Environmentally Benign CO Insertion

摘要 提案标题： 加入产地来源证建议书编号： CTS-9816954主要研究者：Steven S. C.创机构： 阿克伦大学 该提案的目的是发展对在Pd/Al 2 O3或路易斯酸促进的催化剂（例如AlCl 3-Pd/SiO2）上通过胺或硝基化合物的直接羰基化合成烷基或芳基氨基甲酸酯/异氰酸酯的机理的基本理解。机理研究将涉及表面中间体和速率决定步骤的表征。它也将揭示刘易斯酸碱性在促进CO插入中的作用。本研究还将包括Pd/Al_2 O_3/MCM-41催化剂的合成，通过Pd羰基和三甲基铝的CVD。 实验技术包括红外光谱、瞬态和稳态同位素动力学以及表面分析。 这项工作的主要重要性是确定工业合成异氰酸酯/氨基甲酸酯的单步路线，替代目前使用危险的光气和胺的商业工艺。异氰酸酯和氨基甲酸酯用作精细化工和医药中间体。

ABSTRACT Proposal Title: Environmentally Benign CO Insertion Proposal Number: CTS-9816954 Principal Investigators: Steven S. C. Chuang Institution: University of Akron The proposal objective is to develop fundamental understanding of the mechanism of synthesis of alkyl or aryl carbamate/isocyanate by direct carbonylation of the amine or nitrocompound, over Pd/Al2O3 or Lewis-acid promoted catalysts, e.g. AlCl3-Pd/SiO2. The mechanistic study would involve the characterization of surface intermediates and rate determining steps. It will also reveal the role of Lewis acidity and basicity in promoting CO insertion. The study will also include the synthesis of Pd/Al2O3/MCM-41 catalysts by CVD of Pd carbonyl and trimethylaluminum. Experimental techniques include infrared spectroscopy, transient and steady state isotopic kinetics, and surface analysis. The primary importance of the work is the identification of single-step routes to the industrial synthesis of isocyanate/carbamate, alternative to the currently commercial process using the hazardous phosgene and amines. Isocyanates and carbamates are used as fine chemical and pharmaceutical intermediates.