An Effective Heterogeneous Copper Catalyst System for C–N 
Coupling and Its Application in the Preparation of 
2-Methyl-4-methoxydiphenylamine (MMDPA)

Zhou Yi; Manna Huang; Yiqian Wan; Xinhai Zhu

doi:10.1055/s-0037-1609578

Synthesis, Table of Contents

Synthesis 2018; 50(19): 3911-3920
DOI: 10.1055/s-0037-1609578

paper

An Effective Heterogeneous Copper Catalyst System for C–N Coupling and Its Application in the Preparation of 2-Methyl-4-methoxydiphenylamine (MMDPA)

Zhou Yi

^aSchool of Chemical Engineering and Technology, Guangdong Engineering Technology Research Center for Platform Chemicals from Marine Biomass and Their Functionalization, Sun Yat-sen University, Guangzhou 510275, P. R. of China Email: huangmn25@mail.sysu.edu.cn

,

Manna Huang *

^aSchool of Chemical Engineering and Technology, Guangdong Engineering Technology Research Center for Platform Chemicals from Marine Biomass and Their Functionalization, Sun Yat-sen University, Guangzhou 510275, P. R. of China Email: huangmn25@mail.sysu.edu.cn

,

Yiqian Wan

^aSchool of Chemical Engineering and Technology, Guangdong Engineering Technology Research Center for Platform Chemicals from Marine Biomass and Their Functionalization, Sun Yat-sen University, Guangzhou 510275, P. R. of China Email: huangmn25@mail.sysu.edu.cn

,

Xinhai Zhu

^bInstrument Analysis & Research Center, Sun Yat-sen University, Guangzhou 510275, P. R. of China

› Author Affiliations

Abstract

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Abstract

A ligand-recyclable, environmentally benign heterogeneous catalyst system composed of CuI and polystyrene-supported N(-(4-(aminomethyl)naphthalen-1-yl)-N(-phenyl-1H-pyrrole-2-carbohydrazide (PSAP) has been established for Ullmann type C–N coupling based on the homogeneous catalyst system N′,N′-diphenyl-1H-pyrrole-2-carbohydrazide/CuI. This heterogeneous catalyst system maintained the catalytic effectiveness of the homogeneous catalyst. A variety of functionalized aryl bromides can be efficiently aminated with aryl amines and aliphatic amines with high selectivity for amines over alcohols. Moreover, a practical application of this catalyst system to promote the reaction of commercially available 4-methoxy-2-methylaniline and bromobenzene in 10 mmol scale, provided 2-methyl-4-methoxydiphenylamine (MMDPA) with 93% yield with the merit of the approach being simple operation for work-up and purification.

Key words

heterogeneous catalysis - copper catalysis - C–N coupling - recyclability - 2-methyl-4-methoxydiphenylamine (MMDPA)

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References

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