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Preparation method of 4,6-O-benzylene-3-O-acetyl-D-glucal

A technology of glucone and acetyl group, applied in 4 fields, can solve problems such as high cost of personal safety reagents, unfavorable large-scale production, unfavorable environmental protection, etc., and achieves the effects of easy operation, little pollution, and easy preparation method

Inactive Publication Date: 2012-11-14
SHANGHAI INST OF PHARMA IND
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] The technical problem to be solved by the present invention is to overcome the need to use highly toxic thiophenol in the preparation method of 4,6-O-benzylidene-3-O-acetyl-D-glucene in the prior art, which is inconvenient to operate, It is not conducive to environmental protection and the personal safety of operators and the cost of some reagents used in the reaction is relatively high, which is not conducive to the defects of large-scale industrial production, and a 4,6-O-benzylidene-3-O- A method for preparing acetyl-D-glucoene, which is easy to operate, avoids the use of highly toxic reagents, has little environmental pollution, mild reaction conditions, and high yield, and is suitable for large-scale industrial production

Method used

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  • Preparation method of 4,6-O-benzylene-3-O-acetyl-D-glucal
  • Preparation method of 4,6-O-benzylene-3-O-acetyl-D-glucal

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] Weigh 2.5 g (6 mmol) of 4,6-O-benzylidene-3-O-acetyl-1-bromo-D-glucose (compound 11) and dissolve it in 7.5 mL of dichloromethane. Add Zn (1.95g, 30mmol), NH 4 Cl(1.6g, 30mmol), VO(AcAc) 2 (3mg, 0.012mmol) and AcOH (0.03mL, 0.6mmol), stirred at 10°C for 24h. TLC monitoring, the reaction is complete. Filter, wash the filter residue with 10mL dichloromethane, dilute the filtrate with 20mL dichloromethane, then wash twice with 15mL water, once with 15mL of saturated sodium bicarbonate solution, once with 15mL of saturated saline, once with anhydrous Na 2 SO 4 dry. After filtration, the filtrate was spin-dried and purified by silica gel column chromatography to obtain 0.38 g of a white solid (compound 1) with a yield of 57%. The purity was greater than 99% as determined by HPLC.

[0023] Its structural identification data are as follows:

[0024] 1 H NMR: δ6.39 (dd, 1H, J 1，2 =6.1,J 1，3 =1.7Hz, H-1), 4.80(dd, 1H, H-2), 5.45(dt, 1H, J 2，3 =1.9,J 3，4 =8.8Hz, H-3), ...

Embodiment 2

[0027] Weigh 1.0 g (2.4 mmol) of 4,6-O-benzylidene-3-O-acetyl-1-bromo-D-glucose (compound 11) and dissolve it in 15 mL of MeCN. Add Zn (1.56g, 24.08mmol), NH 4 Cl (1.29g, 24.08mmol), VO(AcAc) 2 (6.5mg, 0.024mmol) and AcOH (0.13mL, 2.4mmol), stirred at 30°C for 12h. TLC monitoring, the reaction is complete. Filter, wash the filter residue with 10mL ethyl acetate, dilute the filtrate with 25mL ethyl acetate, then wash twice with 15mL water, once with 15mL of saturated sodium bicarbonate solution, once with 15mL of saturated saline, once with anhydrous Na 2 SO 4 dry. After filtration, the filtrate was spin-dried and purified by silica gel column chromatography to obtain 0.57 g of a white solid (compound 1) with a yield of 85.6%. The purity was greater than 99% as determined by HPLC.

Embodiment 3

[0029] Weigh 1.0 g (2.4 mmol) of 4,6-O-benzylidene-3-O-acetyl-1-bromo-D-glucose (compound 11) and dissolve it in 10 mL of MeCN. Add Zn (1.56g, 24.08mmol), NH 4 Cl (1.29g, 24.08mmol), VO(Salon) (15.8mg, 0.048mmol), AcOH (1.36mL, 24mmol), stirred at 25°C for 10h. TLC monitoring, the reaction is complete. Filter and wash the filter residue with 10 mL of ethyl acetate. After diluting the filtrate with 20 mL of ethyl acetate, wash it twice with 15 mL of water, once with 15 mL of saturated sodium bicarbonate solution, once with 15 mL of saturated saline, and once with anhydrous Na 2 SO4 dry. After filtration, the filtrate was spin-dried and purified by silica gel column chromatography to obtain 0.59 g of a white solid (compound 1) with a yield of 89.5%. The purity was greater than 99% as determined by HPLC.

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Abstract

The invention discloses a preparation method of 4,6-O-benzylene-3-O-acetyl-D-glucal, comprising the following step: carrying out reduction reaction on a compound 11 in an organic solvent in the presence of complex of vanadium, acetic acid, zinc and ammonium salt, wherein the molar ratio of the acetic acid to the compound 11 is 0.1:1-20:1, the complex of vanadium is a complex of vanadium represented by formula 12 and / or formula 13, and the ammonium salt is ammonium chloride and / or ammonium bromide. The method has simple operation, avoids the usage of toxic reagents, has the advantages of low environmental pollution, mild reaction conditions, and high yield, and is suitable for industrial large-scale production.

Description

technical field [0001] The invention relates to a preparation method of 4,6-O-benzylidene-3-O-acetyl-D-glucocene. Background technique [0002] 4,6-O-benzylidene-3-O-acetyl-D-glucene is a key intermediate in the preparation of 2-position deoxysugars, which has a wide range of applications and plays an important role in sugar chemistry. [0003] Gridley, Jonathan J.; Hacking, Andrew J.; Osborn, Helen M.I.; Spackman, David G.; Synlett; nb. 12; (1997); Mallet, J.-M.; Sinay, P.; Bulletin de la Societe Chimique de France; vol.130; nb.3; (1993); p.256-265 on 4,6-O-benzylidene-3 The preparation method of -O-acetyl-D-glucosene is reported, and its synthetic route is as follows: [0004] [0005] Reaction conditions: a. Pyridine, Ac 2 O; b. BF 3 ·Et 2 O, PhSH; c. MeONa, MeOH; d. camphorsulfonic acid, benzaldehyde dimethyl acetal, DMF; e. pyridine, Ac 2 O; f. RuCl 3 , NaIO 4 ; g. Hexamethylphosphoric triamide, SmI 2 . [0006] The synthetic route uses D-glucose as the sta...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D493/04
Inventor 林峰苏颀朱晓峰
Owner SHANGHAI INST OF PHARMA IND
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