2-苯基/环己基取代环十二酮肟衍生物的合成及晶体结构  

Synthesis and Crystal Structure of 2-Phenyl/cyclohexyl Cyclododecane Oxime Derivatives

作　　者：杨明艳[1] 张晓腾[1] 王道全[1] 王明安[1] 

机构地区：[1]中国农业大学应用化学系,北京100193

出　　处：《有机化学》2016年第2期399-405,共7页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21172254)资助项目~~

摘　　要：以环十二酮为原料,分别与溴代环己烷或苯基锂试剂反应制得2-环己基环十二酮和2-苯基环十二酮,还意外获得了副产物1,1'-二羟基-1,1'-联环十二烷.2-环己基环十二酮和2-苯基环十二酮与盐酸羟胺反应制备了2-环己基环十二酮肟和2-苯基环十二酮肟,与亚硝酸钠-盐酸体系反应获得了3-环己基-1,2-环十二二酮单肟和3-苯基-1,2-环十二二酮单肟.在溶液中结晶获得其中四个化合物单晶并进行了X射线衍射,结果表明1-苯基环十二醇和1,1'-二羟基-1,1'-联环十二烷在晶体中的十二元环均采取[3333]构象,两个取代基在角碳上;在晶体中2-环己基环十二酮肟的十二元环采取[3333]-2-酮构象,而3-苯基-1,2-环十二二酮单肟的十二元环则改变为[4233]-3,4-二酮构象,取代基均在边碳外向位,量子力学计算的结果与晶体衍射的结果一致.1,1'-二羟基-1,1'-联环十二烷在晶体中采取摞光盘一样完全重叠的自组装排列方式.2-Cyclohexylcyclododecanone and 2-phenylcyclododecanone were synthesized via reaction of cyclododecanone with bromocyclohexane and lithium phenide using cyclododecanone as raw material, respectivey. The 1,1＇-dihydroxy-1,1＇-bicyclododecane was also obtained unexpected. 2-Cyclohexylcyclododecanone oxime and 2-phenylcyclododecanone oxime were prepared by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with hydroxylamine chloride,3-cyclohexylcyclododecan-1,2-dione monooxime and 3-phenyl-cyclododecan-1,2-dione monooxime were synthesized by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with Na NO2-HCl system. Their crystals were obtained in the solution and X-ray diffraction analyses were carried out. The results showed that [3333] conformation was took by the cyclododecane ring of 1-phenylcyclododecanol and 1,1＇-dihydroxy-1,1＇-bicyclododecane, the two substituted groups were at corner position, while 2-cyclohexylcyclododecanone oxime took [3333]-2-one, 3-phenylcyclododecan-1,2-dione monooxime took [4233]-3,4-dione conformation and the substituted groups were at side-exo position in their crystals. The results of quantum mechanics calculation were consistent with those of X-ray diffraction. In the crystal structure of 1,1＇-dihydroxy-1,1＇-bicyclododecane, the molecules exhibited unique self-assembly property of complete disc overlapping between two molecular layers in the a-axis direction with intermolecular hydrogen bond.

关 键 词：环十二酮肟 1 2-环十二二酮单肟 构象 -2-酮 -3 4-二酮 

分 类 号：O621.3[理学—有机化学]