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Ionic liquid-catalyzed aza-michael addition of amines and unsaturated amides

An ionic liquid, unsaturated technology, applied in chemical instruments and methods, organic chemical methods, carboxylic acid amide preparation, etc., can solve problems such as long reaction time, harsh reaction conditions, excessive reagents, etc.

Active Publication Date: 2016-01-13
TAIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, Chinese and foreign scholars have conducted a lot of research on Michael addition, and many catalysts have emerged, such as: InCl 3 , CeCl 3 ·7H 2 O-NaI,SnCl 4 / FeCl 3 , Yb(OTf) 3 , PEG, β-cyclodextrin and enzymes, etc. Although these methods have achieved some success, most of them are caused by excessive amounts of reagents, long reaction times, harsh reaction conditions and some toxic solvents such as dichloromethane and acetonitrile. use, which is contrary to the idea of ​​green chemistry

Method used

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  • Ionic liquid-catalyzed aza-michael addition of amines and unsaturated amides
  • Ionic liquid-catalyzed aza-michael addition of amines and unsaturated amides
  • Ionic liquid-catalyzed aza-michael addition of amines and unsaturated amides

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Add 4-picoline (5mmol), acrylamide (5mmol), and 0.5mmol ionic liquid into a 50mL one-necked bottle in sequence, stir at room temperature for 1.5 hours, TLC detection, the raw materials disappear, extract the reaction solution with ethyl acetate, and combine the organic phases , column chromatography separation to obtain the product, the yield is 95%, and the content is 98%. 3-(4-methylpiperidin-1-yl)propanamide: 1 HNMR (400MHz, CDCl 3 )(ppm):8.18(s,1H),5.80(s,1H),3.42(d,2H,J=12.0Hz),2.72(t,2H,J=6.4Hz),2.49(d,2H,J =6.4Hz),2.17(m,2H),1.69(d,2H,J=13.2Hz),1.30(s,1H),1.27(d,2H,J=9.6Hz),0.94(d,3H,J = 6.4Hz); 13 CNMR (100MHz, CDCl 3 )(ppm): 175.2, 72.4, 61.6, 53.8, 53.1, 33.6, 31.9, 30.3, 21.5.

Embodiment 2

[0022] Add 4-picoline (5mmol), N,N-dimethylacrylamide (5mmol), and 0.5mmol ionic liquid into a 50mL one-necked bottle in turn, stir at room temperature for 1.5 hours, TLC detection, the raw materials disappear, and use ethyl acetate The ester was extracted from the reaction solution, the organic phases were combined, and the product was separated by column chromatography with a yield of 91% and a content of 95%.

[0023] N,N-dimethyl-3-(4-methylpiperidin-1-yl)propanamide: 1 HNMR (400MHz, CDCl 3 )(ppm):3.71(d,1H,J=4.8Hz),3.60(d,1H,J=4.8Hz),3.05(d,2H,J=11.6Hz),3.00(s,3H),2.92( s,3H),2.85-2.89(m,2H),2.66(d,2H,J=8.0Hz),2.17-2.23(m,2H),1.96(s,1H),1.66(d,2H,J= 11.6Hz), 0.92(d,3H,J=6.0Hz); 13 CNMR (100MHz, CDCl 3 )(ppm): 171.2, 72.5, 61.6, 53.6, 53.4, 37.2, 35.4, 32.9, 30.1, 30.0, 21.5.

Embodiment 3

[0025] Add 4-picoline (5mmol), N-methylolacrylamide (5mmol), and 0.5mmol ionic liquid to a 50mL single-necked bottle in turn, stir at room temperature for 1 hour, TLC detection, the raw materials disappear, and extract with ethyl acetate The reaction solution was combined with the organic phases, and the product was obtained by column chromatography separation with a yield of 93% and a content of 95%. N-(hydroxymethyl)-3-(4-methylpiperidin-1-yl)propanamide: 1 HNMR (400MHz, CDCl 3 )(ppm):8.98(s,1H),4.69(d,1H,J=6.0Hz),3.70(d,1H,J=3.2Hz),3.58(d,1H,J=3.2Hz),3.09( d,2H,J=11.6Hz),2.82(s,2H),2.52(s,2H),2.19-2.24(m,2H),1.96(s,1H),1.68(d,2H,J=13.2Hz ),1.44(s,1H),1.30-1.43(m,2H),0.92(q,3H,J=6.4Hz); 13 CNMR (100MHz, CDCl 3 )(ppm): 173.2, 72.4, 63.7, 61.4, 53.4, 53.0, 33.3, 32.9, 31.9, 29.9, 21.4.

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Abstract

The invention relates to an ionic liquid catalyzed amine and unsaturated amide aza-Michael addition method which is realized under the reaction conditions of an efficient and environment-friendly catalyst, no solvent and room temperature. The method comprises the step of with an ionic liquid as a catalyst, enabling amines and unsaturated amides to be subjected to aza-Michael addition reaction at room temperature and normal pressure to obtain a corresponding addition product, wherein the ionic liquid is repeatedly used eight times, and the catalytic reaction yield is not remarkably reduced. The method is simple in operation, high in yield, good in reusability of a catalytic reaction system, mild in reaction condition and wide in industrial application prospect.

Description

technical field [0001] The invention relates to a method for catalyzing the aza-Michael addition of amines and unsaturated amides with novel functional ionic liquids under the condition of high efficiency, greenness and solvent-free. technical background [0002] Amide derivatives are important intermediates and are widely used in the fields of fine chemicals and antibiotic medicine. Michael addition is an important method to expand amide derivatives and explore new active molecules of amide drugs. In recent years, Chinese and foreign scholars have conducted a lot of research on Michael addition, and many catalysts have emerged, such as: InCl 3 , CeCl 3 ·7H 2 O-NaI,SnCl 4 / FeCl 3 , Yb(OTf) 3 , PEG, β-cyclodextrin and enzymes, etc. Although these methods have achieved some success, most of them are caused by excessive amounts of reagents, long reaction times, harsh reaction conditions and some toxic solvents such as dichloromethane and acetonitrile. use, which deviates...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07B43/04C07B43/00C07D213/04C07D295/15C07D207/327C07C231/12C07C237/06
Inventor 应安国李志峰胡华南杨健国冯子娟
Owner TAIZHOU UNIV