文档介绍：2007 年第 65 卷化学学报 Vol. 65, 2007 第 16 期, 1657 ~1662 ACTA CHIMICA SINICA No. 16, 1657 ~ 1662 * E-mail: ******@cau. Received March 29, 2007; revised June 21, 2007; accepted A ugust 6, 2007. 国家自然科学基金(No. 20072053) 和教育部留学回国基金资助项目. ·研究论文· α- 单取代环十二***肟及缩氨基硫脲的合成及晶体结构王明安闫晓静刘建平金淑惠李太公杨旭王道全* ( 中国农业大学应用化学系北京 100094) 摘要单晶 X 射线衍射分析表明, α-单取代环十二***与氨衍生物羟***和氨基硫脲发生缩合反应得到两种母体构象均为[3333], 而取代基为边外向或角反向的α- 单取代环十二***肟或缩氨基硫脲. 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. 通常情况下, 试剂从空间障碍小的一面进攻羰基而生成α- 角反取代环十二***肟或缩氨基硫脲. 当试剂与底物的取代基之间能够形成分子间氢键时, 则生成α- 边外取代环十二***肟或缩氨基硫脲. 关键词α- 单取代环十二***肟; α- 单取代环十二***缩氨基硫脲; 晶体结构; 角位羰基参与反应; 记忆效应 Synthesis and Crystal Structure of α-Monosubstituted Cyclododecanone Oxime and Thiosemicarbazone WANG, Ming-An YAN, Xiao-Jing LIU, Jian-Ping JIN, Shu-Hui LI, Tai-Gong YANG, Xu WANG, Dao-Quan * ( Department of Applied Chemistry , China Agricultural University , Beijing 100094 ) Abstract Two kinds of α-monosubstituted cyclododecanone oximes and thiosemicarbazones were synthe- sized by the reaction of α-monosubstituted cyclododecanone with hydroxylamine and 4- p-tolylthiosemicar- bazide. The X-ray diffraction analysis showed that they had different conformations, in which the parent ring takes still [3333] conformation and the substituting group is at α-side- exo or α-corner- anti position. These results were rationalized by “corner-p