The Anomalous Reactions of Some Fluoronitrobenzenes With Some N,N-Dialkylamines

Abstract

The reactions of 1-fluoro-2,4- and -2,6-dinitrobenzene with certain N,N- dialkylamines in dimethyl sulfoxide solution in the presence of potassium carbonate give the corresponding dinitrophenyl N,N- dialkylcarbamates as well as the corresponding N,N- dialkyldinitroanilines. The extent of carbamate formation is governed by steric factors. The corresponding reactions of 1-fluoro-4-nitrobenzene with diisopropylamine and di-s-butylamine give poor yields of the corresponding 4-nitrophenyl N,N- dialkylcarbamates but none of the corresponding N,N-dialkyl-4-nitroanilines; in these reactions, the major product is 4,4'-dinitrodiphenyl ether. The 1H and 13C n.m.r. spectra of the 2,4- and 2,6-dinitrophenyl N,N- dialkylcarbamates reveal that their aliphatic protons and carbon atoms are magnetically non-equivalent.