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以邻氨基二苯甲酮为原料,经自身缩合环化合成了3种二苯并[1,5]二氮杂芳辛四烯衍生物(1a~1c);以邻苯二甲酸酐和溴苯为原料经傅-克反应制得中间体2-(4-溴苯甲酰溴)苯甲酸(M1);M1经叠氮化后自缩合制得6,12-二(4-溴苯基)二苯并[b,f][1,5]二氮杂环辛四烯(1d);以邻氨基苯甲酸甲酯为原料,经自身缩合环化制得中间体二苯并[b,f][1,5]二氮杂环辛四烯-6,12(5H,11H)-二酮(M2);M2经氯化合成6,12-二氯二苯并[b,f][1,5]二氮杂环辛四烯(1e),化合物1a~1e的结构经~1H NMR,~(13)C NMR和ESI-MS表征,其中化合物1c为新化合物。利用超临界色谱(SFC)技术对化合物1a~1e实现了手性拆分,获得5对具有高旋光度的光学活性异构体(ee>99%)。
Three kinds of dibenzo [1,5] diazocotetraene derivatives (1a ~ 1c) were synthesized from o-aminobenzophenone by condensation and cyclization. Phthalic anhydride and bromine Benzene as raw material to obtain intermediate 2- (4-bromobenzoylbromide) benzoic acid (M1) via Friedel-Crafts reaction; M1 was self-condensed after azidation to obtain 6,12-bis ) Dibenzo [b, f] [1,5] diazacyclooctatetetraene (1d); the intermediate benzoic acid methyl ester as the raw material, through its own condensation cyclization intermediate dibenzo [b, (1, 5] diazacyclooctate-6,12 (5H, 11H) -dione (M2); M2 was chlorinated to 6,12-dichlorodibenzo [b, f] 1,5] diazocine (1e). The structures of compounds 1a ~ 1e were characterized by ~ 1H NMR, ~ 13CNMR and ESI-MS. Among them, compound 1c was a new compound. Chiral resolution of compounds 1a ~ 1e was achieved by using supercritical fluid chromatography (SFC), and 5 pairs of optically active isomers (ee> 99%) with high optical rotation were obtained.