四烃基二锡氧烷的催化缩醛化性能研究  

Acetalization of Crotonaldehyde and Glycol to Acetal Catalyzed by Tetraorganodistannoxane

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研究所元素有机化学国家重点实验室,天津300071

出　　处：《催化学报》2001年第5期423-426,共4页

基　　金：国家自然科学基金资助项目 ( 2 9972 0 2 5 )

摘　　要：合成了一系列含不同烃基和官能团的二锡氧烷 ,并考察了其对巴豆醛与乙二醇缩合反应的催化作用 .结果表明 ,四烃基二锡氧烷是高效的缩醛化反应催化剂 ,烃基对催化活性的影响主要归因于其空间位阻效应 .二锡氧烷结构中内外锡原子上的烃基都对反应有影响 ,直链烃基催化剂的活性高于环烃基催化剂 ,碳数少的直链烃基催化剂的活性高于碳数多的 .二锡氧烷上桥联基团的活性顺序为NCS >CH3O >Cl>CH3COO .这与其同乙二醇取代反应的难易程度相关联 .A series of distannoxane with various alkyl groups and functional groups were synthesized. Acetalization of crotonaldehyde and glycol catalyzed by the distannoxane including p-CH3C6H4SO3H, Bu2SnO, Bu2SnCl2 and ClBu2SnOSnBu2Cl was studied. The results indicated that the distannoxane has high activity in the reaction, and the activity depends on the alkyl group R on endocyclic Sn sites and R' on exocyclic Sn sites owing to their different steric hindrance effects. The distannoxane with chain alkyl group is more active than that with cyclo-alkyl group, and the distannoxane with long chain alkyl group is less active than that with short chain alkyl group. The catalytic activity of the distannoxane is also influenced by the endocyclic group Y owing to its ability of being substituted by glycol. The catalytic activity of tetrabutyldistannoxane with different functional groups (X = Y) is in the following sequence, NCS > MeO > Cl > CH3COO. The catalytic mechanism for acetalization of crotonaldehyde and glycol has been proposed.

关 键 词：有机锡化合物 巴豆醛 乙二醇 乙缩醛 四氢基二锡氧烷 催化性能 缩醛化反应 催化剂 

分 类 号：O643.3[理学—物理化学]