4,8,9,10-四官能化的2-氮杂金刚烷及其2-氮杂原金刚烷骨架异构体的合成  

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

作　　者：蔡荣斌 李冰[1] 周琪[1] 朱隆懿 罗军[1] Cai Rongbin;Li Bing;Zhou Qi;Zhu Longyi;Luo Jun(School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094)

机构地区：[1]南京理工大学化学与化工学院,南京210094

出　　处：《有机化学》2023年第6期2217-2225,共9页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.22075144);江苏省自然科学基金(BK20200459)资助项目。

摘　　要：小分子法多步合成结构刚性的、多官能化的氮杂金刚烷骨架一直是金刚烷化学领域的一大挑战.本工作以双环[3.3.1]壬烷-2,6-二酮为原料,经缩酮化、溴代、消除、Prilezhaev氧化得到双环氧化物中间体,并在120℃下氨解关环合成9,10-二羟基-2-氮杂金刚烷-4,8-二酮双(乙二醇缩酮),后经N,O-硝化合成了9,10-二硝酰氧基-2-硝基-2-氮杂金刚烷-4,8-二酮双(乙二醇缩酮),六步反应总收率10%;而该双环氧化物中间体在135℃下氨解得到2-氮杂原金刚烷(2-氮杂三环[4.3.1.03,8]-癸烷)的骨架异构体4,10-二羟基-2-氮杂原金刚烷-5,9-二酮双(乙二醇缩酮),后经N-乙酰化、硝化-去缩酮化得到相应的O-硝化及N,O-硝化衍生物.为后续多官能化的2-氮杂金刚烷及其骨架异构体2-氮杂原金刚烷的衍生提供了可靠的方法,可用作高能量密度笼型化合物的结构框架.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.

关 键 词：氮杂金刚烷 氮杂原金刚烷 官能化 氨解 环化 硝胺 合成设计 

分 类 号：O626[理学—有机化学]