硒催化的乙二胺、乙醇胺和环胺的氧化羰基化反应

研究了以硒粉作催化剂，一氧化碳为羰基化试剂的乙二胺、乙醇胺和一些环胺的羰基化反应，考察了氧化剂对反应的影响。发现氧气是该反应较好的氧化剂，而没有氧化剂存在时，几乎没有羰基化反应发生。在硒／氧化剂体系存在下，乙二胺和乙醇胺这样一些分子内具有相邻两个亲基团物质的羰基化反应易趋向于分子内羰基化形成较为稳定的五元环产物，产率和选择性较高；而环胺如哌啶和吗啡啉的羰基化可生成相应的四取代脲产物。对反应机理进行

Studies on the Selenium-Catalyzed Oxidative Carbonylation of Ethylenediamine, Ethanolamine and Some Cyclic Amines

The carbonylation of ethylenediamine, ethanolamine and cyclic amines with selenium as catalyst in the presence of carbon monoxide was studied. The influence of some oxidants on the carbonylation was examined. Oxygen was found to be the best oxidant and almost no reaction was observed without adding any oxidant. It was found that the carbonylation of ethylenediamine and ethanolamine which have two neighbouring nucleophilic groups in molecule tends to form intramolecular carbonylated products with fairly high yields and selectivity in the presence of some appropriate oxidants, and that of cyclic amines can give corresponding tetra substituted ureas with moderate yield. Possible reaction pathways were postulated and discussed.