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 large catalyst usage, difficult separation of products and catalysts, and corrosion of equipment, etc. The effect of avoiding the use of highly toxic chemical raw materials, wide application range of substrates and mild reaction conditions

Inactive Publication Date: 2012-03-28
EAST CHINA NORMAL UNIVERSITY
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Problems solved by technology

[0002] At present, the catalysts used in the Ferrier rearrangement reaction of 3,4,6-tri-O-benzylglucoene include ammonium cerium nitrate, trifluoroacetic acid, acid zeolite and ferric sulfate hydrate, etc., but the main catalysts are ammonium cerium nitrate As a catalyst for the Ferrier rearrangement of 3,4,6-tri-O-benzylglucoene (K. Pachamuthu, Y. D. Vankar, J. Org. Chem. 2001, 66, 7511-7513), the method obtained A mixture of rearrangement products and deoxyglycoside products, the yield is low, thus limiting the wide application of this method; trifluoroacetic acid (Hui-Chang Lin, et al, Tetrahedron Lett. 2005, 46, 5071-5076), this method The obtained mixture of rearrangement product and deoxyglycoside product also has a very low yield, and the catalyst uses a relatively large equivalent, which corrodes equipment, thus limiting its wide application; acid zeolite (A. P. Rauter, T. Almeida, J. Mol. Catal. A: Chem., 2007, 275, 206-213), this method needs to be carried out at a relatively high temperature of 85°C, using the more toxic 1,2-dichloroethane as a solvent, and the reaction is

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Take 40 mg (0.096 mmol) of 3,4,6-tri-O-benzyl-D-glucene and 1 mL of dichloromethane, mix them, add 0.035 mL (0.384 mmol) of n-butanol under stirring, and then add FeCl3 prepared by the above method / C solid acid catalyst 9mg, react at room temperature, TLC plate tracking and monitoring the reaction (PE:EA=10:1), after 2 hours, TLC monitors that the reaction of the raw material is complete, filter the catalyst, and the filtrate is concentrated and purified to obtain a colorless liquid product. 34.3 mg of 4,6-di-O-benzyl-D-glucurene n-butanoside, the yield of the rearrangement reaction was 90%.

[0015] The resulting product 4,6-di-O-benzyl-D-glucosene n-butanoside was analyzed, and the test data were as follows:

[0016] 1H-NMR data: 1H NMR (500 MHz, CDCl3): δ=7.35-7.24 (m, 10H), 6.07(d, J=10.2Hz, 1H), 5.77 (d, J=10.2, 1H), 5.10 (s, 1H, H-1β), 5.01 (s, 1H, H-1α), 4.65 (d, J=12.1Hz, 1H), 4.60 (d, J=11.6Hz, 1H), 4.51 (d, J =12.1Hz, 1H), 4.44 (d, J=11.5Hz, 1H), 4.17 (d, J...

Embodiment 2

[0018] Take 40mg (0.096mmol) of 3,4,6-tri-O-benzyl-D-glucene and mix 1mL of dichloromethane, add 50.4 mg (0.192mmol) of dehydroepiandrosterone under stirring, and then add the above method to prepare FeCl3 / C solid acid catalyst 6mg, reacted at room temperature, TLC plate tracking and monitoring the reaction (PE:EA=10:1), after 3.5h, TLC monitored the raw material reaction was complete, filtered off the catalyst, and the filtrate was concentrated and silica gel column chromatography Separation (PE:EA=25:1), 47 mg of pure white solid 4,6-di-O-benzyl-α-D-glucosene dehydroepiandrosterone was obtained, and the yield of its rearrangement reaction was 82 %.

[0019] The resulting product 4,6-di-O-benzyl-α-D-glucosene dehydroepiandrosterone glycoside was analyzed, and the test data were as follows:

[0020] 1H-NMR data: 1H NMR (500 MHz, CDCl3): δ=7.35-7.24 (m, 10H), 6.07 (d, J=10.3Hz, 1H), 5.75 (d, J=10.2Hz, 1H), 5.27 (s, 1H), 5.17(s, 1H, H-1α), 4.65 (d, J=12.1Hz, 1H), 4.60 (d, J=11...

Embodiment 3

[0022]Take 200mg (0.48mmol) of 3,4,6-tri-O-benzyl-D-glucene and mix 6mL of dichloromethane, add 290mg (1.92mmol) of p-tert-butylphenol under stirring, and then add the above method to prepare FeCl3 / C solid acid catalyst 180mg, reacted at room temperature, TLC plate tracking and monitoring the reaction (PE:EA=10:1), after 60min, TLC monitored the raw material reaction was complete, filtered off the catalyst, and the filtrate was concentrated and separated by silica gel column chromatography (PE:EA=25:1), 175 mg of pure white solid 4,6-di-O-benzyl-D-glucosene p-tert-butylphenol glycoside was obtained, and the yield of rearrangement reaction was 80%.

[0023] The resulting product 4,6-di-O-benzyl-D-glucosene p-tert-butylphenol glycoside was analyzed, and the test data were as follows:

[0024] 1H-NMR data: 1H NMR (500 MHz, CDCl3): δ=7.33-7.26 (m, 12H), 7.06-7.05 (m, 2H),6.19 (d, J=10.5Hz, 1H), 5.90 (d , J=10.0Hz, 1H), 5.76(s, 1H, H-1β), 5.66 (s, 1H, H-1α), 4.65-4.46 (m, 4H), 4.2...

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Abstract

The invention discloses a method for preparing 4,6-dibenzyl 2,3-unsaturated glucoside. The method is characterized by comprising the following steps of: mixing 3,4,6-tri-O-benzyl glucal and dichloromethane in a mole/volume ratio of 1mmol: (10-40)ml, adding an acceptor with stirring, performing 3,4,6-tri-O-benzyl glucal rearrangement reaction at room temperature under the action of a FeCl3/C solid acid catalyst, concentrating and purifying the filtrate after the reaction is finished, and thus obtaining the 4,6-dibenzyl 2,3-unsaturated glucoside. Compared with the prior art, the method has the advantages that: the method has simple process, low production cost, high yield and milder reaction conditions, is convenient to operate, avoids the use of high-toxicity chemical raw materials, does not pollute the environment, and is a method for synthesizing a 3,4,6-tri-O-benzyl glucal rearrangement product with the advantages of wider substrate application range, environment friendliness, economical efficiency and high efficiency.

Description

technical field [0001] The invention relates to the technical field of synthesis of pharmaceutical intermediates, in particular to a preparation method of 4,6-dibenzyl 2,3-unsaturated glycoside. Background technique [0002] At present, the catalysts used in the Ferrier rearrangement reaction of 3,4,6-tri-O-benzylglucoene include ammonium cerium nitrate, trifluoroacetic acid, acid zeolite and ferric sulfate hydrate, etc., but the main catalysts are ammonium cerium nitrate As a catalyst for the Ferrier rearrangement of 3,4,6-tri-O-benzylglucoene (K. Pachamuthu, Y. D. Vankar, J. Org. Chem. 2001, 66, 7511-7513), the method obtained A mixture of rearrangement products and deoxyglycoside products, the yield is low, thus limiting the wide application of this method; trifluoroacetic acid (Hui-Chang Lin, et al, Tetrahedron Lett. 2005, 46, 5071-5076), this method The obtained mixture of rearrangement product and deoxyglycoside product also has a very low yield, and the catalyst uses...

Claims

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Application Information

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IPC IPC(8): C07H15/04C07H1/00C07J17/00C07H15/203
Inventor 张剑波李娟周家芬司文帅
Owner EAST CHINA NORMAL UNIVERSITY
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