Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (6): 2217-2225.DOI: 10.6023/cjoc202210027 Previous Articles     Next Articles


蔡荣斌, 李冰, 周琪, 朱隆懿*(), 罗军*()   

  1. 南京理工大学化学与化工学院 南京 210094
  • 收稿日期:2022-10-24 修回日期:2022-11-28 发布日期:2022-12-21
  • 作者简介:
  • 基金资助:
    国家自然科学基金(22075144); 江苏省自然科学基金(BK20200459)

Synthesis of 4,8,9,10-Tetrafunctionalized 2-Azaadamantanes and Their 2-Azaprotoadamantane Skeleton Isomers

Rongbin Cai, Bing Li, Qi Zhou, Longyi Zhu*(), Jun Luo*()   

  1. School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094
  • Received:2022-10-24 Revised:2022-11-28 Published:2022-12-21
  • Contact: E-mail:;
  • About author:
    These authors contributed equally to this work
  • Supported by:
    National Natural Science Foundation of China(22075144); Natural Science Foundation of Jiangsu Province(BK20200459)

The multi-step synthesis of rigid and multifunctionalized azaadamantane skeletons from small molecules has always been a challenge in the field of adamantane chemistry. In this work, the bisepoxidized intermediate was obtained via ketalization, bromination, elimination, and Prilezhaev oxidation using bicyclo[3.3.1]nonane-2,6-dione as the raw material, which was then ammonolyzed and cyclized to generate 9,10-dihydroxy-2-azaadamantane-4,8-dione bis(ethylene ketal) with ammonia at 120 ℃. After that, 9,10-dinitroyloxy-2-nitro-2-azaadamantane-4,8-dione bis(ethylene ketal) was synthesized by N,O-nitration with the overall yield of 10% over six steps. Furthermore, when the bisepoxidized intermediate was ammonolyzed at 135 ℃, a skeleton isomer 4,10-dihydroxy-2-azaprotoadamantane-5,9-dione bis(ethylene ketal) was formed, which was then transformed to the corresponding O-nitrated and N,O-dinitrated derivatives through N-acetylation, deketalization and nitration, respectively. These provide a reliable method for the subsequent derivation of multifunctional 2-azaadamantane and its skeleton isomer 2-azaprotoadamantane, which might be used as basic scaffolds for high energy density cage-like compounds.

Key words: azaadamantane, azaprotoadamantane, functionalization, ammonolysis, cyclization, nitramine, synthesis design