合成文拉法星的2-氮杂-1,3-丁二烯杂Diels-Alder反应与其单分子环合竞争反应的研究  

Hetero Diels-Alder Reaction versus Intramolecular Cyclization of 2-Aza-butadiene in the Synthesis of Venlafaxine

作　　者：穆小静[1,2] 夏之宁[1,2] 王春燕[1] Panunzio Mauro 曾礼娜[1] 

机构地区：[1]重庆大学化学化工学院 [2]重庆大学生物工程学院 [3]ISOF-CNR Dipartimento di Chimica "G. Camician"Via Selmi,I-40126 Bologna,Italy

出　　处：《有机化学》2009年第1期61-65,共5页Chinese Journal of Organic Chemistry

基　　金：科技部国际合作计划(No.2006DFA43520);国家自然科学基金(No.20775096);重庆市自然科学基金(No.CQCSTC2006BB5011)资助项目

摘　　要：研究了不同的Lewis酸催化剂、温度、微波等条件下,4-(4-甲氧苯基)-1-苯基-3-三甲基硅氧基-2-氮杂-1,3-丁二烯(2-ABDE)和亲二烯体环己酮发生杂Diels-Alder反应生成[4+2]的六元环合产物噁嗪酮衍生物,伴随的2-ABDE的[2+2]单分子环合,生成单环β-内酰胺衍生物.结果表明:在低温条件下如(-78℃)[4+2]反应占主导;而在高温条件下(如135℃)仅进行[2+2]反应.微波加热方式可显著提高[2+2]反应的速率和产率.不同的Lewis酸催化剂对[2+2]反应和[4+2]反应的催化效率不同.Lewis酸的酸性强弱、软硬对2-ABDE的[2+2]反应的催化能力起决定性作用.During the hetero Diels-Alder reaction （HAD） between 4-（4-methoxyphenyl）-1-phenyl-3- （trimethylsilyloxy）-2-aza-butadiene （2-ABDE） and hexanone, a unimolecular [2＋2] cyclization of 2-ABDE forming a four-membered monocyclic β-lactam took place. The reaction parameters such as Lewis acid catalysts, temperature and microwave irradiation on the HDA and [2＋2] reactions have been thoroughly studied. The results show that the competition between the [2 ＋2] and [4 ＋2] reactions is largely dependent of temperature. At low temperature as -78 ℃, the product of [4＋2] reaction predominated, while at high temperature as 135 ℃, the product of [2＋2] reaction predominated. Microwave irradiation improved the yield of the [2＋2] reaction significantly. It was also found that the strength and the hardness of the Lewis acid affected the catalytic ability for the [2 ＋ 2] reaction of 2-azabutadiene.

关 键 词：2-氮杂-1 3-丁二烯 杂Diels-Alder反应 [2+2]分子内环合 微波合成 LEWIS酸 

分 类 号：O626[理学—有机化学]