相同取代基α,α′-顺式二取代环十二酮优势构象及其相互转换的理论研究  

Theoretical study on the preferred conformations of α, α,-m-disubstituted cyclododecanone and the interconversion

作　　者：路慧哲[1] 王明安[1] 王道全[1] 

机构地区：[1]中国农业大学应用化学系,北京100094

出　　处：《计算机与应用化学》2005年第11期1073-1075,共3页Computers and Applied Chemistry

基　　金：国家自然科学基金(20072053)资助

摘　　要：为了探讨大环化合物的稳定构象以及构象间的相互转换,在CVFF(Consistent Valence Force Field)力场下,DMSO氛围中,通过分子动力学常温模拟研究相同取代基α,α′-顺式二取代环十二酮的构象特征,获得常温优势构象环骨架为[3333],羰基位于C2位置,取代基分别位于α-边外向位、α-角顺位。也就是说,两个取代基的存在对分子的构象没有根本坏影响,环骨架继续保持[3333]构象,与已有的实验结果一致,但取代基所在边扭曲较大,随着取代基体积的增加,扭曲程度随之增大。动态分析表明,溶液状态下,相同取代基的α,α′-顺式二取代环十二酮存在两种互为镜像的[3333]-2酮构象,两种构象处于动力学平衡之中,其转换能垒随着取代基体积的增加而逐渐升高。In order to analyze the stable structure of large-ring compound and their conformation interversion, the conformations of α,α′-cis-disubstituted cyclododecanones with the same substituents were studied using molecular dynamics stimulation at room temperature based on the CVFF force field and in DMSO. The results showed that the ring skeleton of the preferred conformation was [ 3333 ] , with the carbonyl group being present in C2 position and the substituents being present in α-corner-syn and α′-side-exo position relatively, which was consistent with the experimental results. The side with substituents was distorted and the distorted level was increased with the increase of the volume augmentation of the substituent groups. Dynamic analysis indicated that in solution the two preferred conformations were mirror images and in a dynamic equilibrium. The interconversion energy barrier was increased along with the increase of the volume augmentation of the substituent groups.

关 键 词：α α′-顺式二取代环十二酮 优势构象 分子动力学常温模拟 

分 类 号：O6[理学—化学]