945-81-3Relevant academic research and scientific papers
Regioselective Nitration of N-Alkyl Anilines using tert-Butyl Nitrite under Mild Condition
Chaudhary, Priyanka,Gupta, Surabhi,Muniyappan, Nalluchamy,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
, p. 104 - 119 (2019/01/08)
Regioselective ring nitration of N-alkyl anilines is reported using tert-butyl nitrite. The reactions proceed efficiently with a wide range of substrates providing synthetically useful N-nitroso N-alkyl nitroanilines in excellent yields which can be easily converted into N-alkyl phenylenediamines and N-alkyl nitroanilines using Zn-AcOH and HCl/MeOH, respectively.
The mechanistic origin of regiochemical changes in the nitrosative N-dealkylation of N,N-dialkyl aromatic amines
Teuten, Emma L.,Loeppky, Richard N.
, p. 1097 - 1108 (2007/10/03)
The regioselectivity of the nitrous acid mediated dealkylation of 4-substituted-N-ethyl-N-methylanilines is a function of the acidity of the reaction mixture. At high acidity deethylation predominates, whereas demethylation is the predominant reaction in nitrosamine formation at pH 2 and above. In some cases the regioselectivity of nitrosative dealkylation changes as the run proceeds. Through the use of the corresponding 4-nitroaniline as the primary substrate, CIDNP, kinetics, kinetic deuterium isotope effects and other transformations involving nitrosations with NO2 or NOBF4 in aprotic solvents, a new mechanism of tertiary amine nitrosation has been deduced and proposed to explain regioselective deethylation. The mechanism involves the oxidation of the substrate to the amine radical cation by NO +. This is followed by the abstraction of a hydrogen atom from the carbon adjacent to the amine nitrogen by NO2 to produce an iminium ion which reacts further to produce the corresponding aldehyde and the nitrosamine. Depending upon the acidity, this process competes with three other mechanistic pathways, two of which give the nitrosamine through the iminium ion, and one leads to the formation of C-nitro compounds. The competing pathways to nitrosamine formation involve NOH elimination from a nitrosammonium ion and deprotonation of the radical cation to give an α-amino radical which rapidly oxidized to the iminium ion. Predominant, but not highly regioselective demethylation occurs by these pathways. Nitro compound formation principally arises from the reaction of NO2 with the radical cation followed by deprotonation, but also occurs by para C-nitrosation followed by oxidation. The Royal Society of Chemistry 2005.
N-Dealkylation-N-nitrosation of Tertiary Aromatic Amines by n-Butyl Nitrite
Verardo, Giancarlo,Giumanini, Angelo G.,Strazzolini, Paolo
, p. 7845 - 7852 (2007/10/02)
N,N-Dialkyl aromatic amines with a variety of ring substituents are N-dealkylated and N-nitrosated efficiently by n-butyl nitrite/ammonium chloride/water at reflux temperature.Ring nitrosation was never observed, but minor amounts of m- and p-nitro amines and/or nitrosamines were formed in some cases.Ring nitration is rather a reaction of the initial substrate than a process occurring on formed nitrosamines.The leaving propensities of the initial N-substituents to yield nitrosamines were in the order benzyl >> methyl >> alkyl.Key Words: Nitrosamines; N-Dealkylation; N-Nitrosation; C-Nitration; Alkyl nitrite.
