二氧化锰催化碳氮双键生成
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- 英文论文题名：a-MnO_2 catalyzed C=N formation
- 论文作者：张哲 ; 王敏 ; 王峰
- 英文论文作者：Zhe Zhang ; Min Wang ; Feng Wang ; Dalian Institute of Chemical Physics ; Chinese Academy of Sciences ; University of Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院大连化学物理研究所;中国科学院大学;
- 论文关键词：二氧化锰 ; 亚胺 ; 室温 ; 催化
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第三十三分会：绿色化学
- 语种：中文
- 分类号：O621.251
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第三十三分会 ; 绿色化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：250k
- 原文格式：D
- 会议级别：全国
摘要
亚胺化合物作为合成中间体具有重要的应用价值,是一类重要的化合物。在现有的合成亚胺的手段中,胺类自身氧化偶联得到了广泛关注。我们用叔丁基过氧化氢作氧源,在室温下,二氧化锰催化氧化胺直接转化到亚胺,反应过程简单高效。底物拓展到13个苯环,杂环以及脂肪胺,转化率在82-99%,选择性在95-99%。催化反应为多相催化,催化剂二氧化锰可以循环使用多次,催化活性无明显降低。连续反应装置证实催化剂的稳定性可以持续100小时以上。在此基础上,我们将此催化体系用于合成更复杂但有意义的含有碳氮双键的化合物,如喹唑啉和喹唑啉酮。我们用二氧化锰催化剂,叔丁基过氧化氢为氧化剂,可以高效和高选择性将醇与邻氨基苯甲酰胺或邻氨基苄胺合成喹唑啉酮或喹唑啉。
Imine is a significant class of compounds due to their versatile applications as synthetic intermediates.Herein,we have demonstrated a simple,efficient and eco-friendly protocol for the direct synthesis of imines from amines via a facile α-MnO_2 catalyzed-procedure at room temperature.This catalytic system was easily separable,reusable and suitable for various amines.Up to 13 substituted benzylic amines,normal aliphatic amines,and O-and S-containing heterocyclic amines were highly selectively converted into the corresponding imines with excellent yields.A continuous synthesis approach proved the catalyst's longtime stability in more than 100 h.Having achieved desirable results,we utilized this catalytic procedure to obtain some more complicated compounds containing C=N,such as quinazolinone and quinazoline,which play a significant role in medical intermediates.Here,an α-MnO_2 catalyst is found to be highly active and selective in the oxidative cyclization of anthranilamides or aminobenzylamines with alcohols using TBHP as an oxidant.
Imine is a significant class of compounds due to their versatile applications as synthetic intermediates.Herein,we have demonstrated a simple,efficient and eco-friendly protocol for the direct synthesis of imines from amines via a facile α-MnO_2 catalyzed-procedure at room temperature.This catalytic system was easily separable,reusable and suitable for various amines.Up to 13 substituted benzylic amines,normal aliphatic amines,and O-and S-containing heterocyclic amines were highly selectively converted into the corresponding imines with excellent yields.A continuous synthesis approach proved the catalyst's longtime stability in more than 100 h.Having achieved desirable results,we utilized this catalytic procedure to obtain some more complicated compounds containing C=N,such as quinazolinone and quinazoline,which play a significant role in medical intermediates.Here,an α-MnO_2 catalyst is found to be highly active and selective in the oxidative cyclization of anthranilamides or aminobenzylamines with alcohols using TBHP as an oxidant.
引文
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