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化学学报
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化学学报 ›› 2005, Vol. 63 ›› Issue (7): 603-611. 上一篇    下一篇

研究论文

二丁基氧化锡催化碳酸二甲酯与苯酚酯交换反应机理研究

王越，姚洁，曾毅，王公应*   

  1. (中国科学院成都有机化学研究所 成都 610041)
  • 投稿日期:2004-08-26 修回日期:2004-12-02 发布日期:2010-12-10
  • 通讯作者: 王公应

Mechanism Study of Di-n-butyltin Oxide Catalyzed Transesterification of Dimethyl Carbonate with Phenol

WANG Yue, YAO Jie, ZENG Yi, WANG Gong-Ying*   

  1. (Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041)
  • Received:2004-08-26 Revised:2004-12-02 Published:2010-12-10
  • Contact: WANG Gong-Ying

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2125

被引次数

6

研究了二丁基氧化锡催化碳酸二甲酯与苯酚酯交换合成碳酸二苯酯的反应机理, 发现原料苯酚和产物DPC都能与二丁基氧化锡生成同一种中间体, 并测定了其晶体结构. 该晶体属于单斜晶系, P21/n空间群; 晶胞参数: a＝1.3336(2) nm, b＝1.7208(2) nm, c＝1.3759(3) nm, β＝101.00(2)°; V＝3.0993(9) nm3; Dc＝1.432 g/cm3; Z＝4; F(000)＝1352; μ＝1.635 mm－1. 分析结果显示该中间体是一种新型的二聚四烃基二锡氧烷化合物[Bu2Sn(OPh)OSnBu2O(Ph)]2 (I), 该化合物具有中心对称的层状结构. MS和XPS结果证实I在酯交换反应条件下能稳定存在. 基于实验结果, 本文提出了一个合理的酯交换反应机理.

关键词: 碳酸二甲酯, 碳酸二苯酯, 酯交换机理, 四烃基二锡氧烷, 苯酚

The transesterification mechanism of dimethyl carbonate with phenol to diphenyl carbonate (DPC) over di-n-butyltin oxide was studied. It has been found that both phenol and DPC could react with di-n-butyltin oxide to form an intermediate. Its crystal structure was determined by X-ray single crystal diffraction analysis. The crystal belongs to monoclinic system with space group P21/n. Its unit cell parameters are as follows: a＝1.3336(2) nm, b＝1.7208(2) nm, c＝1.3759(3) nm, β＝101.00(2)°, V＝3.0993(9) nm3, Dc＝1.432 g/cm3, Z＝4, F(000)＝1352, μ＝1.635 mm－1. The identification results show that the intermediate is a novel dimeric tetraorganodistannoxane [Bu2Sn(OPh)OSnBu2O(Ph)]2 (I), which has a layer structure with centric symmetry. The MS and XPS results demonstrate that I exists steadily in the reaction condition. A reasonable transesterification mechanism based on the experimental consequence was then offered in this paper.

Key words: dimethyl carbonate, diphenyl carbonate, transesterification mechanism, tetraorganodistannoxane, phenol