Method for protecting D-glucosamine derivative by using benzaldehyde dimethyl acetal

A technology of benzaldehyde dimethyl acetal and glucosamine, which is applied to the preparation of sugar derivatives, sugar derivatives, sugar derivatives, etc., can solve the problems of complex post-processing, poor raw material utilization, and low reaction conversion rate, and achieve Simplify the post-treatment process, increase the reaction conversion rate, and reduce the cost

Active Publication Date: 2014-02-19
内蒙古佳瑞米精细化工有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] 1. The reaction conversion rate is low, the raw material utilization rate is poor, and the post-treatment is complicated
[0008] 2. Post-treatment needs to remove high boiling point solvent (DMF), high energy consumption, long time, and poor economy

Method used

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  • Method for protecting D-glucosamine derivative by using benzaldehyde dimethyl acetal

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0019] The 250mL four-neck bottle is equipped with mechanical stirring, thermometer and condenser. Add D-glucosamine derivative (10.0g, 29.3mmol, 1.0eq), camphorsulfonic acid (0.18g, 0.77mmol, 0.026eq), benzaldehyde dimethyl acetal (9.7g, 61.8mmol, 2.0eq), tetrahydrofuran (100mL), heated to reflux. Stir for 2 hours with heat preservation, during which 80 mL of condensed tetrahydrofuran was separated out, and 85 mL of tetrahydrofuran was added to keep the volume in the reaction bottle unchanged. After the reaction was completed, the temperature was lowered to room temperature, 50 mL of purified water (0.09 g of sodium bicarbonate was dissolved in it) was added to the reaction flask, and the reaction flask was incubated and stirred in an ice-water bath at 3°C ​​for 2 hours. After filtering, the filter cake was washed twice with 20 mL of methanol*2 to obtain 11.3 g of white solid, which was dried in vacuum to obtain 10.8 g of white solid powder. The normalized content is 99.60%...

Embodiment 2

[0021] The 500mL four-necked bottle is equipped with a mechanical stirrer, a thermometer and a condenser. Add D-glucosamine derivative (10.0g, 29.3mmol, 1.0eq), camphorsulfonic acid (0.68g, 2.93mmol, 0.1eq), benzaldehyde dimethyl acetal (10.3g, 64.5mmol, 2.2eq), acetonitrile (300mL), heated to reflux. Insulated and stirred for 6 hours, during which a total of 350 mL of condensed acetonitrile was separated out, and 380 mL of acetonitrile was added to keep the volume in the reaction bottle constant. After the reaction is completed, desolvate under reduced pressure until 150 mL of the reaction liquid remains in the reaction bottle, add 50 mL of purified water into the reaction bottle, and keep stirring in an ice-water bath at 3°C ​​for 2 hours. After filtering, the filter cake was washed twice with 20 mL of methanol*2 to obtain 11.0 g of white solid, which was dried in vacuum to obtain 10.3 g of white solid powder. The normalized content is 98.99%, and the normalized yield is 8...

Embodiment 3

[0025] Put substrate (1.50kg, 4.44mol, 1.0eq), camphorsulfonic acid (26.1g, 0.11mol, 0.025eq) and benzaldehyde dimethyl acetal (1.37kg, 8.88mol, 2.0eq) into the 30L jacketed kettle in sequence , THF (13.4 kg). Reflux for 8 hours, during which a total of 13.1 kg of condensed tetrahydrofuran was separated out, and 13.5 kg of tetrahydrofuran was added to keep the reaction volume constant. After the reaction is over, distill under reduced pressure until the remaining reaction liquid in the kettle is about 8L, transfer tap water (8.0kg) into the reaction kettle, and lower the temperature to 0°C-5°C. After insulated and stirred for 2 hours, centrifuge. The filter cake was washed with cold methanol (4kg, 0°C-5°C). Finally, 1.98 kg of slightly yellowish white filter cake was obtained. After drying at 45°C, 1.68kg of white solid powder was obtained, the normalized content was 98.22%, and the normalized yield was 89.43%.

[0026] A total of 13.1 kg of THF was extracted, 500 g of cal...

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Abstract

The invention discloses a method for protecting a D-glucosamine derivative by using benzaldehyde dimethyl acetal, and belongs to the chemical field of organic chemical glycosylation. According to the method, D-glucosamine and the derivative of D-glucosamine are taken as substrates, D-glucosamine, the derivate of D-glucosamine and benzaldehyde dimethyl acetal perform reflux in an organic solvent to generate a benzylidene glucose derivative under the catalysis of CSA (camphorsulfonic acid); methyl alcohol generated by reaction is continuously removed during reaction, so that the equilibrium rightward movement is promoted, and the reaction conversion rate is increased; and the removed organic solvent can be recycled and reused after treated, and the reaction economy is improved further.

Description

technical field [0001] The invention relates to a method for protecting D-glucosamine derivatives with benzaldehyde dimethyl acetal, which belongs to the field of organic chemistry and sugar chemistry. Background technique [0002] D-glucosamine and its derivatives are an important class of monosaccharides and pharmaceutical intermediates. Glucosamine is an important part of proteoglycans with strong hydrophilicity. It can synthesize collagen in the human body and is easily absorbed by the human body. At the same time, glucosamine has special functions for bone and joint diseases and is an important class of pharmaceutical intermediates. [0003] During the synthesis of D-glucosamine derivatives, it is often necessary to selectively protect the hydroxyl groups at C4 and C6 for further functionalization. The method of protection is usually to generate acetal or ketal. There are two commonly used methods: [0004] 1. Acetone and D-glucosamine derivatives react under the ac...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07H1/00C07H9/04
Inventor 杜志博张宏毕晨光王乃伟
Owner 内蒙古佳瑞米精细化工有限公司
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