二苯并[b,f][1,5]二氮杂芳辛四烯衍生物的合成及拆分

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

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 dibenzo[ b ,f] [ 1,5 ] diazocine derivatives（1a -1 c） 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） dibenzo[ b ,f] [ 1,5 ] diazocine（ld） was formed by self-condensation of M1. Dibenzo [ b ,f] [ 1,5 ] diazocine-6,12 （5H, 11 H） -dione （ M2 ） was obtained by self-condensation and cy- clization of methyl anthranilate, and then 6,12-dichlorodibenzo[ b ,f] [ 1,5 ] diazocine（le） was synthesized by chlorination of intermediate M2. The structures of 1a - 1e were characterized by ^1H NMR, ^13C NMR and ESI-MS. Compound lc is a new compound. All the raeemates of 1a - 1e were success- fully ehiral resolved by supercritical fluid chromatography（SFC） to give enantiomers with high optical rotation, with ee 〉 99%.