Method for synthesizing amides from oxime

A technology for synthesizing amides and amides, applied in the formation/introduction of amides, preparation of carboxylic acid amides, chemical instruments and methods, etc., to achieve broad development prospects and low catalyst load

Inactive Publication Date: 2015-03-18
NANJING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The disadvantage of the reaction is that it needs to be carried out at 160 ° C, and the reaction also generates by-products such as nitrile

Method used

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  • Method for synthesizing amides from oxime
  • Method for synthesizing amides from oxime
  • Method for synthesizing amides from oxime

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Embodiment 1: benzamide

[0021] benzamide

[0022]

[0023] Benzaldehyde oxime (60.6mg, 0.5mmol), [Cp*Ir(H 2 O) 3 ][OTf] 2 (5.1mg, 0.0075mmol, 1.5mol%) and water (1ml) were sequentially added to a 25ml Schlenk reaction flask. After the reaction mixture was reacted at 110°C for 12 hours, it was cooled to room temperature, water was removed by rotary evaporation, and the target product was obtained by column separation with a yield of 89%.

[0024] 1 H NMR (500MHz, CDCl 3 )δ7.82(d,J=7.6Hz,2H,ArH),7.54(t,J=7.3Hz,1H,ArH),7.45(t,J=7.6Hz,2H,ArH),6.16(br s, 1H,NH),6.00(br s,1H,NH); 13 C NMR (125MHz, CDCl 3 )δ169.7, 133.3, 131.9, 128.6, 127.3.

Embodiment 2

[0025] Embodiment 2:4-Methylbenzamide

[0026] 4-methylbenzamide

[0027]

[0028] 4-Methylbenzaldehyde oxime (67.6mg, 0.5mmol), [Cp*Ir(H 2 O) 3 ][OTf] 2 (5.1mg, 0.0075mmol, 1.5mol%) and water (1ml) were sequentially added to a 25ml Schlenk reaction flask. After the reaction mixture was reacted at 110°C for 12 hours, it was cooled to room temperature, water was removed by rotary evaporation, and the target product was obtained by column separation with a yield of 93%. ; 1 H NMR (500MHz, CDCl 3 )δ7.71(d,J=7.9Hz,2H,ArH),7.25(d,J=7.9Hz,2H,ArH),6.12(br s,1H,NH),5.87(br s,1H,NH) ,2.41(s,3H,CH 3 ); 13 CNMR (125MHz, CDCl 3 )δ169.5, 142.5, 130.4, 129.2, 127.3, 21.4.

Embodiment 3

[0029] Embodiment 3:4-isopropylbenzamide

[0030] 4-isopropylbenzamide

[0031]

[0032] 4-Isopropylbenzaldehyde oxime (81.6mg, 0.5mmol), [Cp*Ir(H 2 O) 3 ][OTf] 2 (5.1mg, 0.0075mmol, 1.5mol%) and water (1ml) were sequentially added to a 25ml Schlenk reaction flask. After the reaction mixture was reacted at 110°C for 12 hours, it was cooled to room temperature, water was removed by rotary evaporation, and the target product was obtained by column separation with a yield of 92%. mp152-153℃; 1 H NMR (500MHz, CDCl 3 )δ7.75(d,J=8.2Hz,2H,ArH),7.30(d,J=8.2Hz,2H,ArH),6.09(br s,1H,NH),5.84(br s,1H,NH) ,2.96(heptet,J=6.9Hz,1H,CH),1.27(d,J=6.9Hz,6H,CH 3 ); 13 C NMR (125MHz, CDCl 3 )δ169.8, 153.2, 130.8, 127.5, 126.6, 34.1, 23.7.

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Abstract

The invention discloses a method for synthesizing amides from oxime. The method is characterized by adding oxime, water and a water-soluble iridium complex catalyst to a reaction vessel, cooling a reactant to the room temperature after the reaction mixture reacts at 80-120 DEG C for several hours, removing water through selective evaporation, and obtaining a target product through column separation. Compared with existing methods for synthesizing amides through oxime rearrangement in water through transition metal catalysis, the method has the advantages that the used catalyst is low in load and does not contain phosphine ligands severely polluting the environment, so that the reaction can be carried out in the air, without nitrogen protection; therefore the reaction meets the green chemical requirements and has an extensive development prospect.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis chemistry, and in particular relates to a method for synthesizing amides. Background technique [0002] Amides are important functional groups of proteins and are also used as intermediates in the synthesis of fine chemicals, natural products and polymers, etc. The traditional method for the synthesis of amides is through the reaction of carboxylic acid derivatives (eg, acid chlorides, anhydrides, and esters) with ammonia. Although widely used, the raw materials used in this method are highly toxic and corrosive to equipment. The reaction releases a large amount of energy and produces a large amount of waste acid. Sex is low. The other is under the condition of strong acid and high temperature, through the isomerization of oxime, the Beckmann rearrangement reaction occurs to directly generate the target product amide. Although this method has high atom economy, the reaction conditions ...

Claims

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Application Information

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IPC IPC(8): C07B43/06C07C233/65C07C235/46B01J31/22C07D333/38C07D307/54C07C233/11C07C233/05C07C231/10
Inventor 孙春楼渠攀攀李峰
Owner NANJING UNIV OF SCI & TECH
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