六烯丙基六氮杂异伍兹烷的核磁表征

为精确表征六烯丙基六氮杂异伍兹烷(HAIW)的化学结构,在氘代氯仿(CDCl3)及氘代丙酮(acetone-d6)中研究了HAIW的核磁谱图特征。采用一维及二维1 H、13 C、15 N NMR技术对HAIW的NMR信号进行了全归属,利用核磁模拟软件NMR-SIM对氢谱图进行计算机拟合。结果表明,HAIW在丙酮溶液中的1 H NMR的分辨率较好,谱图中存在两类异伍兹烷信号(环内与桥头)及两类烯丙基碳氢信号,其中五元环所连4个烯丙基不能自由旋转导致亚甲基氢不对称出现2组峰,而六元环所连2个烯丙基则能自由旋转使得该亚甲基氢对称重合;两类烯丙基存在的多种偶合使得氢谱谱线较为复杂;由拟合氢谱化学位移及偶合常数获得的1 H NMR谱图与实际图谱完全一致。表明二维核磁共振技术与核磁模拟技术相结合,可用于对复杂谱的精确分析。

NMR Characterization of Hexaallylhexaazaisowurtzitane

To precisely characterize the chemical structure of hexaallylhexaazaisowurtzitane (HAIW) ,the NMR spectrum characteristics of HAIW in chloroform‐d (CDCl3 ) and acetone‐d6 solution were studied ,and 1D ,2D 1 H NMR ,13C NMR and 15N NMR techniques were used for the assignment of all the NMR signals .The computer fit‐ting of hydrogen spectrum was performed by NMR simulation software NMR‐SIM .The results indicate that the 1 H NMR spectra obtained in acetone‐d6 solution show better resolution ,in which there are two kinds of signals for pro‐tons in hexaazaisowurtzitane and two kinds of signals for allylic protons .The limited rotation of four allyls bonded to the five‐membered ring and the free rotation of two allyls bonded to the six‐membered ring make asymmetric methylene protons reveal two sets of peaks and symmetric methylene proton coincidence reveal one set of peak ,re‐spectively .The existence of multiple coupling of two kinds of allyls causes the 1 H NMR spectral line more compli‐cate .1 H NMR spectra obtained by fitting the hydrogen spectrum chemical shifts and coupling constants are consist‐ent with the experimental ones .The combination of 2D NMR techniques and NMR simulation can be used to accu‐ratly analyze the complex spectral analysis .