Oxidative nucleophilic substitution of hydrogen versus ring-opening in the reaction of 4-r-2-nitrothiophenes with amines. The crucial effect of 4-alkyl groups

被引：22

作者：

Bianchi, Lara

Maccagno, Massimo

Petrillo, Giovanni

Sancassan, Fernando

Tavani, Cinzia

Morganti, Stefano

Rizzato, Egon

Spinelli, Domenico

机构：

[1] Univ Genoa, Dipartimento Chim & Chim Ind, I-16146 Genoa, Italy

[2] Univ Bologna, Dipartimento Chim Organ A Mangini, I-40126 Bologna, Italy

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2007年 / 72卷 / 15期

关键词：

MEISENHEIMER-TYPE ADDUCTS; THIOPHENE DERIVATIVES; C-13; NMR; SYNTHETIC EXPLOITATION; BETA-NITROTHIOPHENES; SODIUM METHOXIDE; SECONDARY-AMINES; S(RN)1 REACTIONS; BUILDING-BLOCKS; NITROARENES;

D O I：

10.1021/jo070610i

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

4-Alkyl-2-nitrothiophenes [10: R = CH3, CH(OH)CH3, CH(OCH3)CH3] react with secondary aliphatic amines, in the presence of AgNO3, to give 3-alkyl-2-amino-5-nitrothiophenes (12) through an oxidative nucleophilic substitution of hydrogen (ONSH) of synthetic interest. This behavior is in striking contrast with that of the parent 2-nitrothiophene (6), which was found to undergo ring-opening in analogous reaction conditions. A possible rationale for the crucial effect of alkyl groups is suggested, grounded also on a study of the corresponding Meisenheimer-like adducts.

引用

页码：5771 / 5777

页数：7

共 11 条

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