17835-98-2Relevant academic research and scientific papers
The Kinetics of Hydrogen-isotope Exchange at the Nitrogen Atom of Substituted Ions. Part 2. The Nitrosonium-ion-catalysed Reaction
Mills, Derick J.,Ridd, John H.
, p. 637 - 640 (1980)
Nitrosonium ion catalyse hydrogen-isotope exchange between the N-H protons of NN-dimethylanilinium ions and aqueous sulphuric acid (83-93percent).At the acidities used, the subsequent chemical reactions between the amines and nitrosonium ions occur much more slowly.The rate of the catalysed exchange is proportional to the concentration of the nitrosonium ions and inversely proportional to the appropriate acidity function (h0''').A mechanism is put forward for the catalysed exchange based on the formation of a loose complex between the nitrosonium ion and the anilinium ion followed by proton loss from the nitrogen pole.This process is shown to be related to the direct diazotization of some anilinium ions and to the nitrous-acid-catalysed nitration and oxidation of the NN-dimethylanilinium ion.Substituent effects on the nitrosonium-ion-catalysed exchange are much less than those on the acid-catalysed exchange and resemble those on the acid-catalysed mechanism of diazotisation.
The Kinetics of Hydrogen-isotope Exchange at the Nitrogen Atom of Substituted Anilinium Ions. Part 1. The Acid-catalysed Reaction
Blackborow, John R.,Clifford, David P.,Hollinshead, Ira M.,Modro, Tomasz A.,Ridd, John H.,Worley, Michael C.
, p. 632 - 636 (1980)
The rate of N-H hydrogen-isotope exchange in NN-dimethylanilinium ions has been studied in the solvents sulphuric acid and deuteriosulphuric acid using the difference in the (1)H n.m.r. absorption of the N(1+)Me2H and N(1+)Me2D groups.With the N-deuterio-NN-dimethylanilinium ion, the reaction rate decreases steadily with acidity as expected from previous studies of the reaction mechanism at lower acidities.However, the rate of N-D exchange in the N-deuterio-NN-dimethyl-3,5-xylidinium ion reaches a minimum in 83percent sulphuric aacid and then increases steadily with the acidity.Under the same conditions, hydrogen-isotope exchange occurs in the aromatic ring.The effect of methyl substituents on the rate of the acid-catalysed N-H exchange indicates that this reaction and the C-H exchange have a common initial step involving the donation of a proton or deuteron to the positions in the aromatic ring ortho or para to the nitrogen.The Wheland intermediate, so formed, is considered to be able to lose a proton from either the carbon or the nitrogen.This interpretation of the acid-catalysed exchange is supported by the effect of isotopic substitution in the aromatic ring on the rate of N-H exchange and by preliminary studies on the range of this reaction mechanism.
Relative Reactivities in Aminolysis Reactions of Alkyl Alkenesulfonates
Roberts, David W.,Ward, Robert S.,Hughes, Paul J.
, p. 70 - 71 (2007/10/03)
It is found that N-methylbutylamine is ten times more selective than N-methylaniline for the reaction at a methyl group than at a higher alkyl group, and that the greater reactivity of N-methylbutylamine than N-methylaniline is due to differences in entropy of activation rather than differences in activation energy.
Kinetics of One-Electron Transfer Reactions Involving ClO2 and NO2
Huie, Robert E.,Neta, P.
, p. 1193 - 1198 (2007/10/02)
Rate constants for the one-electron oxidation of ClO2(1-) and NO2(1-) by several organic and inorganic free radicals have been measured along with rate constants for several reactions of ClO2, NO2 and BrO2.The kinetics of the reactions of ClO2 and NO2 are consistent with simple electron-transfer theory, except for the reaction of NO2 with SO3(2-), which appears to be oxygen atom transfer.Equilibrium constants have been determined for the reactions of ClO2 with aniline at pH 6.9 and N,N-dimethylaniline at pH 9.6.This leads to one-electron redox potentials of 1.03 and 0.87 V for these aromatic amines, respectively, at the corresponding pH.
Substituted N,N-Dialkylanilines: Relative Ionization Energies and Proton Affinities through Determination of Ion-Molecule Reaction Equilibrium Constants
Lias, Sharon G.,Jackson, Jo-Anne A.,Argentar, Harold,Liebman, Joel F.
, p. 333 - 338 (2007/10/02)
The relative ionization energies and proton affinities of N,N-dimethyl-, N,N-diethyl-, and N,N-di-n-propylaniline, and meta- and para-methyl-substituted analogues (as well as N,N,3,5-tetramethylaniline and 4-chloro-N,N-diethylaniline) have been determined in the gas phase through measurements of the equilibrium constants of charge-transfer and proton-transfer reactions in an ion cyclotron resonance spectrometer.Absolute values are assigned to the ionization energies and proton affinities generated in these experiments.Comparison atandards were the ionization potential (7.12 eV) and proton affinity (223.4 kcal/mol) for N,N-dimethylaniline taken from the literature.The heats of formation of the parent radical cations, M+, and the corresponding protonated molecules, MH+, vary in the same way, differing from one another by 21 +/- 2 kcal/mol over the entire set; that is, the radical cations of these compounds display a constant hydrogen affinity of 74 +/- 2 kcal/mol.This is interpreted to mean that all the compounds protonate at the nitrogen atom; previous work had suggested that meta-substituted isomers protonate on the ring.Further, it is demonstrated that variations in both the ionization energy and the proton affinity values upon changes in ring substitution can be predicted from the appropriate Hammett ? values, but not from the corresponding ?+ values; changes brought about by differing N-substituents correlate with ?* values.
