Green conjugated double bond reduction method

A technology of conjugated double bonds and conjugated carbon-carbon double bonds, which is applied in the fields of organic reduction, chemical instruments and methods, and the preparation of organic compounds, to achieve the effect of high chemoselectivity and mild reaction conditions

Active Publication Date: 2013-12-25
无锡富泽药业有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, all reported reactions require catalysts and are almost always carried out in toxic organic solvents

Method used

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023]

[0024] The conjugated double bond compound 1 (2-styryl malononitrile, C 10 h 6 N 2 ) (30.8mg, 0.2mmol), dihydropyridinate (60.7mg, 0.24mmol) and 2mL of water were added to a single-mouthed 25mL chicken heart bottle, heated to 100°C, stirred for 24 hours, and extracted by adding 5mL of ethyl acetate (the same method operation three times), the organic layers were combined, dried over magnesium sulfate, evaporated under reduced pressure with a rotary evaporator, and then silica gel column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain 29.0 mg of the product, with a yield of 93%, without colored liquid.

[0025] H NMR spectrum: 1 HNMR (600MHz, CDCl 3 ): 3.28(d, J=6.96Hz, 2H), 3.91(t, J=6.96Hz, 2H), 7.32(d, J=6.72Hz, 2H), 7.38-7.42(m, 3H).

Embodiment 2

[0027]

[0028] The conjugated double bond compound 2 (2-(1-naphthylvinyl)-malononitrile, C 14 h 8 N 2 ) (40.8mg, 0.2mmol), dihydropyridinate (60.7mg, 0.24mmol) and 2mL of water were added to a single-mouthed 25mL chicken heart bottle, heated to 80°C, stirred for 24 hours, and extracted by adding 5mL of ethyl acetate (the same method operation three times), the organic layers were combined, dried over sodium sulfate, evaporated under reduced pressure with a rotary evaporator, and then silica gel column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain 30.1 mg of the product, with a yield of 73%, white solid.

[0029] Proton NMR spectrum: 1HNMR (400MHz, CDCl 3 ): 3.83(d, J=7.60Hz, 2H), 4.10(t, J=7.60Hz, 3H), 7.50-7.67(m, 4H), 7.88-7.98(m, 3H).

Embodiment 3

[0031]

[0032] The conjugated double bond compound 3 (2-(4-bromostyryl)-malononitrile, C 10 h 5 BrN 2 ) (46.4mg, 0.2mmol), dihydropyridinate (60.7mg, 0.24mmol) and 2mL of water were added to a single-mouthed 25mL chicken heart bottle, heated to 80 degrees, stirred for 24 hours, and extracted by adding 5mL of ethyl acetate (the same method operation three times), the organic layers were combined, dried over sodium sulfate, vacuum distillation with a rotary evaporator, and then silica gel column chromatography (petroleum ether: ethyl acetate = 15:1) to obtain 35.1 mg of the product, a colorless liquid, and the yield 75%, 1HNMR (400MHz, CDCl 3 ): 3.27(d, J=6.80Hz, 2H), 3.93(d, J=6.76Hz, 1H), 7.23(d, J=8.32Hz, 2H), 7.57(d, J=8.40Hz, 2H).

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Abstract

The invention relates to a green conjugated double bond reduction method capable of taking water as a solvent and dihydropyridine ester as a hydrogen source, and selectively reducing the conjugated double bond with strong electron-withdrawing groups. By adopting the method, conjugated carbon-carbon double bonds with strong electron-withdrawing groups are selectively reduced by taking water as the solvent and the dihydropyridine ester as the hydrogen source under the condition that no catalyst is needed. The method comprises the following steps: (1) adding a compound of conjugated carbon-carbon double bonds with strong electron-withdrawing groups and the dihydropyridine ester to water according to the molar ratio of (1:1) to (1:3), heating and warming to 60-100 DEG C; stirring and reacting for 5-24 hours at the temperature; (2) adding an organic solvent to the solution obtained in the step (1) to extract for at least three times according to the volume ratio of 2:5; (3) merging, drying and carrying out reduced pressure distillation on an organic layer of the product obtained in the step (2), and then carrying out column chromatography, so as to obtain the reduced product. The green conjugated double bond reduction method has the advantages of being non-toxic, mild in reaction condition, free of adding of a catalyst, high in chemical selectivity and the like.

Description

technical field [0001] The invention relates to a method for reducing conjugated double bonds of organic matter, in particular to a method for selectively reducing green conjugated bonds with strong electron-withdrawing groups using water as a solvent and dihydropyridine ester as a hydrogen source without adding any catalyst. Double bond reduction method. Background technique [0002] Selective reduction of conjugated carbon-carbon double bonds is an essential step in the synthesis of many natural products and pharmaceuticals, and it is a very useful and challenging reaction, especially when many functional groups exist in one molecule. Scientists from all over the world have conducted in-depth research on this reaction, and different hydrogen sources (such as H2, NaBH4, NaBH3CN, alcohols, diimines, PhSiH3, etc.) have been used in this reaction ((a) M.D.Bhor, M.J.Bhanushali, N.S.Nandurkar , B.M.Bhanage, Catal.Commun., 2007, 8, 2064. (b) D.Xue, Y.C.Chen, X Cui, Q.W.Wang, J.Z...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B35/02C07C253/30C07C255/33C07C255/35C07C255/34C07C255/41C07D307/54
Inventor 王周玉蒋珍菊蒋胜前何其
Owner 无锡富泽药业有限公司
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