Chin. J. Org. Chem. ›› 2016, Vol. 36 ›› Issue (2): 399-405.DOI: 10.6023/cjoc201509025 Previous Articles     Next Articles



杨明艳, 张晓腾, 王道全, 王明安   

  1. 中国农业大学应用化学系 北京 100193
  • 收稿日期:2015-09-21 修回日期:2015-10-21 发布日期:2015-11-03
  • 通讯作者: 王明安
  • 基金资助:

    国家自然科学基金(No. 21172254)资助项目.

Synthesis and Crystal Structure of 2-Phenyl/cyclohexyl Cyclododecane Oxime Derivatives

Yang Mingyan, Zhang Xiaoteng, Wang Daoquan, Wang Mingan   

  1. Department of Applied Chemistry, China Agricultural University, Beijing 100193
  • Received:2015-09-21 Revised:2015-10-21 Published:2015-11-03
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21172254).

2-Cyclohexylcyclododecanone and 2-phenylcyclododecanone were synthesized via reaction of cyclododecanone with bromocyclohexane and lithium phenide using cyclododecanone as raw material, respectivey. The 1,1'-dihydroxy-1,1'- bicyclododecane was also obtained unexpected. 2-Cyclohexylcyclododecanone oxime and 2-phenylcyclododecanone oxime were prepared by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with hydroxylamine chloride, 3-cyclohexylcyclododecan-1,2-dione monooxime and 3-phenyl-cyclododecan-1,2-dione monooxime were synthesized by reaction of 2-cyclohexylcyclododecanone and 2-phenylcyclododecanone with NaNO2-HCl system. Their crystals were obtained in the solution and X-ray diffraction analyses were carried out. The results showed that [3333] conformation was took by the cyclododecane ring of 1-phenylcyclododecanol and 1,1'-dihydroxy-1,1'-bicyclododecane, the two substituted groups were at corner position, while 2-cyclohexylcyclododecanone oxime took [3333]-2-one, 3-phenylcyclododecan-1,2-dione monooxime took [4233]-3,4-dione conformation and the substituted groups were at side-exo position in their crystals. The results of quantum mechanics calculation were consistent with those of X-ray diffraction. In the crystal structure of 1,1'-dihydroxy- 1,1'-bicyclododecane, the molecules exhibited unique self-assembly property of complete disc overlapping between two molecular layers in the a-axis direction with intermolecular hydrogen bond.

Key words: cyclododecanone oxime, cyclododecan-1,2-dione monooxime, [3333] conformation, [3333]-2-one, [4233]-3,4- dione