摘要
室温条件下,以蓝色LED为光源诱导四(三苯基膦)钯〔Pd(PPh_(3))_(4)〕催化激活烷基卤代烃生成烷基自由基,与N-苯基甲基丙烯酰胺发生烷基化环化反应来简单高效的合成21个3,3-二取代吲哚酮衍生物。在室温下即可反应,具有较好的底物适用性与官能团包容性,与含有多元环、烯烃、长链烷烃、大位阻的溴代物反应均能以较高的产率得到目标产物,产率为70%~87%,很大程度上提升反应的效率,且可避免底物预官能团化、转化率低、副产物多等问题,是探索制备吲哚酮类化合物和开发新试剂的一种更加绿色高效的方法。通过^(1)HNMR、^(13)CNMR和HR-MS确证产物的结构,选用2,2,6,6-四甲基哌啶-1-氧(TEMPO)来验证该反应可能经过自由基反应过程。
Study on using blue LED as light source to induce alkyl halide to be catalyzed and activated by tetrakis(triphenylphosphine)palladium〔Pd(PPh_(3))_(4)〕to generate the alkyl free radical,which undergo alkylation and cyclization reaction with N-phenylmethacrylamide for concise and efficient synthesis twenty-one 3,3-disubstituted indolinone derivatives at room temperature.This experiment can be reacted at room temperature,with good substrate applicability and functional group inclusiveness.The target products can be obtained in high yield by reacting with brominated compounds containing polycyclic rings,olefins,long-chain alkanes and large steric hindrance,and the yields of the reaction were in the range from 70%to 87%,which could greatly improve the reaction efficiency.It is a more green and efficient method to prepare indolinone and to develop new reagents,which avoids the problems of pre-functional group of substrates,low conversion rate and many by-products.The structures of the products were confirmed by ^(1)HNMR,^(13)HNMR,and HR-MS.Alkyl free radicals were captured by using 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)to verify that the reaction process may have gone through a free radical reaction process.
作者
宋小文
倪珊梅
李萍
刘懿锋
李兆栋
SONG Xiao-wen;NI Shan-mei;LI Ping;LIU Yi-feng;LI Zhao-dong(College of Materials and Energy,South China Agricultural University,Guangzhou 510642,China;Department of Chemical Engineering,Jieyang Institute of Technology,Jieyang 522000,China)
出处
《化学试剂》
CAS
北大核心
2021年第9期1301-1308,共8页
Chemical Reagents
