Nitration of heteroaryltrimethyltins by tetranitromethane and dinitrogen tetroxide: Mechanistic aspects, scope and limitations

被引:43
作者
Fargeas, V
Favresse, F
Mathieu, D
Beaudet, I
Charrue, P
Lebret, B
Piteau, M
Quintard, JP
机构
[1] Fac Sci & Tech Nantes, CNRS, UMR 6513, Synth Organ Lab, F-44322 Nantes 3, France
[2] CEA, F-37260 Monts, France
关键词
aromatic substitution; heterocycles; ionization potentials; nitration; tin;
D O I
10.1002/ejoc.200200611
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The nitration of 2-(trimethylstannyl)heteroarenes by tetra-nitromethane (TNM) or dinitrogen tetroxide has been shown to be possible when the HOMO energy of the heteroaryltin is high enough to allow the formation of the corresponding radical cation. The reaction proceeds through a charge-transfer complex between heteroaryltin and TNM, followed by a single-electron transfer, which is enhanced under sun-lamp irradiation. Accordingly, 2-nitrobenzo[b]furan, 2-nitro-benzo[b]thiophene, 2-nitropyridine and 2-nitroindoles were obtained by this method. However, the nitration of 2-stannylated pyrimidine or of stannylated 1,3,5-triazines has been shown to be impossible, due to the low energy of their HOMO orbitals. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).
引用
收藏
页码:1711 / 1721
页数:11
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