51904-47-3Relevant academic research and scientific papers
N-Alkyl-N-Cyclopropylanilines as Mechanistic Probes in the Nitrosation of N,N-Dialkyl Aromatic Amines
Loeppky, Richard N.,Elomari, Saleh
, p. 96 - 103 (2007/10/03)
A group of N-cyclopropyl-N-alkylanilines has been synthesized, and their reaction with nitrous acid in aqueous acetic acid at 0°C was examined. All compounds reacted rapidly to produce the corresponding N-alkyl-N-nitrosoaniline by specific cleavage of the cyclopropyl group from the nitrogen. The transformations were unaffected by the nature of the alkyl substituent (Me, Et, iPr, Bn). The reaction of 4-chloro-N-2-phenylcyclopropyl-N-methylaniline with nitrous acid gave 4-chloro-N-methyl-N-nitrosoaniline (76%), cinnamaldehyde (55%), 3-phenyl-5-hydroxyisoxazoline (26%), and 5-(N-4-chlorophenylmethylamino)-3-phenylisoxazoline (8%). Both the selective cleavage of the cyclopropyl group from the aromatic amine nitrogen and nature of the products derived from the cyclopropane ring support a mechanism involving the formation of an amine radical cation. This step is followed by rapid cyclopropyl ring opening to produce an iminium ion with a C-centered radical which either combines with NO or is oxidized.
Stereoelectronic Effects in Tertiary Amine Nitrosation: Nitrosative Cleavage vs. Aryl Ring Nitration
Leoppky, Richard N.,Tomasik, Witold
, p. 2751 - 2757 (2007/10/02)
The nitrosation (acetic acid) of N-(4-chlorophenyl)pyrrolidine gives at least 30percent N-(4-chloro-2-nitrophenyl)pyrrolidine while the corresponding aryldibenzylamine gives no nitration and only nitrosative dealkylation at nitrogen.This difference in reaction site has been probed with N-(4-chlorophenyl)diethylamine.This substance undergoes competitive ring nitration to N-(4-chloro-2-nitrophenyl)diethylamine (50percent) and nitrosative dealkylation to (4-chlorophenyl)ethylnitrosamine (50percent).The former compound nitrosates further to give (4-chloro-2-nitrophenyl)ethylnitrosamine.This substance denitrosates to give the corresponding secondary amine.The reactivity differences result from stereoelectronic factors controlling the amine nitrogen unshared pair delocalization into the aryl ring.This interpretation is supported by 13C NMR data and mechanistic arguments.
