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A green and environmentally friendly method for synthesizing amide bonds

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

Active Publication Date: 2018-10-30
JIANGXI NORMAL UNIV
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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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  • A green and environmentally friendly method for synthesizing amide bonds
  • A green and environmentally friendly method for synthesizing amide bonds
  • A green and environmentally friendly method for synthesizing amide bonds

Examples

Experimental program
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Effect test

example 1

[0019]

[0020] 1) Add 0.4mmol of phenylhydrazine hydrochloride and 0.03mmol of Pd(OAc) to a clean 25mL Schlenk tube 2 , 0.2mmol PPh 3 , 0.2mmol of Na 2 CO 3 , In CO:O 2 =3:1 in an atmosphere of 0.2 mmol of morpholine and a mixed solvent (dimethyl sulfoxide: dioxane = 0.1: 0.9 mL), react at 100° C. for 12 h, and TLC spot plate detection.

[0021] 2) After the reaction, the reaction solution was added with 2 mL of water, and then extracted with ethyl acetate for 3-5 times. The organic layer was concentrated and subjected to column chromatography to obtain a pure amide compound as 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 C NMR(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 3mol% of Pd(OAc) into a clean 25mL Schlenk tube 2 ,20mol% PPh 3 , 0.2mmol of Na 2 CO 3 , In CO:O 2 =3:1, inject 0.2 mmol of morpholine and a mixed solvent (dimethyl sulfoxide: dioxane = 0.1: 0.9 mL), react at 100° C. for 12 hours, and detect by TLC dot plate.

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

[0028] 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

[0030]

[0031] 1) Add 0.4mmol 4-tert-butylphenylhydrazine hydrochloride and 0.03mmol Pd(OAc) into a clean 25mL Schlenk tube 2 , 0.2mmol PPh 3 , 0.2mmol of Na 2 CO 3 , In CO:O 2 =3:1 in an atmosphere of 0.2 mmol of morpholine and a mixed solvent (dimethyl sulfoxide: dioxane = 0.1: 0.9 mL), react at 100° C. for 12 h, and TLC spot plate detection.

[0032] 2) After the completion of the reaction, the reaction solution was added with 2 mL of water, and then extracted with ethyl acetate 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%.

[0033] 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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Abstract

A green and environmentally friendly method for synthesizing amide bonds is to use arylhydrazine compounds under the oxidation of O2, use Pd(OAc)2 as a catalyst, and PPh3 as a ligand to form a C-Pd bond first, and then CO gas as a carbonyl The source is inserted between the carbon-palladium bonds to form acyl palladium species, and after the amine acts as a nucleophile to attack the carbonyl palladium, a reductive elimination is carried out to obtain the final product amide. The invention realizes the synthesis of amides by using hydrazine compounds through the method of carbonyl insertion, using CO as the carbonyl source, and the by-products do not contain excessive pollutants such as hydrohalic acid, so that the potential application value can be better realized.

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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Patent Type & Authority Patents(China)
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 UNIV
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