高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (1): 120.

• 研究论文 • 上一篇    下一篇

α-单取代环十二酮构象间相互转换的理论研究

路慧哲, 王明安, 王道全   

  1. 中国农业大学应用化学系, 北京 100094
  • 收稿日期:2003-01-29 出版日期:2004-01-24 发布日期:2004-01-24
  • 通讯作者: 王道全(1944年出生),男,博士,教授,博士生导师,从事大环化合物化学和农药化学研究.E-mail:wangdq@cau.edu.cn E-mail:wangdq@cau.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20072053)资助

Theoretical Study on the Interconversion of α-Monosubstituted Cyclododecanone Conformations

LU Hui-Zhe, WANG Ming-An, WANG Dao-Quan   

  1. Department of Applied Chemistry, China Agricultural University, Beijing 100094, China
  • Received:2003-01-29 Online:2004-01-24 Published:2004-01-24

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摘要： 在CVFF力场下,DMSO氛围中,通过分子动力学常温模拟研究α-单取代环十二酮的构象,常温优势构象为α-边外取代[3333]-2-酮,环骨架为[3333],羰基位于C2位置,取代基位于α-边外向位.动态分析带有不同取代基的α角顺取代和α-边外取代[3333]-2-酮构象的相互转化的结果表明,它们的转换路径基本一致,转换能垒随着取代基体积的增大而升高.氯和溴取代环十二酮转换过程中最高能垒分别为43.9和44.3kJ/mol,相应的构象为α-边外取代[31233]-2-酮;甲基、乙基和叔丁基取代环十二酮最高转换能垒达53.9kJ/mol,相应的构象为α-边外取代[31233]-2-酮;存在活泼质子的氨基和羟基环十二酮转换能垒中最高能量构象为α-边外取代[31323]-1-酮;苯硫基和苄基取代环十二酮除出现α-边外取代[3333]-2-酮构象外,转换过程中还出现了较α-角顺取代[3333]-2-酮构象更稳定的α-边外取代[4233]-3-酮构象.

关键词: &alpha, -单取代环十二酮, 优势构象, 分子动力学模拟

Abstract: Under the CVFF force field and in DMSO, the conformations of α-monosubstituted cyclododecanones were studied by molecular dynamics at room temperature. The results show that the ring skeleton of the preferred conformation is [3333], with the carbonyl group being present in the C2 position, which is consistent with the experimental results. The interconversion between α-corner-syn-[3333]-2-one and α-side-exo-[3333]-2-one was analyzed by using dynamics mimesis method. The calculated results show that their interconversion paths are consistent basically, the preferred conformation is α-side-exo-[3333]-2-one and the interconversion energy barrier is increased along with the increase of the volume augmentation of the substituent groups. For α-chloro- and bromo-cyclododecanones, the maximum barriers are 43.9 and 44.3 kJ/mol, respectively, and the corresponding conformation is α-side-exo-[31233]-2-one. For α-alkylcyclododecanones, the maximum barrier is as high as 53.9 kJ/mol, and the corresponding conformation is α-side-exo-[31233]-2-one. While α-amino- and hydroxy-cyclododecacones, the conformation of the maximum energy is α-side-exo-[31323]-1-one, and α-phenylthio- and benzyl-cyclododecanones, apart from {α-side-}exo-[3333]-2-one conformation, the another stable conformation is α-side-exo-[4233]-3-one instead of α-corner-syn-[3333]-2-one.

Key words: Monosubstituted cyclododecanone, Preferred conformation, Molecular dynamical mimesis

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