One step C-N bond formation from alkylbenzene and ammonia over Cu-modified TS-1 zeolite catalyst
One step C-N bond formation from alkylbenzene and ammonia over Cu-modified TS-1 zeolite catalyst
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Cu 改性 TS-1 沸石催化剂上烷基苯和氨一步形成 C-N 键
DOI：
10.1039/c4cy00472h
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发表时间：
2014
影响因子：
5
通讯作者：
Hu Changwei
中科院分区：
文献类型：
--
作者：
Xia Sheng;Yu Tianhua;Liu Huihui;Li Guiying;Hu Changwei
将铜掺杂的TS-1沸石样品用于催化甲苯环链和侧链以及其他烷基苯环上C-N键的形成。甲苯胺化反应的产率为3.4%，硝基苯产率为1.0%。侧链上的C-N键产物为氰基苯，产率为1.0%。C-N键生成的选择性为52.4%。该催化剂促进氨和过氧化氢生成羟胺中间体，然后瞬间生成的氨基阳离子与底物反应，在环和侧链上形成C-N键。氰基苯是由氨和甲苯反应生成的苯甲胺脱水而成的。对于单取代苯环上C-N键的形成具有正向取向优势。随着甲基取代基数的增加，环状产物的产率下降，这可能是由于空间位阻引起的。
A Cu doped TS-1 zeolite sample was applied to catalyze the formation of C–N bonds on both the ring and the side chain of toluene, as well as other alkylbenzenes. A yield of 3.4% of toluidine was obtained for the amination of toluene, with a 1.0% yield of nitrobenzene. Cyanobenzene was also obtained as the C–N bond product on the side chain with a yield of 1.0%. The selectivity for C–N bond formation was 52.4%. The catalyst promoted the formation of a hydroxylamine intermediate from ammonia and hydrogen peroxide, and then the instantaneously generated amino cation reacted with the substrate to form C–N bonds on both the ring and side chain. Cyanobenzene was produced from the dehydration of benzylamine, formed via the reaction of ammonia and toluene. The formation of C–N bonds on the ring had an ortho-orientation advantage for mono-substituted-benzenes. With the increase in the number of methyl substituents, the yield of the ring products decreased, which might be caused by steric hindrance.