对苯二亚甲基联二高三蝶烯的合成.pdfVIP

2010 年第68 卷 化 学 学 报 Vol. 68, 2010 第20 期, 2069～2076 ACTA CHIMICA SINICA No. 20, 2069～2076 ·研究论文· 对苯二亚甲基联二高三蝶烯的合成 蒋晓乾 李志云 曹德榕* (华南理工大学化学与化工学院 广州 510640) 摘要 报道了一种从蒽酮出发制备对苯二亚甲基联二高三蝶烯的合成方法. 以蒽酮为原料, 经缩合、加氢还原以及 Williamson 烷基化反应得到一系列的联二蒽酮衍生物 10e, 12f～12h. 受其 10 位取代基等因素的影响, 12f～12g 在 NaBH4 还原和酸催化条件下发生选择性的 1,7-跨环脱水成环反应, 高产率地得到了联二高三蝶烯 14f～14g. 在相同条 件下, 10e 和12h 却发生了1,4-脱水和重排反应生成了联二蒽衍生物15i～15j, 而不是预期的螺环类联二高三蝶烯产物 16i～16j. 另外, 在制备过程中还得到了一些结构新颖的副产物如蒽醇过氧化物5a～5c, 以及蒽醚酮类衍生物11a, 13a 等. 关键词 三蝶烯; 高三蝶烯; 联二高三蝶烯; 联二蒽酮; 蒽醇过氧化物; 蒽 Synthesis of 10,10-(p-Xylylene)-bishomotriptycenes Jiang, Xiaoqian Li, Zhiyun Cao, Derong* (School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640) Abstract 10,10-(p -Xylylene)-bishomotriptycenes 14f～14g were prepared from bisanthrone derivatives 12f～12g. Bisanthrone derivatives were synthesized starting from anthrone through condensation, Pd/C hy- drogenation and Williamson alkylation reactions. Reduction of 12f～12g by NaBH4 in diglyme with micro- wave irradiation and subsequently a selective 1,7-dehydration-cyclization reaction with acid as catalyst gave bishomotriptycenes 14f～14g in quantitative yields. However, reduction of 10e, 12h and subsequently 1,4-dehydration and rearrangement reaction gave two novel bisanthracene derivatives 15i～15j instead of expected bishomotriptycenes 16i～16j. In addition, novel anthracene derivatives 11a, 13a and endoperox- ides 5a～5c were also obtain