharide compound is the material that people live and activity in production is indispensable, and sugar is also being played the part of pivotal player in the life entity process simultaneously, and it is with nucleic acid, protein and be called three big living matters.In recent years, along with the development of glycobiology and the people great attention to the carbohydrate medicine, carbohydrate chemistry gets into the period of a fast development, and domestic and international increasing chemist and scientific research group put in the research to carbohydrate chemistry.At present, the use of carbohydrate medicine and Absatzvolumen have been occupied very big ratio on pharmaceutical market.According to statistics, kind surplus the quantity nearly 500 of the current carbohydrate medicine of on market, selling.Because carbohydrate medicine great majority all act on cell surface, and do not get into cell interior, so this type medicine is for whole cell and then to the interference of whole machine body, than get into tenuigenin, endonuclear medicine is much little.In this regard, the carbohydrate medicine should be the minimum medicine of toxic side effect.In addition, it has himself advantage as medicine or raw material, and is cheap like raw material, be easy to get, and has natural chirality and structure diversity.Therefore, the application of saccharide compound in medicine obtained extensive studies, and the carbohydrate medicine also more and more obtains people's attention.
In the synthetic and organic reaction, glycal is being played the part of extremely important role as important intermediate always at medicine.Glycal is most important a kind of verivate of unsaturated monose, and it is widely used in glucosides, nucleoside compound and biomacromolecule synthetic of various oligosaccharides, oligose, glucide, O-or C-.Its verivate is at Medicines and Health Product, and the application in the daily cosmetics is also increasingly extensive, and the demand of glycal also increases year by year, and people are dense day by day to the interest of its preparation method.But owing to receive the restriction glycal market price of its synthesis condition high, limited its application in every respect, therefore, develop efficient a, cheapness, be applicable to that the route of mass preparation glycal has very high learning value and economic benefit.
Aftertreatment patent and document about glycal are all fewer, generally all are to utilize chromatography column to purify or directly washing, and the method that salt is washed is handled refining.At Jiangxi Normal University's model is the Master degree candidate's academic dissertation " the synthetic and sign of the Arabic glycal of L-" that stands; The 17 page of paper; Gained 3, the thick product of the Arabic glycal of 4-two-O-ethanoyl-L-can separate eluent V (sherwood oil): V (acetic acid ethyl ester)=4:1 through silica gel column chromatography; Obtain colourless oil liquid, gas chromatographic analysis content is 98.6%.But this separation method can only be used for small amount of sample and separate, for a large amount of refining will be very loaded down with trivial details, both lost time and energy, also waste a large amount of eluents.For direct washing, the method that salt is washed not only makes glycal purity descend, and also can reduce the product yield greatly.
Summary of the invention
In order to solve the problem that man-hour is long, the eluent consumption is big, yield is low, purity is low that exists in the above glycal aftertreatment; It is a kind of time saving and energy saving to the invention provides, and saves cost and can make the purity of products obtained therefrom and the post-treating method of the glycal reaction solution that yield improves.
The present invention realizes through following measure:
A kind of post-treating method of glycal reaction solution, the glycal reaction solution was used pickling in one hour be acidity or neutral to water pH, it is neutral or alkaline being washed till water pH again, separates organic phase, is drying to obtain the purified glycal.
Described post-treating method, hydrionic volumetric molar concentration is 1.14mol/L-2.85mol/L in the said acid, the temperature of acid is 0-10 ℃.
Described post-treating method, acid pH are 4-7, and alkaline pH is 7-10.
Described post-treating method, being washed till water pH again is that 7-10 uses alkali or water to wash.
Described post-treating method, said glycal are the Arabic glycal of acetylize, acetylated glucal, acetylize gala glycal, acetylize rhamnal, acetylize Fructus Hordei Germinatus glycal, acetylize breast glycal or acetylize Fructus Hordei Germinatus three glycals.
Described post-treating method; Said glycal is 3, the Arabic glycal of 4-two-O-ethanoyl-L-, three-O-ethanoyl-D-glucal, three-O-ethanoyl-D-gala glycal, two-O-ethanoyl-L-rhamnal, six-O-ethanoyl-D-Fructus Hordei Germinatus glycal, six-O-ethanoyl-D-breast glycal or nine-O-ethanoyl-D-Fructus Hordei Germinatus three glycals.
Described post-treating method, said alkali are yellow soda ash.
Described post-treating method, said acid are hydrochloric acid or sulfuric acid.
Described post-treating method, said glycal reaction solution adopt in following two kinds of methods any one to make:
A, with reductive agent be distributed in the organic solvent mixture a, halogeno-sugar is got mixture b with organic solvent dissolution, under reflux state, mixture b is added among the mixture a, promptly get;
B, reductive agent is distributed in the water, adds the pH regulator agent, add halogeno-sugar, room temperature reaction promptly gets.
Reductive agent is a zinc powder among the method a, and organic solvent is the mixed solvent of butanone and ETHYLE ACETATE, and halogeno-sugar is 2,3,4-three-O-ethanoyl-1-bromo-L-arabinose;
Reductive agent is a zinc powder among the method b, and halogeno-sugar is four-O-ethanoyl-1-bromo-D-semi-lactosi.
Those skilled in the art knows that glycal is unstable under acidic condition, so in order to improve the yield of glycal; Generally can not use acid that the glycal reaction solution is handled; And technical scheme of the present invention has overcome this technological prejudice exactly, uses diluted acid that the glycal reaction solution is handled at first under certain condition, not only can not reduce the glycal yield; Can improve yield on the contrary, and the purity of the glycal that obtains is also very high.
Beneficial effect of the present invention: the post-treating method of glycal reaction solution of the present invention, time saving and energy saving, save cost, can not produce the useless elutriant that can't handle in a large number, the glycal yield that obtains is high, purity is high, and can be used on a large scale producing.
Embodiment
For further explanation the present invention, below in conjunction with concrete embodiment scheme of the present invention is described, should be appreciated that still these are described is for further help understanding the present invention, rather than the claim of invention is limited.
Embodiment 1: water-less environment is preparation glycal reaction solution down
The preparation of glycal reaction solution: in the 5L flask, add the mixed solvent of butanone and ETHYLE ACETATE, butanone and ETHYLE ACETATE volume ratio are 1:1, add 1.5mol reductive agent zinc powder, stir, and get mixture a; Use the mixed solvent of butanone and ETHYLE ACETATE to dissolve 1mol 2,3,4-three-O-ethanoyl-1-bromo-L-arabinose, stir mixture b; Intensification is heated to mixture a backflow in the flask, and reflux temperature is 80 degree, under reflux state, to wherein dividing 10 batches to add mixture b, promptly gets product 3, the Arabic glycal reaction solution of 4-two-O-ethanoyl-L-.
The aftertreatment of glycal reaction solution: behind the filtering reacting liquid, use Sorensen value as 1.14mol/L, temperature be 2 ℃ dilute hydrochloric acid solution the glycal reaction solution is washed till water pH is 6, the treatment time is 10min; It is that to be washed till water pH be 7 for 8% sodium carbonate solution that massfraction is used in phase-splitting, organic phase again; Phase-splitting, organic phase get product 0.923mol after super-dry concentrates, detecting purity is 95.6%.
The comparative example 1
The preparation of glycal reaction solution is identical with embodiment 1, the method that the aftertreatment of glycal reaction solution adopts chromatography column to purify, and the treatment time is 24 hours, than embodiment more than 1 22 hours consuming time, obtains the elutriant 50L that gives up, and obtains product 0.82mol, purity is 96.7%.
The yield of product will be compared 1 height than embodiment among the embodiment 1, and the post-treating method that glycal reaction solution of the present invention is described is compared with the method that chromatography column is purified, and can improve the product yield, and product purity also can reach a higher level.
Embodiment 2: water environment is preparation glycal reaction solution down
The preparation of glycal reaction solution: in the 10L flask, add 4L water; Add the dissolving of 8mol sodium hydrogencarbonate white powder; Add the 10mol zinc powder then, the dissolving of 72g cupric sulfate pentahydrate solid adds 1mol four-O-ethanoyl-1-bromo-D-semi-lactosi; Room temperature reaction 24 hours promptly gets product three-O-ethanoyl-D-gala glycal reaction solution.
The aftertreatment of glycal reaction solution: behind the filtering reacting liquid, use Sorensen value as the temperature of 2.85mol/L be 10 ℃ dilution heat of sulfuric acid reaction solution is washed till water pH is 5, the treatment time is 20min; It is that to be washed till water pH be 12 for 20% sodium carbonate solution that massfraction is used in phase-splitting, organic phase again; Phase-splitting, organic phase again water to be washed till water pH be 7, separating obtained organic phase is carried out drying and is concentrated, product 0.64mol, purity is 94.2%.
The comparative example 2
The preparation of glycal reaction solution is identical with embodiment 2, the method that the aftertreatment of glycal reaction solution adopts chromatography column to purify, and the treatment time is 28 hours; Than embodiment more than 2 26 hours consuming time; Obtain useless how many 45L of elutriant, obtain product 0.42mol, purity is 96.7%.
The comparative example 3
The preparation of glycal reaction solution is identical with embodiment 2, uses Sorensen value to be 2.85mol/L, and temperature is 20 ℃ a dilute sulphuric acid processing reaction liquid, and other post-processing steps are identical with embodiment 2, gets product 0.51mol, and purity is 63.7%.
The yield of product will be compared than embodiment 2 and comparative example's 3 height among the embodiment 2, explains that the post-treating method of glycal reaction solution of the present invention compares with the method that chromatography column is purified, and can improve the product yield, and product purity also can reach a higher level.
Embodiment 3
In the 5L flask, add methylene dichloride, add 1.5mol reductive agent zinc powder, stir, get mixture a; Use methylene dichloride dissolving 1mol four-O-ethanoyl-1-bromo-D-glucose, stir mixture b; Intensification is heated to mixture a backflow in the flask, and reflux temperature is 40 degree, under reflux state, to wherein dividing 10 batches to add mixture b, promptly gets product three-O-ethanoyl-D-glucal reaction solution.
The aftertreatment of glycal reaction solution: behind the filtering reacting liquid, use Sorensen value as 2mol/L, temperature be 5 ℃ dilute hydrochloric acid solution the glycal reaction solution is washed till water pH is 6.5, the treatment time is 10min; Phase-splitting, organic phase again water to be washed till water pH be 7.2; Phase-splitting, organic phase get product 0.935mol after super-dry concentrates, detecting purity is 94.6%.
Embodiment 4
In the 5L flask, add ETHYLE ACETATE, add 1.5mol reductive agent zinc powder, add 0.32mol ammonium chloride again, stir, get mixture a; Use acetic acid ethyl dissolution 1mol three-O-ethanoyl-1-bromo-L-rhamnosyl, stir mixture b; Intensification is heated to mixture a backflow in the flask, and reflux temperature is 80 degree, under reflux state, to wherein dividing 10 batches to add mixture b, promptly gets product two-O-ethanoyl-L-rhamnal reaction solution.
The aftertreatment of glycal reaction solution: behind the filtering reacting liquid, use Sorensen value as 2.2mol/L, temperature be 7 ℃ dilute hydrochloric acid solution the glycal reaction solution is washed till water pH is 5, the treatment time is 5min; It is 7.2 that phase-splitting, organic phase use 8% sodium carbonate solution to be washed till water pH again; Phase-splitting, organic phase get product 0.915mol after super-dry concentrates, detecting purity is 92.6%.
Claims (10)
1. the post-treating method of a glycal reaction solution is characterized in that the glycal reaction solution was used pickling in one hour be acidity or neutral to water pH, and it is neutral or alkaline being washed till water pH again, separates organic phase, is drying to obtain the purified glycal.
2. post-treating method according to claim 1 is characterized in that hydrionic volumetric molar concentration is 1.14mol/L-2.85mol/L in the said acid, and the temperature of acid is 0-10 ℃.
3. post-treating method according to claim 1 and 2 is characterized in that acid pH is 4-7, and alkaline pH is 7-10.
4. post-treating method according to claim 1 and 2, it is characterized in that being washed till water pH is that 7-10 uses alkali or water to wash again.
5. post-treating method according to claim 1 and 2 is characterized in that said glycal is the Arabic glycal of acetylize, acetylated glucal, acetylize gala glycal, acetylize rhamnal, acetylize Fructus Hordei Germinatus glycal, acetylize breast glycal or acetylize Fructus Hordei Germinatus three glycals.
6. post-treating method according to claim 1 and 2; It is characterized in that said glycal is 3, the Arabic glycal of 4-two-O-ethanoyl-L-, three-O-ethanoyl-D-glucal, three-O-ethanoyl-D-gala glycal, two-O-ethanoyl-L-rhamnal, six-O-ethanoyl-D-Fructus Hordei Germinatus glycal, six-O-ethanoyl-D-breast glycal or nine-O-ethanoyl-D-Fructus Hordei Germinatus three glycals.
7. post-treating method according to claim 4 is characterized in that said alkali is yellow soda ash.
8. post-treating method according to claim 1 and 2 is characterized in that said acid is hydrochloric acid or sulfuric acid.
9. post-treating method according to claim 1 and 2 is characterized in that said glycal reaction solution adopts in following two kinds of methods any one to make:
A, with reductive agent be distributed in the organic solvent mixture a, halogeno-sugar is got mixture b with organic solvent dissolution, under reflux state, mixture b is added among the mixture a, promptly get;
B, reductive agent is distributed in the water, adds the pH regulator agent, add halogeno-sugar, room temperature reaction promptly gets.
10. post-treating method according to claim 9 is characterized in that
Reductive agent is a zinc powder among the method a, and organic solvent is the mixed solvent of butanone and ETHYLE ACETATE, and halogeno-sugar is 2,3,4-three-O-ethanoyl-1-bromo-L-arabinose;
Reductive agent is a zinc powder among the method b, and halogeno-sugar is four-O-ethanoyl-1-bromo-D-semi-lactosi.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936270A (en) * | 2012-11-28 | 2013-02-20 | 济南圣泉唐和唐生物科技有限公司 | Addition method of glycal and alcohol compounds |
| CN103694208A (en) * | 2013-12-23 | 2014-04-02 | 江西苏克尔新材料有限公司 | Preparation method of acetylated L-arabinal |
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| WO2008069440A1 (en) * | 2006-12-06 | 2008-06-12 | Samchully Pharm. Co., Ltd. | The preparation method of 2-de0xy-l-rib0se |
| CN101245057A (en) * | 2007-02-13 | 2008-08-20 | 中国科学院成都生物研究所 | Process for producing glucal |
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2012
- 2012-06-08 CN CN201210186510.3A patent/CN102702276B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008069440A1 (en) * | 2006-12-06 | 2008-06-12 | Samchully Pharm. Co., Ltd. | The preparation method of 2-de0xy-l-rib0se |
| CN101245057A (en) * | 2007-02-13 | 2008-08-20 | 中国科学院成都生物研究所 | Process for producing glucal |
Non-Patent Citations (1)
| Title |
|---|
| 徐淑周 等: "2-脱氧-D-葡萄糖的合成", 《应用化工》, vol. 39, no. 6, 30 June 2010 (2010-06-30), pages 946 - 948 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102936270A (en) * | 2012-11-28 | 2013-02-20 | 济南圣泉唐和唐生物科技有限公司 | Addition method of glycal and alcohol compounds |
| CN102936270B (en) * | 2012-11-28 | 2015-04-22 | 济南圣泉唐和唐生物科技有限公司 | Addition method of glycal and alcohol compounds |
| CN103694208A (en) * | 2013-12-23 | 2014-04-02 | 江西苏克尔新材料有限公司 | Preparation method of acetylated L-arabinal |
| CN103694208B (en) * | 2013-12-23 | 2015-08-05 | 江西苏克尔新材料有限公司 | The preparation method of acetylize L-arabinose alkene |
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