2-苯基/环己基取代环十二酮肟衍生物的合成及晶体结构

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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. Starting from cyclododecanone and reacting respectively with bromocyclohexane or phenyl lithium reagent to obtain 2-cyclohexyl cyclododecanone and 2-phenylcyclododecanone, by-products 1,1 ’-dihydroxy-1,1’-dicyclododecane. 2-Cyclohexylcyclododecanone and 2-phenylcyclododecanone were reacted with hydroxylamine hydrochloride to prepare 2-cyclohexylcyclododecanone oxime and 2 -phenylcyclododecanone oxime and reacting with sodium nitrite-hydrochloric acid system to obtain 3-cyclohexyl-1,2-cyclododecanone monooxime and 3-phenyl-1,2-cyclododecanedione Mono-oxime. Crystallization in solution yielded four single crystals of the compound and subjected to X-ray diffraction. The results showed that 1-phenylcyclododecanol and 1,1’-dihydroxy-1,1’-bicyclododecane The twelve membered rings in the crystal adopt the conformation of [3333] and the two substituents are on the carbon. The conformation of [3333] -2-one is taken in the twelve membered ring of 2-cyclohexylcyclododecanone oxime in the crystal. While the 12-membered ring of 3-phenyl-1,2-cyclododecanone monooxime changes to the [4233] -3,4-dione conformation with substituents all in the exo-position of the side carbons. Quantum mechanics calculated The results are consistent with the results of the crystal diffraction.1,1’-dihydroxy-1,1’-dicyclododecane in the crystal stack as a complete overlap Assembly arrangement.
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