3,6-二烃基咔唑-1-甲醛和3,6-二烃基咔唑-1,8-二甲醛的高效合成  

Efficient Synthesis of 3,6-Dialkylcarbazole-1-formaldehyde and 3,6-Dialkylcarbazole-1,8-diformaldehyde

作　　者：赵雨 刘阳 王鑫鑫 洪莹莹 满英秀 王进军[2] 李家柱[1] Zhao Yu;Liu Yang;Wang Xinxin;Hong Yingying;Man Yingxiu;Wang Jinjun;Li Jiazhu(College of Chemistry and Chemical Engineerings Yantai University,Yantai,Shandong 264005;Department of Food&Biological Engineerings Wenjing College,Yantai University,Yantai,Shandong 264005)

机构地区：[1]烟台大学化学化工学院,山东烟台264005 [2]烟台大学文经学院食品与生物工程系,山东烟台264005

出　　处：《有机化学》2021年第6期2435-2444,共10页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.51472212);山东省自然科学基金(No.ZR2015BQ012)资助项目。

摘　　要：已报道的咔唑-1-甲醛或咔唑-1,8-二甲醛的合成方法要么合成步骤长,产率低,要么试剂毒性较大或者操作具有较大危险性,严重影响了后续衍生物合成和应用的进展.在本研究中,用2-(三甲硅烷基)乙氧甲基氯(SEMCl)保护溴代咔唑9-NH,成功利用正丁基锂/N,N-二甲基甲酰胺(DMF)代替叔丁基锂/DMF完成甲酰化,降低了操作的危险性,获得了一种更安全高效、适合规模化制备的3,6-二烃基咔唑-1-甲醛或1,8-二甲醛的制备方法.此外,还对咔唑-1-甲醛或1,8-二甲醛的反应活性进行探索,成功制备了一系列三齿氮或双齿氮型配体.The currently reported synthesis methods of carbazole-1-formaldehyde or carbazole-1,8-diformaldehyde have some drawbacks,such as long synthetic steps with low yield,high toxicity of reagents,or high risk of operation,which affected the progress of synthesis and application of subsequent derivatives.In this work,the 9-NH of bromocarbazole was protected by 2-(trimethylsilyl)ethoxymethyl chloride(SEMCl),the subsequent formylation was successfully accomplished by n-butyllithium/N,N-dimethylformamide(DMF)instead of tert-butyllithium/DMF to reduce the risk of operation process.Finally,a safe and efficient method that is more suitable for large-scale preparation of 3,6-dialkylcarbazole-1-formaldehyde or 1,8-diformaldehyde was developed.In addition,the reactivity of carbazole-1-formaldehyde or 1,8-diformaldehyde was explored,and a series of tridentate or bidentate ligands were successfully prepared.

关 键 词：咔唑 甲酰化 咔唑-1-甲醛 咔唑-1 8-二甲醛 

分 类 号：O626[理学—有机化学]