二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

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(ee99%)。

Synthesis and Resolution of Dibenzo[ b,f] [1,5] diazocine Derivatives

Three dibenzob,f]1,5]diazocine derivatives(1a～1c) were synthesized by self-conden-sation and cyclization using 2-aminobenzophenone as raw material .2-( 4-Bromobenzoyl ) benzoic acid ( M1 ) was synthesized by Friedel-Crafts reaction of o-phthalic anhydride with bromobenzene , and then 6,12-bis(4-bromophenyl)dibenzob,f]1,5]diazocine(1d) was formed by self-condensation of M1. Dibenzob,f]1,5]diazocine-6,12(5H,11H)-dione(M2) was obtained by self-condensation and cy-clization of methyl anthranilate, and then 6,12-dichlorodibenzob,f]1,5]diazocine(1e) was synthe-sized by chlorination of intermediate M2.The structures of 1a～1e were characterized by 1 H NMR, 13 C NMR and ESI-MS.Compound 1c is a new compound.All the racemates of 1a～1e were success-fully chiral resolved by supercritical fluid chromatography ( SFC) to give enantiomers with high optical rotation, with ee>99％.