反式-3-苯基-12-取代环十二酮的合成及晶体结构

摘要

2-Cyclododecenone was prepared via oxidation of cyclododecanone with o-iodylbenzoic acid (IBX),then 3-phenyl cyclododecanone was synthesized by 2-cyclododecenone and phenyl boronic acid under catalysis of palladium acetate.A series of 3-phenyl-12-substitutedcyclododecanone was regioselectively prepared by the reaction of 3-phenylcyclododecanone with different reagents,and their structures were characterized by 1H NMR,13C NMR and HR-MS.The crystals for four compounds were obtained in the solution and X-ray diffraction analyses were carried out.The results showed that [3333]-2-one conformation was took by the cyclododecanone ring of 3-phenyl-12-substituted cyclododecanone with trans-configuration of two substituted groups.One case was that the two substituted groups were at the same side,phenyl was at β-corner-anti position of the carbon atom in one side of carbonyl,and the other groups were at α-corner-syn position of the carbon atom in the other side of carbonyl in their crystals.The other case was that the two substituted groups were at the different sides,both phenyl and the other groups were at side-exo position of the carbon atoms in two sides of carbonyl in their crystals.The results of quantum mechanics calculation were consistent with those of X-ray diffraction.%以环十二酮为原料,经2-碘酰基苯甲酸(IBX)氧化制备2-环十二烯酮,在醋酸钯和三苯基磷催化下,2-环十二烯酮与苯硼酸反应制得3-苯基环十二酮.经3-苯基环十二酮与不同试剂发生区域选择性反应制备了一系列新的3-苯基-12-取代环十二酮衍生物,采用核磁共振波谱(NMR)和液相色谱-高分辨质谱(HRMS)表征了其结构.在溶液中结晶,获得了4个代表性化合物的单晶并进行X射线衍射分析,结果表明,3-苯基-12-取代环十二酮晶体中的十二元环仍采取[3333]-2-酮构象,2个取代基为反式构型,取代基存在2种情形:2个取代基在同一条边上,苯基位于与羰基间隔1个亚甲基的β-角碳反向位,而另1个取代基位于与羰基另一侧相邻的α-角碳顺向位;或2个取代基在2条边上,苯基位于与羰基间隔1个亚甲基另一条边的卢-边碳外向位,而另1个取代基位于与羰基另一侧相邻并在同一条边的α-边碳外向位,量子力学计算结果与晶体衍射分析结果一致.