Acta Chimica Sinica ›› 2011, Vol. 69 ›› Issue (11): 1354-1360. Previous Articles     Next Articles

Full Papers

a-单取代-1,2-环十二二酮单肟的合成及晶体结构

陈守聪,张春艳,张莉,王道全,王明安*   

  1. (中国农业大学应用化学系 北京 100193)
  • 投稿日期:2010-11-11 修回日期:2010-12-27 发布日期:2011-02-17
  • 通讯作者: 王明安 E-mail:wangma@cau.edu.cn
  • 基金资助:

    国家自然科学基金

Synthesis and Crystal Structure of Novel a-Monosubstituted Cyclododecan-1,2-dione Monooxime

Shou-Cong Chen 2,2,Wang Ming-An2   

  1. (Department of Applied Chemistry, China Agricultural University, Beijing 100193)
  • Received:2010-11-11 Revised:2010-12-27 Published:2011-02-17
  • Contact: Wang Ming-An E-mail:wangma@cau.edu.cn

A series of a-monosubstituted cyclododecan-1,2-dione monooxime were prepared by the reaction of a-monosubstituted cyclododecanone and nitrosyl chloride, and their structures were confirmed by the 1H NMR, 13C NMR, ESI-MS and elemental analysis data. X-ray diffraction and quantum mechanics calculation results showed that the products take two different [4233]-3-one and [3333]-2-one conformation, a-substituted groups present at a-side-exo or a-corner-anti position, the C=N and C=O double bonds present at side chain with the torsion angles in the range of 162°~174°, and the C=N double bond of oximes have E-configuration when they are synthesized with the reaction of a-monosubstituted cyclododecanone and nitrosyl chloride. These two different conformations exist in a dynamic equilibrium with the C2-pseudorotation transferring pathway in the solution, and the preferred conformation was taken when it crystallized from the solution. The analysis of structure characteristics indicated that p-p and p-p interaction may be the main factor which makes the skeleton conformation change of the twelve-membered ring of a-monosubstituted cyclododecan-1,2-dione monooxime.

Key words: a-monosubstituted cyclododecan-1,2-dione monooxime, X-ray diffraction, quantum mechanics calculation, conformation analysis