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Method for preparing N-aryl amide without solvent and catalyst

A kind of aryl amide and catalyst technology, which is applied in the field of solvent-free and catalyst-free preparation of N-aryl amide, and can solve problems such as expensive

Inactive Publication Date: 2017-05-17
CHANGSHA UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

More recently, thiocarboxylates such as potassium salts have also been used to condense amines to produce amides (H. Liu, et al, ACS Catal , 2016, 6 , 1732-1736), and the reaction can be achieved under light in an open air environment, but requires the use of an expensive ruthenium homogeneous catalyst
Despite the emergence of methods for the synthesis of amides, there are still great challenges in academia and industry

Method used

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  • Method for preparing N-aryl amide without solvent and catalyst
  • Method for preparing N-aryl amide without solvent and catalyst
  • Method for preparing N-aryl amide without solvent and catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0014] Embodiment 1, 5-(4-methylbenzyl) Michaelis acid and the influence of the ratio of o-methoxyaniline on the acylation reaction of the present invention (with the I-1 compound shown in the formula as an example)

[0015]

[0016] Add 5-(4-methylbenzyl) Michaelis acid and 2-methoxyaniline (5:1, 2:1, 1:1, 1:2, 1:5) in different molar ratios to the reaction tube in 100 o C reaction, detecting the influence of the molar ratio of (4-methylbenzyl) Michaelis acid and 2-methoxyaniline on the yield of the acylation reaction. After the reaction, the separation yields of the target amides were 96%, 96%, 97%, 95%, and 94%, respectively. This shows that no matter how the molar ratio of (4-methylbenzyl) Michaelis acid and 2-methoxyaniline changes, the yield of the acylation reaction is very stable (based on the insufficient amount of raw materials), and the (4-methylbenzyl) The optimal molar ratio of benzyl) Michaelis acid to 2-methoxyaniline is 1:1.

[0017] 1 H NMR (500 MHz, CD...

Embodiment 2

[0018] The synthesis of I-2 compound shown in embodiment 2, formula

[0019]

[0020] 5-(4-Methylbenzyl) Michaelis acid (0.2 mmol) and 3-methoxyaniline (0.2 mmol) were sequentially added into the reaction flask, and reacted at 100° C. for 5 hours. Water and ethyl acetate were added to the reaction solution, followed by washing with hydrochloric acid (4 mol / L) and saturated aqueous sodium carbonate solution, and the organic phase was dried and desolventized to obtain the target amide as a white solid with a yield of 95%.

[0021] 1 H NMR (500 MHz, CDCl 3 ) δ 7.26 (bs, 1H), 7.22 – 7.18 (m, 2H), 7.15 –7.12 (m, 4H), 6.92 (d, J = 7.8 Hz, 1H), 6.66 (dd, J = 8.0, 1.5 Hz, 1H), 3.81(s, 3H), 3.03 (t, J = 7.6 Hz, 2H), 2.65 (t, J = 7.8 Hz ,2H), 2.34 (s, 3H). 13 CNMR (125 MHz, CDCl 3 ) δ 170.58, 160.11, 139.02, 137.48, 135.92, 129.61, 129.33, 128.27, 111.97, 110.16, 105.58, 55.29, 39.65, 31.12, 21.04.

Embodiment 7

[0022] The synthesis of I-3 compound shown in embodiment 7, formula

[0023]

[0024] Except that the aromatic amine was 2,4-dimethoxyaniline, other reaction conditions were the same as in Example 2 to obtain a white solid with a yield of 98%.

[0025] 1 H NMR (500 MHz, CDCl3 ) δ 8.26 (d, J = 8.5 Hz, 1H), 7.51 (bs, 1H),7.17 (d, J = 8.0 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 6.50 – 6.47 (m, 2H), 3.82(s, 3H), 3.81 (s, 3H), 3.04 (t, J = 7.8 Hz, 2H), 2.69 (t, J = 7.8 Hz, 2H),2.34 (s, 2H). 13 C NMR (125 MHz, CDCl 3 ) δ 169.99, 156.29, 149.11, 137.68, 135.71, 129.22, 128.26, 121.20, 120.73, 103.69, 98.57, 55.64, 55.55, 39.65, 31.20, 21.03.

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PUM

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Abstract

The invention discloses a method for preparing N-aryl amide without a solvent and a catalyst. The method is characterized by obtaining the N-aryl amide under solvent-free and catalyst-free action; a molar ratio of substituted meldrum acid and arylamine is (1 to 5) to (5 to 1). According to the method disclosed by the invention, the defects that acyl chloride, anhydride, a dehydration coupling reagent, the solvent, a phase transfer catalyst or a metal catalyst, and the like are required to be adopted in the prior art are overcome; the method has the following advantages that (1) the substituted meldrum acid is used as an acylating agent, so that pre-activation on carboxylic acid or use of the dehydration coupling reagent is avoided; (2) due to easiness in preparation of the substituted meldrum acid, certain difficult-to-obtain or expensive carboxylic acid and activated derivatives are prevented from being used; (3) a solvent-free mode is adopted, so that the use of a toxic organic solvent or emission of wastewater is avoided; (4) no acid, base or metal catalysts exist, the influence of the acid and the base on sensitive groups and equipment and the residue of metal ions in a product are avoided. A synthesis method disclosed by the invention can play an important role in industrial production for preparing the N-aryl amide and particularly for preparing the N-aryl amide with complex carboxylic acid.

Description

technical field [0001] The present invention relates to a method for preparing N-arylamide without solvent and catalyst, in particular, it relates to a method of directly converting substituted Michaelis acid and aromatic amine to prepare N-arylamide under solvent-free and catalyst-free conditions. method. Background technique [0002] As a dominant structural module, amides widely exist in biomolecules such as proteins, natural products, marketed drugs and various intermediates, and are the most basic organic functional groups. Therefore, its synthesis has attracted extensive attention of chemists and has made great progress. Generally, amides are prepared by condensation of carboxylic acids or their derivatives with amines (R. M. de Figueiredo, J. S. Suppo and J. M. Campagne, Chem. Rev., 2016, 116 , 12029-12122; Taylor, J. E. and S. D. Bull. 6.11 N-Acylation Reactions of Amines A2 -Knochel, Paul. Comprehensive Organic Synthesis II (Second Edition) .Amsterdam, Elsevier...

Claims

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Application Information

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IPC IPC(8): C07C231/02C07C233/29C07C233/15C07C233/25C07C233/11C07C233/07C07B43/06
CPCC07B43/06C07C231/02C07C233/29C07C233/15C07C233/25C07C233/11C07C233/07
Inventor 李江胜陈郭芹达玉栋
Owner CHANGSHA UNIVERSITY OF SCIENCE AND TECHNOLOGY
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