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Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid

An ionic liquid, nitrile and amide technology, applied in chemical instruments and methods, organic chemistry methods, cyanide reaction preparation, etc., can solve the problems of excess, harsh reaction conditions, long reaction time, etc.

Inactive Publication Date: 2010-06-09
ZHEJIANG MEDICINE CO LTD XINCHANG PHAMACEUTICAL FACTORY +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Over the years, many catalysts have emerged, such as: SnCl 4 / FeCl 3 , InCl 3 , CeCl 3 ·7H 2 O-NaI, Yb(OTf) 3 , CAN, Bi(NO 3 ) and LiClO 4 etc. Although these methods have achieved certain success, there are some defects in them, such as: the need for a large excess of reagents, long reaction time, harsh reaction conditions and the use of some toxic solvents such as dichloromethane and acetonitrile

Method used

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  • Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid
  • Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid
  • Novel method for preparing beta-aminoketone, ester, nitrile and amide derivatives through catalysis of functional ionic liquid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Morpholine (5mmol), methyl acrylate (5.5mmol), and 1mmol lactic acid ionic liquid [DBU][Lac] were sequentially added to a 50mL single-necked bottle, stirred at room temperature for 2 hours, and detected by TLC, the raw materials disappeared, and the reaction solution was extracted with ether. The organic phases were combined and separated by column chromatography to obtain the product with a yield of 95% and a content of 98%. 3-(1-Morpholinyl)-propionic acid methylester: 1 H NMR (400MHz, CDCl 3 )(ppm): 3.66(s, 3H, OCH 3 ), 3.67-3.65 (m, 4H, morpholinyl), 2.65 (t, 2H, J=6Hz, CH 2 ), 2.48(t, 2H, J=6Hz, CH 2 ), 2.43-2.41 (m, 4H, morpholinyl); 13 C NMR (100MHz, CDCl 3 )(ppm): 172.8, 66.8, 53.8, 53.3, 51.6, 31.7.

Embodiment 2

[0025] Add n-propylamine (5mmol), methyl acrylate (5.5mmol), and 1mmol n-propionic acid ionic liquid [DBU][Pr] into a 50mL single-necked bottle in turn, stir at room temperature for 2 hours, TLC detects that the raw materials disappear, and extract the reaction with ether liquid, combined the organic phases, and separated by column chromatography to obtain the product with a yield of 86% and a content of 95%. 3-(1-Propylamine)-propionic acidmethyl ester: 1 H NMR (400MHz, CDCl 3 )(ppm): 3.63(s, 3H, OCH 3 ), 2.62(t, 2H, J=6.4Hz, CH 2 ), 2.45(t, 2H, J=6.4Hz, CH 2 ), 2.58 (m, 2H, CH 2 ), 1.41 (m, 2H, CH 2 ), 0.90 (m, 3H, CH 3 ); 13 C NMR (100MHz, CDCl 3 )(ppm): 170.5, 66.8, 52.8, 52.1, 44.9, 28.1, 12.3.

Embodiment 3

[0027] Piperidine (5mmol), methyl acrylate (5.5mmol), and 1mmol acetic acid ionic liquid [DBU][Ac] were sequentially added to a 50mL single-necked bottle, stirred at room temperature for 1.5 hours, and detected by TLC, the raw materials disappeared, and the reaction solution was extracted with ether. The organic phases were combined and separated by column chromatography to obtain the product with a yield of 96% and a content of 98%. 3-(1-Piperidinyl)-propionic acidmethyl ester: 1 H NMR (400MHz, CDCl 3 )(ppm): 3.86(s, 3H, OCH 3 ), 2.86(t, 2H, J=6Hz, CH 2 ), 2.68(t, 2H, J=6Hz, CH 2 ), 1.80-1.75 (m, 4H, piperidinyl), 1.61-1.44 (m, 4H, piperidiny), 1.42-1.26 (m, 2H, piperidinyl); 13 C NMR (100MHz, CDCl 3 )(ppm): 173.8, 54.2, 53.8, 52.9, 31.8, 29.3, 25.8, 24.6, 23.1.

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Abstract

The invention relates to a method for generating beta-aminoketone, ester, nitrile and amide derivatives by performing aza-Michael addition on amine substances and electron-deficient alkenes through an efficient environment-friendly catalyst under solvent-free mild (room temperature) reaction conditions. The method comprises the steps of taking ionic liquid as the catalyst, subjecting amine substances and electron-deficient alkenes to aza-Michael addition at room temperature under normal pressure and obtaining corresponding beta-aminoketone, ester, nitrile and amide derivatives. The ionic liquid is repeatedly used five times, and reaction yield does not obviously drop. The method has the advantages of simple operation, high yield, good using repeatability of the catalytic reaction system, mild reaction conditions and good prospects for industrialization.

Description

technical field [0001] The invention relates to a method for preparing beta-amino ketones, esters, nitriles and amide derivatives by Michael addition with novel functional ionic liquids as catalysts under efficient, green and solvent-free conditions. technical background [0002] β-Amino ketone, ester, nitrile and amide derivatives are widely used as intermediates in the fields of fine chemical industry and antibiotic medicine. General synthetic methods include Mannich reaction and aza-Michael addition. In contrast, Michael addition is more suitable for the preparation of β-amino ketones, esters, nitriles and amides derivatives. Over the years, many catalysts have emerged, such as: SnCl 4 / FeCl 3 , InCl 3 , CeCl 3 ·7H 2 O-NaI, Yb(OTf) 3 , CAN, Bi(NO 3 ) and LiClO 4 etc. Although these methods have all achieved certain success, there are some defects in them, such as: needing a large excess of reagents, long reaction time, harsh reaction conditions and the use of som...

Claims

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Application Information

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IPC IPC(8): C07B43/04C07B43/00C07C227/06C07D295/14B01J31/02B01J31/04
Inventor 应安国刘泺张国钧吴国锋叶伟东陈新志陈建辉张开元钱胜
Owner ZHEJIANG MEDICINE CO LTD XINCHANG PHAMACEUTICAL FACTORY
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