Nitration in carbon tetrachloride. Kinetics of nitration of N-methyl-N-nitrosoaniline

Abstract

The nitration of N-methyl-N-nitrosoaniline by anhydrous nitric acid has been studied in carbon tetrachloride solution at 25°. With a 5 : 1 or higher ratio of acid to nitrosamine, the reaction is third-order in the former and first-order in the latter. The effect upon the reaction rate of the addition of small quantities of the polar solutes water, acetonitrile, dimethylformamide, and trifluoroacetic acid has been investigated. Rates of exchange have been measured of the ¹⁵N labelled nitroso group between N-methyl-N-[¹⁵N]nitrosoaniline (and its p-nitro-derivative) and nitric acid, in carbon tetrachloride. Simultaneous measurement of the rate of nitration of the former compound to its o- and p-nitro-derivatives has permitted differentiation between several possible reaction pathways for the C-nitration.