DPPA催化芴-9-羧酸的新颖脱羧反应  

An unusual decarboxylation of fluorene-9-carboxylic acid catalyzed by DPPA

作　　者：丛晓丽[1,2] 倪帅帅[1] 朱进[1] 

机构地区：[1]华东理工大学药学院,上海200237 [2]民生药业滨江分公司,浙江杭州310051

出　　处：《化学试剂》2012年第6期542-544,共3页Chemical Reagents

基　　金：国家自然科学基金资助项目(21002028)

摘　　要：以0.096 mmol叠氮磷酸二苯酯(Diphenylphosphorazidate,DPPA)为催化剂,在极性溶剂和0.48 mmol的三乙胺存在的条件下,0.48 mmol芴-9-羧酸可以发生新颖的脱羧反应。考察了水、有机溶剂以及不同物质的量的DPPA和三乙胺对反应收率的影响。并针对反应结果,提出了可能的反应机理,即:反应中芴-9-羧酸形成的碳负离子可以被结构中的五元环稳定,亲核进攻DPPA形成六元环状过渡态,并发生分子内消除反应,得到脱羧产物。Under O. 096 mmol. diphenylphosphorazidate （ DP- PA） catalyzed,0.48 mmol triethylamine and polar solvents conditions,0.48 mmol fluorene-9-carboxylic acid undergoes an unusual decarboxylation process. The effects of various or- ganic solvents, water, and amount of alkaline and DPPA on the reaction were investigated. Based on these results, a plau- sible reaction mechanism involving tri-cyele p -π conjugated carbanion and the formation of a six-center cyclic transition state was provided. This work extended the application of DP- PA.

关 键 词：芴-9-羧酸 脱羧反应 DPPA 

分 类 号：TM344.1[电气工程—电机]