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Method used for reduction of tertiary amide into alcohols and/or amines

A technology for tertiary amides and tertiary amine compounds is applied in the reduction field of selectively reducing tertiary amides to alcohols and/or tertiary amines, which can solve the problems of difficult to control products, toxic and harmful, harsh conditions, etc., and achieves environmental protection and safe operation. Simple, wide-ranging effects

Active Publication Date: 2019-07-26
CHINA AGRI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] The purpose of the present invention is to provide a method for reducing tertiary amides, which solves the problems of complex operations, harsh conditions, and difficult control of the products produced in the reduction methods of amides in the prior art, so that tertiary amides can be selectively reduced to alcohols Compounds and / or tertiary amine compounds, this method does not use noble metal catalysts, toxic and harmful silanes and flammable and explosive metal hydrides, and does not produce toxic by-products, the reaction is more environmentally friendly

Method used

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  • Method used for reduction of tertiary amide into alcohols and/or amines
  • Method used for reduction of tertiary amide into alcohols and/or amines
  • Method used for reduction of tertiary amide into alcohols and/or amines

Examples

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Embodiment 1

[0064]

[0065] In a 10mL single-necked bottle, under nitrogen protection, add 0.50mmol compound 1a, 2.5mL cyclohexane, 10mmol ethanol, 5.0mmol sodium dispersion reagent (34.1wt%, mineral oil suspension, particle size 5-10μm), 0°C It was stirred at 100°C for 5 min, warmed to room temperature, and quenched with saturated aqueous sodium bicarbonate solution. Diethyl ether and saturated brine were added for extraction, the organic phase was dried, concentrated, and separated by column chromatography to obtain 32 mg of the target compound 2a with a yield of 47%.

[0066] 1 H NMR (400MHz, CDCl 3 )δ7.34-7.29(m,2H),7.25-7.19(m,3H), 3.69(t,J=6.3Hz,2H),2.73(t,J=7.8Hz,2H),1.96-1.88(m ,2H),1.76 (br,1H); 13 C NMR (100MHz, CDCl 3 )δ141.9, 128.5, 128.4, 125.9, 62.3, 34.2, 32.1.

Embodiment 2

[0068]

[0069] In a 10mL single-necked bottle, add 0.50mmol compound 1a, 2.5mL toluene, saturated aqueous sodium bicarbonate (H 2 (0:10mmol), 2.0mmol sodium dispersion reagent (34.1wt%, toluene suspension, particle size<100μm), stirred at 0°C for 30min, raised to room temperature, and quenched the reaction with saturated aqueous sodium bicarbonate solution. Diethyl ether and saturated brine were added for extraction, the organic phase was dried, concentrated, and separated by column chromatography to obtain 14 mg of the target compound 3a with a yield of 15%.

[0070] 1 H NMR (300MHz, CDCl 3 )δ7.31-7.22(m,2H),7.21-7.13(m,3H), 2.65(t,J=7.8Hz,2H),2.53-2.41(m,6H),1.84(m,2H),1.80 -1.71(m, 4H); 13 C NMR (75MHz, CDCl 3 )δ142.3, 128.4, 128.3, 125.7, 56.1, 54.2, 34.0, 30.7, 23.5.

Embodiment 3

[0072]

[0073] In a 10mL single-necked bottle, add 0.50mmol compound 1a, 2.5mL toluene, saturated aqueous sodium bicarbonate solution (D 2 O: 10mmol, 2.0mmol sodium dispersion reagent (34.1wt%, toluene suspension, particle size <100μm), stirred at 0°C for 30min, raised to room temperature, quenched with saturated aqueous sodium bicarbonate solution. Diethyl ether and saturated brine were added for extraction, the organic phase was dried, concentrated, and separated by column chromatography to obtain 28.7 mg of the target compound 5a with a yield of 30%.

[0074] 1 H NMR (300MHz, CDCl 3 )δ7.32-7.22(m,2H),7.22-7.13(m,3H), 2.65(t,J=7.6Hz,2H),2.48(m,4H),1.84(t,J=7.6Hz,2H ),1.77(m, 4H); 13 C NMR (75MHz, CDCl 3 )δ142.3, 128.4, 128.3, 125.7, 55.2(m), 54.1, 33.9, 30.4, 23.5.

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Abstract

The invention discloses a method used for reduction of tertiary amide into alcohols and / or amines. The method comprises following steps: tertiary amide, an alkali metal reagent, and a proton donor agent are added into an organic solvent for a following reaction selectively: when the proton donor agent is a raw material alcohol and / or inorganic salt aqueous solution, the reaction product is an alcohol compound and / or tertiary amine compound. The method is capable of realizing selective reduction of tertiary amide into alcohols and tertiary amine compounds, the yield is high, the suitable rangeis wide, operation is safe and simple, the adopted raw materials are cheap and easily available; no precious metal catalyst, toxic silanes, and flammable and combustible metal hydrides are adopted; notoxic by product is generated; reaction is more friendly to the environment; problems in the prior art that amide compound reducing method operation is complex, conditions are strict, and control ofproducts is difficult are solved.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a reduction method for selectively reducing tertiary amides to alcohols and / or tertiary amines. Background technique [0002] Alcohols and amines are among the most common functional groups in pesticides, pharmaceuticals and materials science. Selective reduction of amides in raw materials to alcohols or amines has important research and application value. At the same time, in recent years, the development of deuterated compounds has attracted much attention, and their uses are very wide, and the demand is gradually increasing. In the pharmaceutical industry, the introduction of deuterium can improve the pharmacokinetic properties of the drug, increase the stability of the drug, and reduce the toxicity of the drug (J.Med.Chem.2011,54,2529-2591). The drug is officially on the market. In addition, deuterated compounds can be used as tools for studying chemical reaction mechanism...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B31/00C07B59/00C07C29/00C07C33/20C07C33/46C07C31/125C07C33/025C07C31/135C07C31/137C07C33/24C07D295/03C07D295/023C07C209/50C07C211/27C07C211/03C07C41/26C07C43/23C07D295/096C07D209/12C07C213/00C07C215/08C07C319/20C07C323/19
CPCC07B31/00C07B59/001C07B59/002C07B59/004C07B2200/05C07C29/00C07C41/26C07C209/50C07C213/00C07C319/20C07D209/12C07D295/023C07D295/03C07D295/096C07C33/20C07C33/46C07C31/125C07C33/025C07C31/135C07C31/137C07C33/24C07C211/27C07C211/03C07C43/23C07C215/08C07C323/19
Inventor 安杰李恒朝张斌阎昱好罗仕晖张运通
Owner CHINA AGRI UNIV
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