Method for preparing 4, 6-dibenzyl-2, 3-unsaturated glucoside

An unsaturated and dibenzyl technology is applied in the field of preparation of 4,6-dibenzyl-2,3-unsaturated glycosides, which can solve the problems of easy corrosion of catalysts, narrow reaction scope, limited wide application, etc. To achieve the effect of cheap solvent, low toxicity, wide application range and cheap and easy-to-obtain raw materials

Inactive Publication Date: 2011-05-18
EAST CHINA NORMAL UNIV
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Problems solved by technology

[0002] At present, the catalyst used in the Ferrier rearrangement reaction of 3,4,6-tri-O-benzylglucoene is mainly ceric ammonium nitrate (K. Pachamuthu , Y. D. Vankar, J. Org. Chem.2001, 66, 7511-7513), this method often obtains a mixture of rearrangement products and deoxyglycoside products, due to the complex product , the yield is low, thus limiting the wide application of this method
Others use trifluoroacetic acid as a catalyst (Hui-Chang Lin, Wen-Ping Du, et al, Tetrahedron Lett. 2005, 4...

Method used

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  • Method for preparing 4, 6-dibenzyl-2, 3-unsaturated glucoside

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0015] Add 0.1mmol 3,4,6-tri-O-benzyl-D-glucene 40mg and 1mL dichloromethane respectively in the reaction flask and mix, add 10mg sulfuric acid / silicon dioxide solid catalyst (H 2 SO 4 / SiO 2 ) and 0.5mmol methanol 0.02mL at 0 o The rearrangement reaction was carried out under the condition of C, and the reaction was tracked and monitored by TLC plate (PE:EA=10:1). After 0.5 hours of reaction, TLC monitored that the raw material was not completely converted, and 5 mg of sulfuric acid / silica solid catalyst was added. After 2 hours, the raw material After conversion, the rearrangement reaction of 3,4,6-tri-O-benzyl-D-glucocene is completed, the catalyst is filtered off, and the filtrate is concentrated to obtain a colorless viscous liquid which is 4,6-di-O-benzyl- D-glucosene methyl glycoside 15mg, yield 92%.

[0016] The NMR structure analysis of 4,6-di-O-benzyl-D-glucurene methyl glycoside, the test data is as follows ：

[0017] 1 H NMR (500 MHz, CDCl 3 ): (α:β=8.5:1) ...

Embodiment 2

[0020] Add 0.5mmol 3,4,6-tri-O-benzyl-D-glucene 200mg and 10mL acetonitrile respectively in the reaction flask and mix, add 25mg sulfuric acid / silica solid catalyst (H 2 SO 4 / SiO 2 ) and 1.2mmol dehydroepiandrosterone 0.33g, at 50 o The rearrangement reaction was carried out under the condition of C, and the reaction was followed and monitored by TLC plate (PE:EA=10:1), and the reaction was monitored by TLC after 10 minutes. The catalyst was filtered off, and the filtrate was concentrated to obtain 0.25 g of pure white solid 4,6-di-O-benzyl α-D-glucosene dehydroepiandrosterone glycoside, with a yield of 87%. The deagent is petroleum ether: ethyl acetate=10:1~100:1 (v / v).

[0021] NMR structure analysis of 4,6-di-O-benzyl α-D-glucosene dehydroepiandrosterone glycoside, the test data are as follows ：

[0022] 1 H NMR (500 MHz, CDCl 3 ): δ =7.35-7.23 (m, 10H), 6.09 (d, J =10.2Hz, 1H), 5.77 (m, 1H), 5.27 (m, 1H), 5.17(s, 1H), 4.67 (d, J =12.2Hz, 1H), 4.62 (d, J =11.5H...

Embodiment 3

[0025] Add 0.15mmol 3,4,6-tri-O-benzyl-D-glucoene 40mg and 1mL diethyl ether respectively in the reaction flask and mix, add 50mg sulfuric acid / silicon dioxide solid catalyst (H 2 SO 4 / SiO2 ) and 0.2mmol menthol 30mg, in 10 o The rearrangement reaction was carried out under the condition of C, and the reaction was tracked and monitored by TLC plate (PE:EA=10:1). After 50 minutes, TLC monitored the reaction to be complete, filtered off the catalyst, and concentrated the filtrate to obtain 3,4,6-tri-O-benzyl 45 mg of the rearrangement product of D-glucosene, the product was separated by silica gel column chromatography (100-200 mesh, PE:EA=25:1), and the pure colorless syrup 4,6-di-O-benzyl was obtained Base-D-glucosene menthol glycoside 40.2mg, yield 90%.

[0026] NMR structure analysis of 4,6-di-O-benzyl-D-glucosene menthol glycoside, the test data is as follows ：

[0027] 1 H NMR (500 MHz, CDCl 3 ): (α:β=10:1) δ =7.35-7.23 (m, 10H), 6.07 (d, J =10.2Hz, 1H), 5.80-5.7...

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Abstract

The invention discloses a method for preparing 4, 6-dibenzyl-2, 3-unsaturated glucoside, which is characterized by comprising the following steps of: mixing 3, 4, 6-tri-O-benzyl glucal and dichloromethane, acetonitrile, tetrahydrofuran, N, N-dimethylformamide, acetone or diethyl ether in a molar volume ratio of 1 mol: (5-50) L, adding a sulfuric acid/silica catalyst and an oxygen- or sulfur-containing nucleophilic receptor under stirring, undergoing a rearrangement reaction of 3, 4, 6-tri-O-benzyl glucal at a temperature of 0-50 DEG C, filtering out the catalyst after the reaction ends, and concentrating the filter liquor to obtain the 4, 6-dibenzyl-2, 3-unsaturated glucoside. The method for preparing the 4, 6-dibenzyl-2, 3-unsaturated glucoside has the advantages of simple process, convenience in operating, high yield, low production cost and no environmental pollution; the reagent used for synthesis is cheap and easy to get; the dissolvent is cheap and easy to get and has little toxicity; and the method for preparing the 4, 6-dibenzyl-2, 3-unsaturated glucoside is a method for an Ferrier rearrangement reaction of 3, 4, 6-tri-O-benzyl glucose ene with a very good application prospect.

Description

technical field [0001] The invention relates to the technical field of synthetic chemical industry, in particular to a preparation method of 4,6-dibenzyl-2,3-unsaturated glycoside. Background technique [0002] At present, the catalyst used in the Ferrier rearrangement reaction of 3,4,6-tri-O-benzylglucoene is mainly cerium ammonium nitrate (K. Pachamuthu, Y. D. Vankar, J. Org. Chem. 2001, 66, 7511-7513), this method often obtains a mixture of rearrangement products and deoxyglycoside products, and the wide application of this method is limited due to the complex products and low yield. Others use trifluoroacetic acid as a catalyst (Hui-Chang Lin, Wen-Ping Du, et al , Tetrahedron Lett. 2005, 46, 5071-5076), the product obtained by this method is still a mixture of rearrangement products and deoxyglycoside products, and the catalyst is easy to corrode equipment, thus limiting its wide application. Another example is using acid zeolite to catalyze the rearrangement rea...

Claims

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Application Information

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IPC IPC(8): C07H15/18C07H15/207C07J1/00
Inventor 张剑波张博李娟周家芬
Owner EAST CHINA NORMAL UNIV
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