一种含氧桥环结构的蒽衍生物的合成

Synthesis of An Anthracene Derivative Containing Oxygen-bridged Ring Structure

以1,2,4-三溴苯(2)为起始原料,在正丁基锂作用下原位生成苯炔中间体,与呋喃发生Diels-Alder反应,得到6-溴-1,4-二氢-1,4-环氧萘(3);化合物3再与3,6-二(吡啶-2-基)-1,2,4,5-四嗪(4)发生逆Diels-Alder反应,得到5-溴异苯并呋喃(5);最后,[5-(甲氧羰基)-2-(三甲基硅)苯基](苯基)碘鎓三氟甲烷磺酸盐(6)所形成的苯炔中间体与化合物5发生Diels-Alder反应,得到目标化合物7-溴-9,10-二氢-9,10-环氧蒽-2-甲酸甲酯(1)。对目标化合物1进行衍生化研究发现,目标化合物1经过插羰反应,得到9,10-二氢-9,10-环氧蒽-2,7-二甲酸二甲酯(7)。各化合物结构均经1HNMR和ESI-MS确证。该研究为含氧桥环结构的蒽衍生物的合成提供了参考。

Firstly,benzyne intermediate was in situ synthesized by using 1,2,4-tribromobenzene(2)as a starting raw material in the presence of n-butyllithium,and then 6-bromo-1,4-dihydro-1,4-epoxynaphthalene(3)is obtained by Diels-Alder reaction of furan with the benzyne intermediate.Then,5-bromo-2-benzofuran(5)was obtained by retro Diels-Alder reaction of the compound 3 with 3,6-di(pyridyl-2-yl)-1,2,4,5-tetrazine(4).Finally,the target compound methyl 7-bromo-9,10-dihydro-9,10-epoxyanthracene-2-carboxylate(1)was synthesized by Diels-Alder reaction of the benzyne intermediate formed by(5-(methoxycarbonyl)-2-(trimethylsilyl)phenyl)(phenyl)iodonium trifluoromethane sulfonate(6)with the compound 5.The derivatization of the target compound 1 shows that dimethyl 9,10-dihydro-9,10-epoxanthracene-2,7-dicarboxylate(7)can be obtained by the intercalation carbonyl reaction of the target compound 1.The structures of the compounds were confirmed by 1HNMR and ESI-MS.This study has a reference significance for the synthesis of anthracene derivatives containing oxygen-bridged ring structure.