含有吲哚结构单元的四环化合物的高选择性合成研究

发布时间：2018-12-26 07:13

【摘要】：本论文以2-(2-溴芳基)-1H-吲哚为主要起始原料,基于铜或钯催化串联反应的高效性,研究并建立了四类含有吲哚结构单元的四环化合物(吲哚[1,2-c]喹唑啉、11H-吲哚[3,2-c]喹啉、6H-异吲哚[2,1-a]吲哚-6-酮和茚[1,2-b]吲哚-10(5H)-酮)的高效合成新方法。主要研究内容如下:一、深入研究了铜催化下2-(2-溴芳基)-1H-吲哚、醛和氨水的一锅两步三组份串联反应,通过对反应体系的酸碱性进行简单的调控,可以顺利地实现吲哚[1,2-c]喹唑啉和11H-吲哚[3,2-c]喹啉衍生物的高区域选择性合成。研究表明:在氮气氛围下,通过铜催化的2-(2-溴芳基)-1H-吲哚、醛和氨水的串联反应可以顺利地得到该反应的关键中间体——5,6-二氢吲哚[1,2-c]喹唑啉,之后再将反应体系置于空气中继续加热,可以高选择性地得到吲哚[1,2-c]喹唑啉类化合物;而将反应体系先调至弱酸性(pH=5-6),之后再在空气中加热,则可以高选择性地得到11H-吲哚[3,2-c]喹啉类化合物。二、以2-(2-溴芳基)吲哚和CO为起始原料,借助钯催化的环羰基化反应,发展了一种高区域选择性合成6H-异吲哚[2,1-a]吲哚-6-酮和茚[1,2-b]吲哚-10(5H)-酮的新方法。研究表明:该反应的区域选择性是由底物的结构来控制的,当选用2-(2-溴芳基)-1H-吲哚为反应物时,该反应可以高选择性地得到6H-异吲哚[2,1-a]吲哚-6-酮;而当反应物为N-取代-2-(2-溴芳基)-1H-吲哚时,则可以选择性地得到茚[1,2-b]吲哚-10(5H)-酮。
[Abstract]:In this paper, based on the high efficiency of copper or palladium catalyzed series reaction, four kinds of tetracyclic compounds (indole [1n 2 c] quinazoline) containing indole structural units were studied and established using 2-(2 bromoaryl) -1H indole as the main starting material. A New method for the Synthesis of 11H-Indole [3H _ 2-c] Quinoline, 6H _ isoindole [2o _ 1-a] Indole-6-one and Indene [1H _ 2-b] Indole-10 (5H) -one). The main contents are as follows: 1. The two-step three-component series reaction of 2- (2-bromoaryl) -1H-indole, aldehydes and ammonia catalyzed by copper was studied. The high regioselective synthesis of indole-2-c quinazoline and 11H-indole-3-quinoline derivatives can be successfully realized. The results showed that the key intermediates of the reaction, 5H _ 6- dihydroindole [1o _ 2-c] quinazoline, could be obtained successfully by the copper-catalyzed series reaction of 2- (2-bromoaryl) -1H-indole, aldehyde and ammonia water in nitrogen atmosphere, and the results showed that the key intermediates of the reaction could be obtained by the series reaction of 2- (2-bromo-aryl) -1H-indole, aldehyde and ammonia water. After reheating the reaction system in air, the indole-2-c quinazoline compounds can be obtained with high selectivity. However, by adjusting the reaction system to weak acid (pH=5-6) and then heating in air, 11H-indole [3O2-c] quinoline compounds can be obtained with high selectivity. Second, using 2- (2-bromoaryl) indole and CO as starting materials, the cyclocarbonylation reaction catalyzed by palladium was used. A new method for the highly regioselective synthesis of 6H-isoindole-6-one and indole-10 (5H) -one was developed. The results show that the regioselectivity of the reaction is controlled by the structure of the substrate, and when 2- (2-bromoaryl) -1H-indole is selected as the reactant, In this reaction, 6H-isoindole-6-one can be obtained with high selectivity. When the reactant is N- substituted-2- (2-bromoaryl) -1H-indole, indole-10 (5H) -one can be obtained selectively.
【学位授予单位】：河南师范大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：O626

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