Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO2 and Methanol

doi:10.1016/S1004-9541(14)60097-5

Chin.J.Chem.Eng. ›› 2014, Vol. 22 ›› Issue (5): 607-610.DOI: 10.1016/S1004-9541(14)60097-5

Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO₂ and Methanol

AN Hualiang, ZHANG Lili, YUAN Baoguo, ZHAO Xinqiang, WANG Yanji

Hebei Provincial Key Lab of Green Chemical Technology and Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China

Received:2013-09-29 Revised:2013-12-31 Online:2014-05-06 Published:2014-05-28
Supported by:
Supported by the National Natural Science Foundation of China (20976035), the Natural Science Foundation of Tianjin City (12JCYBJC12800) and the Key Basic Research Project of Applied Basic Research Plan of Hebei Province (12965642D).

Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO₂ and Methanol

安华良, 张丽丽, 苑保国, 赵新强, 王延吉

Hebei Provincial Key Lab of Green Chemical Technology and Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China

通讯作者: ZHAO Xinqiang,E-mail: zhaoxq@hebut.edu.cn
基金资助:
Supported by the National Natural Science Foundation of China (20976035), the Natural Science Foundation of Tianjin City (12JCYBJC12800) and the Key Basic Research Project of Applied Basic Research Plan of Hebei Province (12965642D).

Abstract

Abstract: Methyl N-phenyl carbamate (MPC), an important organic chemical, can be synthesized from aniline, CO₂ and methanol. Catalyst Cu-Fe/ZrO₂-SiO₂ was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent, the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mechanism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.

Key words: reaction path, methyl N-phenyl carbamate, CO₂, aniline, methanol, Cu-Fe/ZrO₂-SiO₂ catalyst

摘要： Methyl N-phenyl carbamate (MPC), an important organic chemical, can be synthesized from aniline, CO₂ and methanol. Catalyst Cu-Fe/ZrO₂-SiO₂ was first prepared and its catalytic performance for MPC synthesis was evaluated. Then the influence of solvent on the reaction path of MPC synthesis was investigated. It is found that the reaction intermediate is different with acetonitrile or methanol as a solvent. With acetonitrile as a solvent, the synthesis of MPC follows the reaction path with diphenyl urea as the intermediate, while with methanol as a solvent the reaction occurs via the reaction path with dimethyl carbonate as the intermediate. The catalytic mechanism of cooperative catalysis comprising metal sites, Lewis acid sites and Lewis base sites is proposed according to different reaction intermediates.

关键词: reaction path, methyl N-phenyl carbamate, CO₂, aniline, methanol, Cu-Fe/ZrO₂-SiO₂ catalyst

AN Hualiang, ZHANG Lili, YUAN Baoguo, ZHAO Xinqiang, WANG Yanji. Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO₂ and Methanol[J]. Chin.J.Chem.Eng., 2014, 22(5): 607-610.

安华良, 张丽丽, 苑保国, 赵新强, 王延吉. Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO₂ and Methanol[J]. Chinese Journal of Chemical Engineering, 2014, 22(5): 607-610.

References

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Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO₂ and Methanol

Influence of Solvent on Reaction Path to Synthesis of Methyl N-Phenyl Carbamate from Aniline, CO₂ and Methanol

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