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.

ABSTRACT

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.