苯炔与Mannich碱反应制备稠合四氢喹啉  被引量:2

Synthesis of fused tetrahydroquinoline via tandem reaction of benzyne and mannich base

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作  者:李文娟[1] 骆学松 郭亮[1] 何林[1] 代斌[1] 郭旭虹[1] LI Wenjuan LUO Xuesong GUO Liang HE Lin Dai Bin GUO Xuhong(School of Chemistry and Chemical Engineering,Shihezi University/Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan /Key Laboratory of Materials-Oriented Chemical Engineering of Xinjiang Uygur Autonomous Region,Shihezi, Xinjiang 832003 ,Chin)

机构地区:[1]石河子大学化学化工学院/新疆兵团化工绿色过程重点实验室/材料化工新疆维吾尔自治区重点实验室,新疆石河子832003

出  处:《石河子大学学报(自然科学版)》2017年第3期273-280,共8页Journal of Shihezi University(Natural Science)

基  金:国家自然科学基金项目(21462034);兵团高校优秀青年教师资助项目;石河子大学第5批"3152"人才支持计划(编号CZ0210)

摘  要:苯炔是一种高活性反应中间体,在有机合成化学和天然产物的合成领域有着广泛的应用。本文采用活泼的苯炔前体与Mannich碱构建稠合的取代四氢喹啉环。实验结果表明:苯炔前体和Mannich碱比例为1∶1.5,KF为氟源,18-冠-6为添加剂,乙腈为溶剂,室温下反应2 h条件下可得到最优的产率;共制备15种稠合取代四氢喹啉,产率在23%-70%之间。其反应机理可能是:钾离子与18-crown-6相络合,使氟离子游离,从而进攻苯炔前体中的三甲基硅基,进行1,2消除反应,原位生成苯炔;Mannich碱中的氮原子进攻苯炔的三键进行亲电加成反应,同时苯炔三键的另一端对羰基碳原子进行亲核加成,从而得到稠合四氢喹啉产物。Benzene is a highly reactive intermediate, which has a wide range of applications in the field of organic synthesis chemistry and synthesis of natural products. In this paper, we use benzyne precursors and Mannich bases to construct fused substituted tetrahydroquinoline rings. The experimental results show the optimal experiment condition that the ratio of benzyne and Mannich base is 1: 1.5 and KF/18-crown-6 is fluorine source and acetonitrile is the solvent and time is 2 hours at room temperature. Fifteen kinds of fused-substituted quinones were obtained in a yield of 23%-70%. Possible reaction mechanism:18-crown-6 complexes with the potassium ion of KF and release the free fluoride ion, which subsequently attack the silica atom of o-trimethylsilylphenyl triflate to produce the active benzyne intermediate in situ. The nitrogen atom in the Mannich base attack the the tri-bond of benzyne through electrophilic addition reaction, and the nucleophilic addition of the carbonyl carbon atom at the other end of the benzyne the triple bond to obtain the cyclic target product.

关 键 词:苯炔 MANNICH碱 插入环化反应 构建 稠合取代四氢喹啉 

分 类 号:O626.323[理学—有机化学]

 

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