四丁基二锡氧烷催化合成碳酸二酯类化合物的新方法  

A New Method of Synthesizing Dialkyl Carbonates Catalyzed by Tetrabutyldistannoxane

作　　者：兰支利[1] 吕妍[1] 李靖[1] 谢庆兰[1] 

机构地区：[1]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《催化学报》2002年第1期77-80,共4页

基　　金：国家自然科学基金资助项目 ( 2 9972 0 2 5 )

摘　　要：以四丁基二锡氧烷为催化剂 ,通过尿素的醇解反应 ,合成了四种高沸点碳酸二酯化合物 .研究结果表明 ,尿素的第一步醇解反应较易进行 ,产物收率大于 6 0 % ;第二步从氨基甲酸酯醇解变为碳酸二酯的反应较难进行 .尿素醇解反应与所用的醇有密切的关系 ,其中尿素与苯甲醇醇解为碳酸二酯的反应最易进行 ,正己醇次之 ,而正辛醇反应最难进行 .提高反应温度到195℃ ,以官能团为NCS的四丁基二锡氧烷代替官能团为Cl的四丁基二锡氧烷为催化剂时 ,适当提高醇的配比 ,尿素与正辛醇醇解为碳酸二酯的产物收率有较大的提高 .Process for manufacturing dialkyl carbonates from urea and alcohol catalyzed by tetrabutyldistannoxane was described. Tetrahutyldistannoxane was found to have high catalytic activity for synthesis of alkyl carbamates by alcoholysis of urea with alcohol, the yields are 77%, 61%, 72% and 68% for PhCH2OH, C8H17 OH, C6H13OH and cyclohexyl alcohol respectively. The second step alcoholysis of alkyl carbamates is difficult, the yields of dialkyl carbonates are 86.7%, 14.3%, 24.6% and 21.5% respectively for alcoholysis of corresponding alkyl carbamates with PhCH2OH, C8H17OH, C6H13OH and cyclohexyl alcohol. The yields of dialkyl carbonates are 74.3%, 10.9%, 19.6% and 17.3% for direct alcoholysis of urea with PhCH2OH, C8H17OH, C6H13OH and cyclohexyl alcohol respectively. For alcoholysis of urea with C8H17OH, when ClBu2SnOSnBu2Cl catalyst is replaced by (SCN)Bu2SnOSnBu2(NCS), the yield of dialkyl carbonate is changed from 10.9% to 24.4%, when reaction temperature is increased from 170degreesC to 195degreesC, the yield of dialkyl carbonate is increased from 10.9% to 41.3%; as the molar ratio of alcohol to urea is 3, 4 and 5, the yields are 9.2%, 10.9% and 11.8% respectively. The possible mechanism of the reaction is proposed.

关 键 词：四丁基二锡氧烷 尿素 碳酸二酯 氨酯甲酸酯 催化合成 催化剂 醇解反应 催化活性 

分 类 号：O643.3[理学—物理化学] O623.624[理学—化学]