- N-Alkyl-N-Cyclopropylanilines as Mechanistic Probes in the Nitrosation of N,N-Dialkyl Aromatic Amines
-
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.
- Loeppky, Richard N.,Elomari, Saleh
-
-
- Evidence for radical cations in linked mechanisms of N,N-Dialkyl aromatic amine nitration and nitrosative dealkylation
-
N,N,-Dialkyl aromatic amines react rapidly with nitrous acid to competitively produced a nitrosamine and a nitro compound. The mechanism of nitro compound formation involves a reaction of an amine radical cation with NO2, while the nitrosamine
- Loeppky, Richard N.,Singh, Sukhjeet P.,Elomari, Saleh,Hastings, Riley,Theiss, Thomas E.
-
p. 5193 - 5202
(2007/10/03)
-