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Environment-friendly amido bond synthesis method

A technology for synthesizing amides and phenylhydrazine, which is applied in the field of green and environmentally friendly synthesizing amide bonds, can solve problems such as waste and excessive use of stoichiometry, and achieve the effect of realizing application value

Active Publication Date: 2016-10-12
JIANGXI NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] Although the traditional method of chemical synthesis of amides relying on coupling reagents and the method of inserting carbonyl with halobenzene are very effective and useful, the stoichiometric or even excessive use of toxic coupling reagents, the by-products of the reaction (equivalent hydrohalic acid ) have brought great pressure to environmental protection, and also caused a lot of waste. From the perspective of "atom economy" and "green synthesis" strategic directions, these disadvantages will affect their wide application

Method used

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  • Environment-friendly amido bond synthesis method

Examples

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Effect test

example 1

[0019]

[0020] 1) Add 0.4mmol of phenylhydrazine hydrochloride and Pd(OAc) to a clean 25mL Schlenk tube 3 (1.3mg, 3mol%), PPh 3 (10.5mg, 20mol%), Na 2 CO 3 (21.2mg, 0.2mmol), in CO:O 2 =3:1, inject morpholine (17.4mg, 0.2mmol) and mixed solvent (dmso:dioxane =0.1:0.9mL), react at 100°C for 12h, TLC spot plate detection.

[0021] 2) After the reaction, the reaction solution was added with 2 mL of water, and then extracted with EA for 3-5 times. The organic layer was concentrated and subjected to column chromatography to obtain a pure amide compound, a yellow liquid, with a yield of 76%.

[0022] 1 H NMR(400MHz, CDCl 3 )δ7.45-7.36 (m, 5H), 3.77-3.46 (m, 8H). 13 CNMR(100MHz, CDCl 3 )δ170.5, 135.3, 129.9, 128.6, 127.1, 66.9 (2C), 48.1, 42.5.

example 2

[0024]

[0025] 1) Add 0.4mmol of m-methylphenylhydrazine hydrochloride and Pd(OAc) into a clean 25mL Schlenk tube 3 (1.3mg, 3mol%), PPh 3 (10.5mg, 20mol%), Na 2 CO 3 (21.2mg, 0.2mmol), in CO:O 2 =3:1 inject morpholine (17.4mg, 0.2mmol) and mixed solvent (dmso:dioxane=0.1:0.9mL), react at 100℃ for 12h, TLC dot plate detection;.

[0026] 2) After the reaction, the reaction solution was added with 2 mL of water, and then extracted with EA for 3-5 times. The organic layer was concentrated and subjected to column chromatography to obtain a pure amide compound, a yellow liquid, with a yield of 79%.

[0027] 1 H NMR(400MHz, CDCl 3 )δ7.31-7.16 (m, 4H), 3.73-3.45 (m, 8H), 2.37 (s, 3H). 13 C NMR(100MHz, CDCl 3 )δ170.6, 138.5, 135.5, 130.6, 128.4, 127.7, 124.0, 66.9 (2C), 48.2, 42.4, 21.4.

example 3

[0029]

[0030] 1) Add 0.4mmol 4-tert-butylphenylhydrazine hydrochloride and Pd(OAc) to a clean 25mL Schlenk tube 3 (1.3mg, 3mol%), PPh 3 (10.5mg, 20mol%), Na 2 CO 3 (21.2mg, 0.2mmol), in CO:O 2 =3:1 inject morpholine (17.4mg, 0.2mmol) and mixed solvent (dmso:dioxane=0.1:0.9mL), react at 100℃ for 12h, TLC dot plate detection;.

[0031] 2) After the reaction, the reaction solution was added with 2 mL of water, and then extracted with EA for 3-5 times. The organic layer was concentrated and subjected to column chromatography to obtain a pure amide compound, a yellow solid, with a yield of 90%.

[0032] 1 H NMR(400MHz, CDCl 3 )δ7.42(d,J=8.3Hz,2H), 7.34(d,J=8.3Hz,2H), 3.69-3.51(m,8H),1.32(s,9H). 13 C NMR(100MHz, CDCl 3 )δ170.7, 153.2, 132.3, 127.0, 125.5, 66.9 (2C), 48.4, 42.4, 34.8, 31.2

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PUM

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Abstract

The invention discloses an environment-friendly amido bond synthesis method, which comprises the following steps: oxidizing an aryl hydrazine compound with O2 to form a C-Pd bond by taking Pd(OAc)2 as a catalyst and taking PPh3 as a ligand, inserting CO to a carbon-palladium bond to form an acyl palladium species as a carbonyl source, attacking carbonyl palladium by virtue of amine as a nucleophilic reagent, and performing reductive elimination to obtain a final product amide. According to the method, synthesis of the amide from the hydrazine compound is implemented by adopting CO as the carbonyl source by virtue of a carbonyl insertion method, and a byproduct does not comprise excessive pollutants such as haloid acid, so that the potential application value can be better achieved.

Description

Technical field [0001] The invention relates to the fields of organic chemistry and biochemistry, in particular to a green and environmentally friendly method for synthesizing amide bonds. Background technique [0002] Amide bond is the basic chemical bond of protein. The process of protein synthesis is the process of repeatedly forming amide bond. Amide bond is also one of the most basic chemical bonds in organic chemistry. In addition to proteins, it is also widely present in organic small molecules, peptides, drugs and polymer materials, and is closely related to people's life activities and daily life. Amide can be formed by dehydration and condensation of carboxylic acid and amine, but this seemingly simple reaction is difficult to occur at room temperature. It is usually heated to high temperature or with the help of coupling reagents to form amide. The traditional amide chemical synthesis method generally uses coupling reagents to activate the carboxylic acid and complete...

Claims

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Application Information

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IPC IPC(8): C07B43/06C07D295/192C07C231/10C07C235/46C07C235/48C07D217/06
CPCC07B43/06C07C231/10C07D217/06C07D295/192C07C235/46C07C235/48
Inventor 王涛黄阳妃赵军锋袁淋范立文
Owner JIANGXI NORMAL UNIVERSITY
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