CN103880897A - Preparation method of p-methylphenyl-beta-D-thioacetylgalactoside - Google Patents
Preparation method of p-methylphenyl-beta-D-thioacetylgalactoside Download PDFInfo
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- CN103880897A CN103880897A CN201410133429.8A CN201410133429A CN103880897A CN 103880897 A CN103880897 A CN 103880897A CN 201410133429 A CN201410133429 A CN 201410133429A CN 103880897 A CN103880897 A CN 103880897A
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Abstract
The invention relates to the field of carbohydrates and particularly relates to a preparation method of p-methylphenyl-beta-D-thioacetylgalactoside. The preparation method comprises the steps of adding acetic anhydride and a catalyst at room temperature; adding D-galactose; after the reaction is ended, dropwise adding the reaction liquid into a thiocresol and methylene dichloride solution; after the reaction is ended, carrying out after-treatment to obtain p-methylphenyl-beta-D-thioacetylgalactoside. The method is used for synthesizing p-methylphenyl-beta-D-thioacetylgalactoside through one-step reaction, and is simple in operation, easy to obtain raw materials and capable of saving operation cost and materials.
Description
technical field
The present invention relates to sugar compounds synthesis technical field, be specifically related to the preparation method of a kind of p-methylphenyl-β-D-thioacetyl galactoside.
Background technology
P-methylphenyl-β-D-thioacetyl galactoside, English name: P-Tolyl-2,3,4,6-tetra-O-acetyl-1-thio-β-D-glucopyranoside, molecular formula C
21h
26o
9s, structural formula is as follows:
Saccharide compound is the sustain life main source of activity institute energy requirement of all living things body, it is not only nutritive substance, and some also has special physiologically active, it is the organic compound that distributed in nature is the most extensive, quantity is maximum, thio glycoside is as a kind of special saccharide compound, because it has unique physiologically active, have a wide range of applications at biomedicine field.
In the prior art, document (Dasgupta Somnath, Mukhopadhyay Balaram, Rajput Vishal Kumar, et al. Journal of Carbohydrate Chemistry. 2007,26 (2): 1054-1061) report directly adopts five acetyl glucose and toluene-ω-thiol under boron trifluoride diethyl etherate effect, to prepare p-methylphenyl-β-D-thioacetyl glucoside, but the boron trifluoride diethyl etherate catalyzer using is inflammable, there is strong impulse and strong corrosion, in damp atmosphere, easily decompose.China Patent Publication No. is that CN103554200A discloses a kind of " a kind of method of preparing parathiocresol-tetra--O-ethanoyl-β-D-semi-lactosi ", and this invention is to prepare parathiocresol-tetra--O-ethanoyl-β-D-semi-lactosi by bromo acetyl sugar and toluene-ω-thiol reaction.This route need first be prepared bromo sugar, and bromo sugar is unstable, perishable.Separately there are document (Weng, Shiue-Shien. Tetrahedron Letters. 2009,50 (46): 6414-6417) report is prepared this compound with five acetyl glucose and iodine and toluene-ω-thiol at dichloromethane solution.But iodine easily distils, harmful, and waste water causes certain harm to environment, and iodine value lattice are more expensive, and cost is higher.
Summary of the invention
In order to solve the larger reagent of the unpleasant toxicity of use existing in the preparation of p-methylphenyl-β in above prior art-D-thioacetyl galactoside, use unstable intermediate, step is various, process trouble, relative cost is higher, operates more numerous and diverse present situation, the invention provides and a kind ofly adopts single stage method, utilizes the catalyzer that toxicity is less, intermediate reaction does not need to process, the preparation method of p-methylphenyl-β-D-thioacetyl galactoside simple to operate, raw material is easy to get.
The technical problem to be solved in the present invention is achieved through the following technical solutions:
A preparation method for p-methylphenyl-β-D-thioacetyl galactoside, comprises the following steps:
A) under room temperature by aceticanhydride and catalyst mix, under stirring, add D-semi-lactosi, temperature control reaction obtains penta-acetyl galactose solution;
B) penta-acetyl galactose solution is dripped in toluene-ω-thiol solution, temperature control stirring reaction aftertreatment obtain p-methylphenyl-β-D-thioacetyl galactoside.
Described preparation method, preferred described aceticanhydride: catalyzer: D-semi-lactosi: be 5.5-6.5: 1-1.5: 1:1.1-1.3 to methylbenzene phenyl-sulfhydrate mol ratio.
Described preparation method, in preferred steps a, temperature of reaction is 50-55 ℃, the reaction times is 2-3 hour.
Described preparation method, in preferred steps a, catalyzer is aluminum chloride.
Described preparation method, in preferred steps b, temperature of reaction is 15-20 ℃, the reaction times is 2-4 hour.
Described preparation method, in preferred steps b, in toluene-ω-thiol solution, solvent is methylene dichloride, the mol ratio of toluene-ω-thiol and methylene dichloride is 1.1-1.3:4.5-5.5.
Described preparation method, in preferred steps b, aftertreatment is cancellation, extraction, washing, concentrating under reduced pressure, mixed solvent crystallization.
Described preparation method, preferably cancellation solvent is deionized water, the mol ratio of D-semi-lactosi and deionized water is 1:8-10.
Described preparation method, preferably extraction solvent is methylene dichloride, the mol ratio of itself and D-semi-lactosi is 3-4:1.
Described preparation method, preferably concentrating under reduced pressure temperature is 30-35 ℃, in mixed solvent, mixed solvent is that mol ratio is the t-butyl methyl ether of 1:2-3 and the solvent mixture of isohexane.
Beneficial effect: the inventive method adopts different reaction systems, comprises catalyzer, temperature of reaction, order of addition(of ingredients) and charging capacity, treatment processs etc., only obtain product by single step reaction, have effectively improved production safety coefficient; Simple to operate, raw material is easy to get, and has saved running cost and material, and products obtained therefrom purity is more than 99%, and yield is more than 90%.
Accompanying drawing explanation
Fig. 1 is embodiment, the HPLC spectrogram of 4 products that obtain,
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the product that obtains of embodiment 4.
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.
embodiment 1 5.5: 1: 1:1.1:4.5
A) room temperature adds 5.5mol aceticanhydride and 1mol aluminum chloride in reactor, temperature control adds 1molD-semi-lactosi at 50-55 ℃, react 2 hours, after having reacted, reaction solution is added dropwise in the dichloromethane solution of 1.1mol toluene-ω-thiol and 4.5mol, temperature control reacts 2 hours at 15-20 ℃, after completing, obtains 0.904mol p-methylphenyl-β-D-thioacetyl galactoside through processing later, yield is 90.4%, purity 99.78%.
In step a, aftertreatment is to drip the deionized water and stirring of 0-5 ℃ of 10mol 1 hour, with the dichloromethane extraction water layer of 4mol, separate organic phase 8mol deionized water wash organic phase three times, separate organic phase concentrated, add the isohexane mixed solution crystallization of 1mol t-butyl methyl ether and 3mol, filter, dry.
embodiment 2 5.5: 1.5: 1:1.2:4.5
A) room temperature adds 5.5mol aceticanhydride and 1.5mol aluminum chloride, temperature control adds 1molD-semi-lactosi at 50-55 ℃, react 3 hours, after having reacted, reaction solution is added dropwise in the dichloromethane solution of 1.2mol toluene-ω-thiol and 4.5mol, temperature control reacts 3 hours at 15-20 ℃, after completing, obtains 0.911mol p-methylphenyl-β-D-thioacetyl galactoside through processing later, yield is 91.1%, purity 99.81%.
In step a, aftertreatment is to drip the deionized water and stirring of 0-5 ℃ of 10mol 1 hour, with the dichloromethane extraction water layer of 4mol, separate organic phase 8mol deionized water wash organic phase three times, separate organic phase concentrated, add the isohexane mixed solution crystallization of 1mol t-butyl methyl ether and 3mol, filter, dry.
embodiment 36: 1.5: 1:1.3:5.0
A) room temperature adds 6mol aceticanhydride and 1.5mol aluminum chloride, temperature control adds 1molD-semi-lactosi at 50-55 ℃, react 2.5 hours, after having reacted, reaction solution is added dropwise in the dichloromethane solution of 1.3mol toluene-ω-thiol and 5.0mol, temperature control reacts 4 hours at 15-20 ℃, after completing, obtains 0.907mol p-methylphenyl-β-D-thioacetyl galactoside through processing later, yield is 90.7%, purity 99.76%.
In step a, aftertreatment is to drip the deionized water and stirring of 0-5 ℃ of 8mol 1 hour, with the dichloromethane extraction water layer of 4mol, separate organic phase 8mol deionized water wash organic phase three times, separate organic phase concentrated, add the isohexane mixed solution crystallization of 1mol t-butyl methyl ether and 2mol, filter, dry.
embodiment 46: 1: 1:1.1:5.5
A) room temperature adds 6mol aceticanhydride and 1mol aluminum chloride, temperature control adds 1molD-semi-lactosi at 50-55 ℃, react 2 hours, after having reacted, reaction solution is added dropwise in the dichloromethane solution of 1.1mol toluene-ω-thiol and 5.5mol, temperature control reacts 2 hours at 15-20 ℃, after completing, obtain 0.914mol p-methylphenyl-β-D-thioacetyl galactoside through processing later, yield is 91.4%, purity 99.87%, see Fig. 1, product carries out proton nmr spectra detection, the results are shown in Figure 2, show that the reaction product obtaining is p-methylphenyl-β-D-thioacetyl galactoside.
In step a, aftertreatment is to drip the deionized water and stirring of 0-5 ℃ of 8mol 1 hour, with the dichloromethane extraction water layer of 4mol, separate organic phase 8mol deionized water wash organic phase three times, separate organic phase concentrated, add the isohexane mixed solution crystallization of 1mol t-butyl methyl ether and 2mol, filter, dry.
embodiment 5 comparative examples
A) room temperature adds 5.5mol aceticanhydride and 0.05mol perchloric acid, controls at 20-25 ℃ of temperature and adds 1molD-semi-lactosi, reacts 2.5 hours, after having reacted, add the deionized water of 10mol, separate out yellow solid, obtain the five acetyl semi-lactosis of 0.78mol through the acetone recrystallization of 6mol;
B) the five acetyl semi-lactosis of 0.78mol are added in the methylene dichloride of 10mol, add the boron trifluoride diethyl etherate of 0.98mol, temperature control adds the toluene-ω-thiol of 0.83mol at 15-20 ℃, stir 3 hours, react aftertreatment and obtained p-methylphenyl-β-D-thioacetyl galactoside of 0.82mol, yield is 82%, purity 99.57%.
In step b, aftertreatment is to drip the deionized water and stirring of 0-5 ℃ of 10mol 2 hours, with the dichloromethane extraction water layer of 4mol, separate organic phase 10mol deionized water wash organic phase three times, separate organic phase concentrated, add the isohexane mixed solution crystallization of 0.6mol t-butyl methyl ether and 1.2mol, filter, dry.
Claims (10)
1. a preparation method for p-methylphenyl-β-D-thioacetyl galactoside, is characterized in that comprising the following steps:
A) under room temperature by aceticanhydride and catalyst mix, under stirring, add D-semi-lactosi, temperature control reaction obtains penta-acetyl galactose solution;
B) penta-acetyl galactose solution is dripped in toluene-ω-thiol solution, temperature control stirring reaction aftertreatment obtain p-methylphenyl-β-D-thioacetyl galactoside.
2. preparation method according to claim 1, is characterized in that described aceticanhydride: catalyzer: D-semi-lactosi: be 5.5-6.5: 1-1.5: 1:1.1-1.3 to methylbenzene phenyl-sulfhydrate mol ratio.
3. preparation method according to claim 1, is characterized in that in step a, temperature of reaction is 50-55 ℃, and the reaction times is 2-3 hour.
4. preparation method according to claim 1, is characterized in that in step a, catalyzer is aluminum chloride.
5. preparation method according to claim 1, is characterized in that in step b, temperature of reaction is 15-20 ℃, and the reaction times is 2-4 hour.
6. preparation method according to claim 1, is characterized in that in step b in toluene-ω-thiol solution that solvent is methylene dichloride, and the mol ratio of toluene-ω-thiol and methylene dichloride is 1.1-1.3:4.5-5.5.
7. preparation method according to claim 1, is characterized in that in step b, aftertreatment is cancellation, extraction, washing, concentrating under reduced pressure, mixed solvent crystallization.
8. preparation method according to claim 7, is characterized in that cancellation solvent is deionized water, and the mol ratio of D-semi-lactosi and deionized water is 1:8-10.
9. preparation method according to claim 7, is characterized in that extraction solvent is methylene dichloride, and the mol ratio of itself and D-semi-lactosi is 3-4:1.
10. preparation method according to claim 7, is characterized in that concentrating under reduced pressure temperature is 30-35 ℃, and in mixed solvent, mixed solvent is that mol ratio is the t-butyl methyl ether of 1:2-3 and the solvent mixture of isohexane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070011A (en) * | 2018-01-05 | 2018-05-25 | 河南科技大学 | A kind of galactolipin sugar ester base compound donator and preparation method thereof |
Citations (3)
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| CN103554200A (en) * | 2013-11-19 | 2014-02-05 | 济南卡博唐生物科技有限公司 | Method for preparing parathiocresol-tetra-O-acetyl-beta-D-galactose |
| CN103665063A (en) * | 2013-12-12 | 2014-03-26 | 济南卡博唐生物科技有限公司 | Method for preparing isopropyl-beta-D-isopropylthiogalactoside |
| CN103665064A (en) * | 2013-12-12 | 2014-03-26 | 济南卡博唐生物科技有限公司 | Method for preparing 2,3,4,6-tetra-O-benzyl -D-galactose |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554200A (en) * | 2013-11-19 | 2014-02-05 | 济南卡博唐生物科技有限公司 | Method for preparing parathiocresol-tetra-O-acetyl-beta-D-galactose |
| CN103665063A (en) * | 2013-12-12 | 2014-03-26 | 济南卡博唐生物科技有限公司 | Method for preparing isopropyl-beta-D-isopropylthiogalactoside |
| CN103665064A (en) * | 2013-12-12 | 2014-03-26 | 济南卡博唐生物科技有限公司 | Method for preparing 2,3,4,6-tetra-O-benzyl -D-galactose |
Non-Patent Citations (2)
| Title |
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| GEETANJALI AGNIHOTRI, ET AL.,: "One-pot synthesis of per-O-acetylated thioglycosides from unprotected reducing sugars.", 《CARBOHYDRATE RESEARCH》 * |
| SHIQIANG YAN, ET AL.,: "A Facile and Efficient Method for the One-Pot Synthesis of Per-O-acetylated Thioglycosides from Unprotected Sugars.", 《JOURNAL OF CARBOHYDRATE CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108070011A (en) * | 2018-01-05 | 2018-05-25 | 河南科技大学 | A kind of galactolipin sugar ester base compound donator and preparation method thereof |
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Application publication date: 20140625 |