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.
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 hydrogenation and Williamson alkylation reactions.Reduction of 12f～12g by NaBH4 in diglyme with microwave 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 endoperoxides 5a～5c were also obtained as by-products.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2010年第20期2069-2076,共8页
Acta Chimica Sinica
基金
国家自然科学基金(No.20872038)
高等学校博士学科点专项科研基金(No.20060561024)资助项目
