Citation: Zhang Xiaopeng, Jing Huanzhi, Peng Weiyu, Li Yafang, Fan Xuesen, Zhang Guisheng. Selenium-Catalyzed Carbonylation to Phenylcarbamates and Methylene Diphenyl Dicarbamates[J]. Chinese Journal of Organic Chemistry, ;2017, 37(2): 411-417. doi: 10.6023/cjoc201609013 shu

Selenium-Catalyzed Carbonylation to Phenylcarbamates and Methylene Diphenyl Dicarbamates

Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007

Corresponding author: Zhang Xiaopeng, zhangxiaopengv@sina.com Zhang Guisheng, zgs@htu.cn
Received Date: 12 September 2016
Revised Date: 12 October 2016

Fund Project: the Program for Innovative Research Team in Science and Technology in University of Henan Province 15IRTSTHN003the Young Backbone Teachers Training Fund of Education Department of Henan Province 2013GGJS-059the Young Backbone Teachers Training Fund of Henan Normal University 2011-8

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A clean, economical and efficient approach to phenylcarbamates and methylene diphenyl dicarbamates was reported. With cheap and easily available nonmetal selenium as the catalyst, carbon monoxide instead of virulent phosgene as the carbonylation reagent, oxygen as the oxidant, the selenium-catalyzed oxidative carbonylation reaction of aniline could proceed smoothly with alcohols to afford phenylcarbamates mostly in moderate to good yields. Then, catalyzed by HCl/ZnCl₂, the condensation of formaldehyde with the generated phenylcarbamates gave methylene diphenyl dicarbamates in moderate to good yields. The applicability of the substrates was good. Catalyst selenium could be easily recovered due to its function of phase-transfer catalysis and could be recycled. High atomic economy, low cost, no emission of corrosive waste, and phosgene-free condition make this approach very promising. The possible reaction mechanisms were also proposed.
- selenium-catalysis,
- carbonylation,
- phenylcarbamate,
- methylene diphenyl dicarbamate
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