中文摘要：

单晶X射线衍射分析表明,几个新的α-单取代环十二酮与氨衍生物羟胺发生反应得到三种母体构象分别为[3333]和[2334],而取代基为边外向或角反向的α-单取代环十二酮肟.利用底物的＂角位羰基参与反应＂原理,＂记忆效应＂及进攻试剂与底物是否形成氢键解释了这一实验结果.通常取代基体积较大以及α-取代基与羰基形成分子内氢键情况下,试剂从空间障碍小以及远离氢键的一面进攻羰基生成α-角反取代环十二酮肟;当试剂与底物的取代基之间能够形成强的分子间氢键时,生成α-边外取代环十二酮肟;当试剂与底物的取代基之间只能形成弱的分子间氢键以及底物的取代基较小时,试剂从两面进攻羰基同时生成α-角反取代环十二酮肟和α-边外取代环十二酮肟.

英文摘要：

Three kinds of novel α-monosubstituted cyclododecanone oximes were synthesized by the reac-tion of α-monosubstituted cyclododecanone with hydroxylamine. The X-ray diffraction analysis showed that they had different conformations,in which the parent ring took [3333] and [2334] conformation and the sub-stituting group was at α-side-exo or α-corner-anti position. These results were rationalized by ＂cor-ner-position carbonyl participation＂ of raw materials,＂memory effect＂,and hydrogen-bonding between hydroxylamine and α-monosubstituted cyclododecanone. In general,an amine molecule approaches cyclo-dodecanone with the bigger groups or intramolecular H-bonding from the side with less hindrance or not breaking hydrogen-bond,resulting in α-corner-anti monosubstituted cyclododecanone oximes,whereas an approach of an amine molecule from the other side with a strong hydrogen bonding network gives rise to α-side-exo monosubstituted cyclododecanone oximes. When cyclododecanone with smaller groups or weak intermolecular H-bonding,an amine molecule approaches from both sides to afford α-side-exo and α-corner-anti monosubstituted cyclododecanone oximes.