新型多取代Tr(o)ger's base衍生物的合成及其晶体结构

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.%6,12-Diaryldibenzo[b,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-tetrahydrodibenzo[b,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.