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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (11): 1064-1070. 上一篇    下一篇

研究论文

有机锡催化苯氨基甲酸甲酯分解的研究

戴云生1,2, 王越1, 姚洁1, 王庆印1, 刘良明1, 崔黎黎3, 赵永峰3, 王公应*,1   

  1. (1中国科学院成都有机化学研究所 成都 610041)
    (2中国科学院研究生院 北京 100039)
    (3胜利油田胜利化工有限公司 东营 257503)
  • 投稿日期:2006-09-30 修回日期:2006-12-18 发布日期:2007-06-14
  • 通讯作者: 王公应

Study on Organotin-catalyzed Decomposition of Methyl N-phenyl Carbamate

DAI Yun-Sheng1,2; WANG Yue1; YAO Jie1; WANG Qing-Yin1; LIU Li-ang-Ming1; CUI Li-Li3; ZHAO Yong-Feng3; WANG Gong-Ying*,1   

  1. (1 Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041)
    (2 Graduate School of the Chinese Academy of Sciences, Beijing 100039)
    (3 Shengli Chemical Company Limited of Shengli Oil Field, Dongying 257503)
  • Received:2006-09-30 Revised:2006-12-18 Published:2007-06-14
  • Contact: WANG Gong-Ying

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837

被引次数

36 | 5

对几种锡化合物催化苯氨基甲酸甲酯(MPC)热分解制苯基异氰酸酯(PI)反应进行了研究, 发现二丁基氧化锡具有较高的催化活性. 用HPLC-MS确定了分解的未知副产物为二苯基碳化二亚胺(DPCD). 分析认为生成N,N'-二苯基脲(DPU)和DPCD的反应为合成PI的主要竞争反应. 常压下以Bu2SnO为催化剂时的适宜反应条件为以邻二氯苯(ODCB)为溶剂, 溶剂用量为MPC用量的15倍(质量比), Bu2SnO用量为MPC用量的0.075 (摩尔比), 反应时间1 h. 此条件下MPC转化率为85.17%, PI收率为67.65%.

关键词: 苯氨基甲酸甲酯, 苯基异氰酸酯, 催化分解, 二丁基氧化锡

The synthesis of phenyl isocyanate (PI) was studied by thermal decomposition of methyl N-phenyl carbamate (MPC) over tin catalysts. It has been found that di-n-butyltin oxide had higher activity. The unknown byproduct was determined as diphenylcarbodiimide (DPCD) by HPLC-MS. The results show that the formation of N,N'-diphenylurea (DPU) and DPCD are the main competitive reactions to the synthesis of PI. At normal pressure, the conversion of MPC is 85.17% and the yield of PI is 67.65% over Bu2SnO under the optimal reaction condition, which is as follows: solvent, o-dichlorobenzene (ODCB); m(ODCB)/ m(MPC)＝15; n(Bu2SnO)/n(MPC)＝0.075; reaction time, 1 h.

Key words: methyl N-phenyl carbamate, phenyl isocyanate, catalytic decomposition, di-n-butyltin oxide