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新型多取代Tr(o)ger's base衍生物的合成及其晶体结构
引用本文:李正义,庄跃,朱美兰,殷乐,孙小强.新型多取代Tr(o)ger's base衍生物的合成及其晶体结构[J].合成化学,2017,25(8).
作者姓名:李正义  庄跃  朱美兰  殷乐  孙小强
作者单位:1. 常州大学 石油化工学院,江苏 常州,213164;2. 常州四药制药有限公司,江苏 常州,213004
基金项目:国家自然科学基金资助项目,江苏省高校自然科学研究重大项目,江苏省先进催化与绿色制造协同创新中心资助项目
摘    要:以邻氨基二苯甲酮为原料,经两分子环化缩合反应制得6,12-二芳基二苯并b,f]1,5]二氮杂环辛四烯(2a~2d);2a~2d经LiAlH4还原制得6,12-二芳基-5,6,11,12-四氢二苯并b,f]1,5]二氮杂环辛(3a~3d);3a~3d与醛(或酮)反应,合成了一系列新型的多取代Tr(o)ger's base衍生物(4a~4d和5a~7a),其结构经1H NMR, 13C NMR, HR-MS(ESI)和X-射线单晶衍射表征.通过分析架桥前后3a(CCDC: 1498564)和6a(CCDC: 1498555)的晶体结构,解释了该类化合物1H NMR中NCH质子及桥上取代基质子裂分的原因,并进一步证实了4~7为非C2轴对称结构.

关 键 词:多取代Tr(o)ger'sBase衍生物  合成  晶体结构  质子裂分

Synthesis and Crystal Structures of Multi-substitutedTr(o)ger's Base Derivatives
LI Zheng-yi,ZHUANG Yue,ZHU Mei-lan,YIN Yue,SUN Xiao-qiang.Synthesis and Crystal Structures of Multi-substitutedTr(o)ger's Base Derivatives[J].Chinese Journal of Synthetic Chemistry,2017,25(8).
Authors:LI Zheng-yi  ZHUANG Yue  ZHU Mei-lan  YIN Yue  SUN Xiao-qiang
Abstract:6,12-Diaryldibenzob,f]1,5]diazocines(2a~2d) were obtained by two molecules cyclizative condensation, using 2-aminobenzophenones as raw material.6,12-Diaryl-5,6,11,12-tetrahydrodibenzob,f]1,5]diazocines(3a~3d) were achieved by LiAlH4-reduction of 2a~2d.A series of novel multi-substituted Tr(o)ger's base derivatives(4a~4d and 5a~7a) were synthesized by the reaction of 3a~3d with different alydehydes or ketones.The structures were characterized by 1H NMR, 13C NMR, HR-MS(ESI) and X-ray single crystal diffraction.The splitting of protons of NCH and substituents in bridge in 1H NMR was well explained by analyzing crystal structures of 3a(CCDC: 1498564) and 6a(CCDC: 1498555), which further confirmed that 4~7 adopted non-C2-axisymmetric structure.
Keywords:multi-substituted Tr(o)ger's base derivative  synthesis  crystal structure  proton spliting
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