CN103665064A - Method for preparing 2,3,4,6-tetra-O-benzyl -D-galactose - Google Patents
Method for preparing 2,3,4,6-tetra-O-benzyl -D-galactose Download PDFInfo
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Abstract
The invention relates to the field of sugar compounds and in particular relates to a method for preparing 2,3,4,6-tetra-O-benzyl -D-galactose. The method comprises the steps of preparing benzothiazolylthioacetyl galactose from galactose in the presence of acetic anhydride, catalysts and 2-mercaptobenzothiazole, preparing benzothiazolylthiotetrabenzyl galactose from benzothiazolylthioacetyl galactose in the presence of potassium hydroxide and benzyl chloride, and preparing 2,3,4,6-tetra-O-benzyl -D-galactose from benzothiazolylthiotetrabenzyl galactose in the presence of N-bromosuccinimide. The method has the beneficial effects that 2,3,4,6-tetra-O-benzyl -D-galactose is synthesized by a three-step reaction method, so that the purity and yield of the product are effectively increased; the method is simple to operate; the raw materials are accessible; the operating cost and the materials are saved.
Description
technical field
The present invention relates to sugar compounds field, be specifically related to a kind of method of preparing 2,3,4,6-, tetra--oxygen-benzyl-D-galactopyranose.
background technology
2,3,4,6-, tetra--oxygen-benzyl-D-galactopyranose, claims again 2,3,4,6-, tetra--O-benzyl-D-galactopyranoside, English name: 2,3,4,6-Tetra-O-benzyl-D-galactose, No. CAS: 53081-25-7, molecular formula: C34H36O6, structural formula is as follows:
In the prior art, generally adopt semi-lactosi and Methanol for semi-lactosi first glycosides, then by semi-lactosi first glycosides, prepare tetrabenzyl semi-lactosi, then use triphenyl Tetrafluoroboric acid carbon demethylating.As Mild and Efficient Chemoselective Deprotection of Anomeric O-Methyl Glycosides with Trityl Tetrafluoroborate, Journal of Organic Chemistry, 2008, vol. 73, # 15 p. 5993 – 5995, aforesaid method catalyzer triphenyl Tetrafluoroboric acid carbon ratio is more expensive, cost is too high, or adopt semi-lactosi to carry out acetylize, then prepare p-methylphenyl thioacetyl semi-lactosi, through benzyl, N-bromo-succinimide is sloughed toluene-ω-thiol, thereby preparation 2, 3, 4, 6-tetra--oxygen-benzyl-D-pyrans (type) semi-lactosi, as Synthetic Iminosugar Derivatives as New Potential Immunosuppressive Agents, Journal of Medicinal Chemistry, 2005, vol. 48, # 11 p. 3688 – 3691, in this method, use toxicity more intense, the toluene-ω-thiol that smell is larger.
summary of the invention
In order to solve in above prior art 2,3,4, the cost compare existing in the preparation of 6-tetra--oxygen-benzyl-D-pyrans (type) semi-lactosi is high, the present situation that yield is lower, the invention provides a kind of adopt three-step reaction, the preparation 2,3 that simple to operate, raw material is easy to get, the method of 4,6-, tetra--oxygen-benzyl-D-galactopyranose.
The present invention is achieved by the following measures:
A kind of method of preparing 2,3,4,6-, tetra--oxygen-benzyl-D-galactopyranose, comprises the following steps:
A) room temperature adds aceticanhydride and catalyzer, 10-15 ℃ minute 10 batches add semi-lactosi, after having reacted, add 2-mercaptobenzothiazole, be heated to 50-60 ℃; Through aftertreatment, obtain benzothiazolyl thioacetyl semi-lactosi.
B) potassium hydroxide and benzothiazolyl thioacetyl semi-lactosi are added to and in Benzyl Chloride, are heated to back flow reaction and complete, reacted rear cooling, through aftertreatment, obtain benzothiazolyl sulfo-tetrabenzyl semi-lactosi.
C) benzothiazolyl sulfo-tetrabenzyl semi-lactosi is added in acetone and is dissolved, add water, stir in room temperature and add N-bromo-succinimide, stir 0.5 hour, reacted through aftertreatment and obtained 2,3,4,6-, tetra--oxygen-benzyl-D-galactopyranose.
Described method, described aceticanhydride: catalyzer: semi-lactosi: the mol ratio of 2-mercaptobenzothiazole is 5.5-6.5: 2-3: 1:1.1-1.2
Described method, benzothiazolyl thioacetyl semi-lactosi: Benzyl Chloride: the mol ratio of potassium hydroxide is 1:10-15: 4-8.
Described method, the mol ratio of benzothiazolyl sulfo-tetrabenzyl semi-lactosi and N-bromo-succinimide is 1:1.1-1.3.
Described method, catalyzer comprises zinc chloride, iron(ic) chloride, zirconium chloride or aluminum chloride.
Described method, in step a, the reaction times is 24-30 hour, in step b, the reaction times is 4-7 hour.
Described method, in step a, aftertreatment is cancellation, extraction, washing, concentrated, add organic solvent crystallization.
Described method, in step b, aftertreatment is water cancellation, is extracted with ethyl acetate, and through 3 washings, is concentrated into dryly, adds mixed solvent crystallization.
Described method, in step c, aftertreatment adds 5% sodium carbonate solution after being, separates organic layer, and water layer is extracted with ethyl acetate, and separates organic phase, through concentrated, adds mixed solvent crystallization.
Described method, in step a, described organic solvent is t-butyl methyl ether, methyl alcohol or ethanol.
In described method steps b, mixed solvent is that mol ratio is the t-butyl methyl ether of 2:4-6 and the solvent mixture of isohexane.
Described method, in step c, mixed solvent is that mol ratio is the t-butyl methyl ether of 2:2-3 and the solvent mixture of isohexane.
Beneficial effect: the inventive method adopts different reaction systems, comprises reaction raw materials, treatment processs etc., only obtain product by 3 step reactions, have effectively improved purity and the yield of product; Simple to operate, raw material is easy to get, and has saved running cost and material.
Accompanying drawing explanation
The product 2,3,4 that accompanying drawing 1 prepares for embodiment 1, the nuclear magnetic spectrogram of 6-tetra--O-benzyl-D-galactopyranoside.
Embodiment
In order further to understand the present invention, below in conjunction with specific embodiment, the process of this programme is described, but should be appreciated that these are described is for further instruction the features and advantages of the present invention, rather than limiting to the claimed invention.
A) room temperature adds 5.5mol aceticanhydride and 2mol zinc chloride, 10-15 ℃ minute 10 batches add 1mol semi-lactosi, after having reacted, add 1.1mol 2-mercaptobenzothiazole, be heated to 50-60 ℃; Through aftertreatment, obtain 0.87mol benzothiazolyl thioacetyl semi-lactosi.
B) 3.48mol potassium hydroxide and 0.87mol benzothiazolyl thioacetyl semi-lactosi are added in 8.7mol Benzyl Chloride and are heated to reflux, react rear cooling, pass through aftertreatment and obtain 0.79mol benzothiazolyl sulfo-tetrabenzyl semi-lactosi.
C) 0.79mol benzothiazolyl sulfo-tetrabenzyl semi-lactosi is added in 4mol acetone and is dissolved, add 2mol water, stir in room temperature and add 0.87mol N-bromo-succinimide, stir 0.5 hour, reacted through aftertreatment and obtained 0.71mol2,3,4,6-tetra--oxygen-benzyl-D-galactopyranose, yield is 71%.
In step a, aftertreatment is stirred 2 hours for dripping the water of 0-5 ℃ of 10mol, and the ethyl acetate extraction aqueous layer extracted with 5mol, separates 10mol water washing organic phase for organic phase, separates organic phase concentrated, adds the crystallization of 1mol t-butyl methyl ether, filters, dry.
In step b, aftertreatment for to add 5mol water in reaction system, stir 30 minutes, ethyl acetate extraction aqueous layer extracted with 5mol, separate 5mol water washing organic phase for organic phase, wash three times, separate organic phase concentrated, be concentrated into dry, add the t-butyl methyl ether of 0.2mol and the crystallization of 0.4mol isohexane, filter, dry.
In step c, aftertreatment adds the sodium carbonate solution of 3mol 5% after being, separate organic layer, 3mol ethyl acetate extraction for water layer, separate organic phase, merge organic phase, with the water washing of 5mol, separate organic phase concentrated, add the t-butyl methyl ether of 0.2mol and the crystallization of 0.3mol isohexane, filter, dry
embodiment 26: 2: 1:1.2
A) room temperature adds 6mol aceticanhydride and 2mol zinc chloride, 10-15 ℃ minute 10 batches add 1mol semi-lactosi, after having reacted, add 1.2mol 2-mercaptobenzothiazole, be heated to 50-60 ℃; Through aftertreatment, obtain 0.88mol benzothiazolyl thioacetyl semi-lactosi.
B) 3.6mol potassium hydroxide and 0.88mol benzothiazolyl thioacetyl semi-lactosi are added in 9.2mol Benzyl Chloride and are heated to reflux, react rear cooling, pass through aftertreatment and obtain 0.81mol benzothiazolyl sulfo-tetrabenzyl semi-lactosi.
C) 0.81mol benzothiazolyl sulfo-tetrabenzyl semi-lactosi is added in 4mol acetone and is dissolved, add 2mol water, stir in room temperature and add 0.94mol N-bromo-succinimide, stir 0.5 hour, reacted through aftertreatment and obtained 0.72mol2,3,4,6-tetra--oxygen-benzyl-D-galactopyranose, yield is 72%.
In step a, aftertreatment is stirred 2 hours for dripping the water of 0-5 ℃ of 10mol, and the ethyl acetate extraction aqueous layer extracted with 5mol, separates 10mol water washing organic phase for organic phase, separates organic phase concentrated, adds the crystallization of 1mol t-butyl methyl ether, filters, dry.
In step b, aftertreatment for to add 5mol water in reaction system, stir 30 minutes, ethyl acetate extraction aqueous layer extracted with 5mol, separate 5mol water washing organic phase for organic phase, wash three times, separate organic phase concentrated, be concentrated into dry, add the t-butyl methyl ether of 0.2mol and the crystallization of 0.4mol isohexane, filter, dry.
In step c, aftertreatment adds the sodium carbonate solution of 3mol 5% after being, separate organic layer, 3mol ethyl acetate extraction for water layer, separate organic phase, merge organic phase, with the water washing of 5mol, separate organic phase concentrated, add the t-butyl methyl ether of 0.2mol and the crystallization of 0.3mol isohexane, filter, dry
embodiment 3 6.5: 2: 1:1.2
A) room temperature adds 65mol aceticanhydride and 20mol aluminum chloride, 10-15 ℃ minute 10 batches add 10mol semi-lactosi, after having reacted, add 12mol 2-mercaptobenzothiazole, be heated to 50-60 ℃; Through aftertreatment, obtain 8.9mol benzothiazolyl thioacetyl semi-lactosi.
B) 44.5mol potassium hydroxide and 8.9mol benzothiazolyl thioacetyl semi-lactosi are added in 106.8mol Benzyl Chloride and are heated to reflux, react rear cooling, pass through aftertreatment and obtain 8.25mol benzothiazolyl sulfo-tetrabenzyl semi-lactosi.
C) 8.25mol benzothiazolyl sulfo-tetrabenzyl semi-lactosi is added in 40mol acetone and is dissolved, add 20mol water, stir in room temperature and add 9.6mol N-bromo-succinimide, stir 0.5 hour, reacted through aftertreatment and obtained 7.33mol2,3,4,6-tetra--oxygen-benzyl-D-galactopyranose, yield is 73.3%.
In step a, aftertreatment is stirred 2 hours for dripping the water of 0-5 ℃ of 100mol, and the ethyl acetate extraction aqueous layer extracted with 50mol, separates 100mol water washing organic phase for organic phase, separates organic phase concentrated, adds the crystallization of 10mol t-butyl methyl ether, filters, dry.
In step b, aftertreatment for to add 50mol water in reaction system, stir 30 minutes, ethyl acetate extraction aqueous layer extracted with 50mol, separate 50mol water washing organic phase for organic phase, wash three times, separate organic phase concentrated, be concentrated into dry, add the t-butyl methyl ether of 2mol and the crystallization of 4mol isohexane, filter, dry.
In step c, aftertreatment adds the sodium carbonate solution of 30mol 5% after being, separate organic layer, 30mol ethyl acetate extraction for water layer, separate organic phase, merge organic phase, with the water washing of 05mol, separate organic phase concentrated, add the t-butyl methyl ether of 2mol and the crystallization of 3mol isohexane, filter, dry
A) room temperature adds 6mol aceticanhydride and 2mol zinc chloride, 10-15 ℃ minute 10 batches add 1mol semi-lactosi, after having reacted, add 1.2mol toluene-ω-thiol, be heated to 50-60 ℃; Through aftertreatment, obtain 0.75mol p-methylphenyl thioacetyl semi-lactosi.
B) 3mol potassium hydroxide and 0.75mol p-methylphenyl thioacetyl semi-lactosi are added in 7.5mol Benzyl Chloride and are heated to reflux, react rear cooling, pass through aftertreatment and obtain 0.71mol p-methylphenyl sulfo-tetrabenzyl semi-lactosi.
C) 0.71mol p-methylphenyl sulfo-tetrabenzyl semi-lactosi is added in 4mol acetone and dissolves, add 2mol water, stir in room temperature and add 0.94mol N-bromo-succinimide, stir 0.5 hour, reacted through aftertreatment and obtained 0.62mol2,3,4,6-tetra--oxygen-benzyl-D-galactopyranose, yield is 62%.
Claims (10)
1. a method of preparing 2,3,4,6-, tetra--oxygen-benzyl-D-galactopyranose, is characterized in that comprising the following steps:
A) under room temperature, in reaction vessel, add aceticanhydride and catalyzer, 10-15 ℃ minute 10 batches add semi-lactosi, after having reacted, add 2-mercaptobenzothiazole, be heated to 50-60 ℃; Through aftertreatment, obtain benzothiazolyl thioacetyl semi-lactosi;
B) potassium hydroxide and benzothiazolyl thioacetyl semi-lactosi are added to and in Benzyl Chloride, are heated to back flow reaction and complete, reacted rear cooling, through aftertreatment, obtain benzothiazolyl sulfo-tetrabenzyl semi-lactosi;
C) benzothiazolyl sulfo-tetrabenzyl semi-lactosi is added in acetone and is dissolved, add water, stir in room temperature and add N-bromo-succinimide, stir 0.5 hour, reacted through aftertreatment and obtained 2,3,4,6-, tetra--oxygen-benzyl-D-galactopyranose.
2. method according to claim 1, is characterized in that aceticanhydride in step a: catalyzer: semi-lactosi: the mol ratio of 2-mercaptobenzothiazole is 5.5-6.5:2-3:1:1.1-1.2.
3. method according to claim 1, is characterized in that benzothiazolyl thioacetyl semi-lactosi in step b: Benzyl Chloride: the mol ratio of potassium hydroxide is 1:10-15: 4-8.
4. method according to claim 1, is characterized in that in step c, the mol ratio of benzothiazolyl sulfo-tetrabenzyl semi-lactosi and N-bromo-succinimide is 1:1.1-1.3.
5. method according to claim 1, described method, catalyzer is more than one in zinc chloride, iron(ic) chloride, zirconium chloride and aluminum chloride.
6. method according to claim 1, is characterized in that, in step a, the reaction times is 24-30 hour, and in step b, the reaction times is 4-7 hour.
7. method according to claim 1, is characterized in that in step a, aftertreatment is cancellation, extraction, and washing, concentrated, add organic solvent crystallization.
8. method according to claim 1, is characterized in that in step b, aftertreatment is water cancellation, is extracted with ethyl acetate, and through 3 washings, is concentrated into dryly, adds mixed solvent crystallization.
9. method according to claim 1, is characterized in that aftertreatment in step c adds 5% sodium carbonate solution after being, separates organic layer, and water layer is extracted with ethyl acetate, and separates organic phase, through concentrated, adds mixed solvent crystallization.
10. method according to claim 9, is characterized in that in step c, and mixed solvent is that mol ratio is the t-butyl methyl ether of 2:2-3 and the solvent mixture of isohexane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880897A (en) * | 2014-04-04 | 2014-06-25 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of p-methylphenyl-beta-D-thioacetylgalactoside |
| WO2019239425A1 (en) * | 2018-06-11 | 2019-12-19 | Aarti Industries Limited | Improved process for preparation of 2,3,4,6-tetra-o-benzyl-d-galactose |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880897A (en) * | 2014-04-04 | 2014-06-25 | 济南圣泉唐和唐生物科技有限公司 | Preparation method of p-methylphenyl-beta-D-thioacetylgalactoside |
| WO2019239425A1 (en) * | 2018-06-11 | 2019-12-19 | Aarti Industries Limited | Improved process for preparation of 2,3,4,6-tetra-o-benzyl-d-galactose |
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