二卤海因参与的(取代苯基)-(吡啶-2-基)-甲酮类化合物的卤化反应  

Halogenations of(substituted phenyl)-(pyridin-2-yl)-methanones with 1,3-dihalo-5,5-dimethylhydantoin

作　　者：卢大顺 田菊燕 张福梅 陈瑛 张银 刘祈星 周海峰 ZHANG Yin;LIU Qixing;ZHOU Haifeng(Research Center of Green Pharmaceutical Technology and Process,Hubei Key Laboratory of Natural Products Research and Development,College of Biological and Pharmaceutical Sciences,China Three Gorges University,Yichang 443002,Hubei,China)

机构地区：[1]三峡大学生物与制药学院天然产物研究与利用湖北省重点实验室绿色制药技术与工艺研究中心,湖北宜昌443002

出　　处：《精细化工》2020年第10期2144-2149,2160,共7页Fine Chemicals

基　　金：湖北省自然科学基金(2018CFB241)。

摘　　要：以(取代苯基)-(吡啶-2-基)-甲酮类化合物为原料,二溴海因和二氯海因为溴源和氯源,1,2-二氯乙烷为溶剂,通过醋酸钯催化的卤化反应,实现了该类化合物的邻位溴代和氯代,得到18种(卤代苯基)-(吡啶-2-基)-甲酮类化合物,并采用1HNMR、13CNMR对产物进行了结构鉴定。从底物普适性研究可知,对不同取代基的苯基-(吡啶-2-基)-甲酮类化合物进行邻位溴代或氯代,得到中等或良好的产率。研究发现,二溴海因的反应活性比二氯海因高。控制实验表明,该反应为碳氢活化卤代反应,并提出了一种可能的反应机理。Eighteen(halogenated phenyl)-(pyridin-2-yl)-methanones were prepared by Pd(OAc)2 catalyzed C—H halogenation from(substituted phenyl)-(pyridine-2-yl)-methanones with dibromohydantoin and dichlorohydantoin as halogen sources and 1,2-dichloroethane as solvent.Their structures were confirmed by 1 HNMR and 13CNMR.A range of(halogenated phenyl)-(pyridin-2-yl)-methanones with wide functional group tolerance was obtained in moderate to good yields.Furthermore,the results indicated that the halogenation ability of dibromohydantoin was higher than that of dichlorohydantoin.In addition,a possible reaction pathway was proposed as a C—H bond activation-halogenation process based on the results of control experiments.

关 键 词：二溴海因 二氯海因 (取代苯基)-(吡啶-2-基)-甲酮类化合物 碳氢活化 卤代反应 中间体 

分 类 号：TQ031.8[化学工程] O625.42[理学—有机化学]