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Transamination reaction of aromatic amine and amide derivatives under condition without catalysts and accelerants

A technology of amide derivatives and catalysts is applied in the field of synthesis of formamide derivatives, can solve problems such as toxicity, and achieve the effects of overcoming high toxicity, simple operation and high reaction yield

Inactive Publication Date: 2019-03-12
XIANGTAN UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] In view of the deficiencies in the existing methods for synthesizing formamide derivatives, such as the use of toxic formylating reagents, different types of catalysts, by-products and excessive use of acylating reagents, the purpose of the present invention is to provide a catalyst-free 1. Under the condition of no additive, the method for the synthesis and preparation of N-aryl formamide derivatives by the transamination reaction of weakly nucleophilic arylamines and amide derivatives

Method used

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  • Transamination reaction of aromatic amine and amide derivatives under condition without catalysts and accelerants
  • Transamination reaction of aromatic amine and amide derivatives under condition without catalysts and accelerants
  • Transamination reaction of aromatic amine and amide derivatives under condition without catalysts and accelerants

Examples

Experimental program
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Effect test

Embodiment 1

[0032] Put 4-methylaniline (107.2mg, 1.0mmol), formamide (0.4mL, 10.0mmol), and a stirring bar into the reaction tube, and seal the reaction tube under air condition. The reaction tube was placed in an oil bath reaction pot at 150°C, stirred and reacted for 24 hours, cooled to room temperature, diluted with 15 mL of water, and extracted three times with ethyl acetate, 15 mL each time. The extracts were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and the crude product was subjected to column chromatography with ethyl acetate: petroleum ether = 1:3 (containing 1% triethylamine) as the eluent Get pure. Yellow solid, melting point 54-56°C, yield 89%. 1 H NMR (400 MHz, CDCl 3 )δ8.63 (major rotamer, d, J=11.6Hz, 0.55H), 8.49 (major rotamer, br s, 0.51H), 8.33 (minor rotamer, s, 0.45H), 7.64 (minor rotamer, br s, 0.42H), 7.42(d, J=8.4Hz, 0.92H), 7.16-7.11 (m, 2.00H), 6.99(d, J=8.4Hz, 1.08H), 2.32(d, J=7.6Hz, 3....

Embodiment 2

[0034] Put 3-methylaniline (107.3 μL, 1.0 mmol), formamide (0.4 mL, 10.0 mmol), and a stirring bar into a reaction tube, and seal the reaction tube under air condition. The reaction tube was placed in an oil bath reaction pot at 150°C, stirred and reacted for 24 hours, cooled to room temperature, diluted with 15 mL of water, and extracted three times with ethyl acetate, 15 mL each time. The extracts were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and the crude product was subjected to column chromatography with ethyl acetate: petroleum ether = 1:3 (containing 1% triethylamine) as the eluent Get pure. Yellow oil, 80% yield. 1 H NMR (400MHz, CDCl 3 ) δ9.32(major rotamer,br s,0.51H),8.68(major rotamer,d,J=11.2Hz,0.54H),8.52(minor rotamer,br s,0.46H),8.30(minor rotamer,d,J =2.0Hz,0.46H),7.40(s,0.47H),7.34(d,J=8.0Hz,0.49H),7.22-7.15(m,1.00H),6.97(d,J=7.6Hz,0.53H ),6.93-6.90(m,1.51H),2.30(d,J=13.2Hz,3.00H); ...

Embodiment 3

[0036] Aniline (93 μL, 1.0 mmol), formamide (0.4 mL, 10.0 mmol), and a stir bar were put into a reaction tube, and the reaction tube was sealed under air condition. The reaction tube was placed in an oil bath reaction pot at 150°C, stirred and reacted for 24 hours, cooled to room temperature, diluted with 15 mL of water, and extracted three times with ethyl acetate, 15 mL each time. The extracts were combined, dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure, and the crude product was subjected to column chromatography with ethyl acetate: petroleum ether = 1:2 (containing 1% triethylamine) as the eluent Get pure. Yellow oil, yield 83%. 1 H NMR (400MHz, CDCl3) δ8.70 (major rotamer, d, J = 11.6Hz, 0.53H), 8.39 (minor rotamer, s, 0.47H), 8.14 (major rotamer, br, 0.49H), 7.56-7.54 (m,0.90H),7.39-7.32(m,2.39H),7.20(t,J=7.4Hz,0.55H),7.15(t,J=7.6Hz,0.50H),7.11-7.09(m,1.05 H); 13 C NMR (100MHz, CDCl 3 )δminor rotamer 163.1, 1...

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Abstract

The invention discloses high-yield synthesis method of an N-aryl amide derivative by transamination reaction of weakly nucleophilic aromatic amine and amide derivatives under the condition without catalysts and accelerants. The method has the advantages that substrate application range is wide, raw materials and acylation reagents are low in cost and easy to get, reaction yield is high, one-step reaction is achieved, cost is low, reaction selectivity is high, operation is simple and the like. By the method, gram-scale and high-yield synthesis of various pharmaceutical molecules can be achieved. The method has excellent application prospects in the field of synthesis application of the N-aryl amide derivative. The method overcomes the shortcomings that reaction reagents are high in toxicity, different types of catalysts are used, a synthesis method is high in cost and more in reaction step, by-products are more and the like in the prior art.

Description

technical field [0001] The present invention relates to a synthesis method of formamide derivatives, in particular to a transamination reaction of weakly nucleophilic aromatic amines and amide derivatives under the condition of no catalyst and no accelerator, and a high-yield synthesis of N-arylamide derivatives The invention belongs to the field of synthesis of pharmaceutical intermediates and fine organic synthesis. Background technique [0002] The amide skeleton is an important part of protein and is called "the first substance of life". Amides can also be used as multifunctional intermediates in synthetic chemistry and widely exist in drugs, pesticides, natural products and other functional materials (molecular structure formula below). [0003] [0004] Usually amides can be synthesized by coupling amines with carboxylic acid derivatives, aldehydes or alcohols [T.B. Halima, J. Masson-Makdissi, S.G. Newman, Angew. Chem. Int. Ed. 2018, 57, 12925; D. Milstein, J.Am. ...

Claims

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Application Information

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IPC IPC(8): C07C231/12C07C233/03C07C233/25C07C233/43C07C233/15C07D209/08C07D333/54C07D215/40C07D213/75C07D215/08C07D209/34
CPCC07C231/12C07D209/08C07D209/34C07D213/75C07D215/08C07D215/40C07D333/54C07C2603/24C07C233/03C07C233/25C07C233/43C07C233/15
Inventor 龚行尹嘉雯蔡昌群
Owner XIANGTAN UNIV
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