基于1,3-环己二酮砌块的吲哚类似物合成研究  

Synthesis of Indole Analogues Based on 1,3-Cyclohexanedione Building Blocks

作　　者：席爽 王锐[1] Xi Shuang;Wang Rui(School of Petrochemical Engineering,Liaoning Petrochemical University,Fushun Liaoning 113001,China)

机构地区：[1]辽宁石油化工大学石油化工学院,辽宁抚顺113001

出　　处：《辽宁石油化工大学学报》2022年第2期23-29,共7页Journal of Liaoning Petrochemical University

基　　金：国家自然科学基金项目(21402078)。

摘　　要：以廉价易得和具备多种反应性的2位单侧链取代的1,3-环己二酮化合物作为合成砌块,以苯基四氟硼酸重氮盐作为原料,采用经典的Japp-Klingemann费舍尔吲哚合成法,对其进行开环碎裂化,进而环合,得到更有价值的多取代吲哚结构单元。其中,以2-甲基-1,3-环己二酮和苯基四氟硼酸重氮盐作为原料,在对甲苯磺酸作为酸试剂、甲苯为溶剂的回流条件下,反应15.0 h,能以49%的产率得到关环吲哚产物;以2-苄基-1,3-环己二酮和苯基四氟硼酸重氮盐作为原料,在体积分数为30%的盐酸乙醇溶液的封管加热回流条件下,反应0.5 h,能以98%的产率得到关环吲哚产物。该合成方法学可应用于吲哚类生物碱的全合成研究中。In this paper, used cheap, easy-to-obtain and multi-reactive 2-position single-side chain substituted 1, 3-cyclohexanedione compound as a synthetic building block, used phenyl tetrafluoroborate diazonium salt as raw material, and adopt classic Japp-Klingemann fischer indole synthesis method, it is ring-opening fragmentation and following ring-closing to obtain more valuable multi-substituted indole structural units. Among them, 2-methyl-1, 3-cyclohexidone and a diazonium salt of phenyl tetrafluoroborate were used as raw materials, under reflux conditions of p-toluenesulfonic acid as the acid reagent and toluene as the solvent, when the reaction was carried out for 15.0 h, the closed ring indole products were obtained with a yield of 49%;Meanwhile, 2-benzyl-1,3-cyclohexidone and a diazonium salt of phenyl tetrafluoroborate were used as raw materials, under the condition of heating and refluxing in a sealed tube of 30% hydrochloric acid ethanol solution, when the reaction was carried out for0.5 h, the closed ring indole products were obtained with a yield of 98%. This methodology can be applied to the total synthesis of indole alkaloids.

关 键 词：1 3-环己二酮 吲哚类似物 碎裂化 Japp-Klingemann费舍尔吲哚合成法 

分 类 号：TE624[石油与天然气工程—油气加工工程]