53477-44-4Relevant academic research and scientific papers
STRUCTURAL EFFECT ON THE MECHANISTIC PATHWAY OF THE DECOMPOSITION OF 3-ALKYL-1-ARYLTRIAZENES: A KINETIC STUDY
Laila, Abdulhameed A. R.
, p. 453 - 456 (2007/10/02)
A kinetic study of the reaction between 3-alkyl-1-aryltriazenes and substituted acetic acids has been made in solvent acetone over the temperature range 21-37 deg C.Ea is 17.3 +/- 0.3 kcal mol-1 and log A is 10.3 +/- 0.1.Influence of the substituents on the reaction rate has been analyzed.The Hammett correlation with ? gave a ρ value of -0.96 for para-aryl substituted triazenes and +0.35 for meta- and para-substituted phenylacetic acid.The rate of decomposition of triazenes is also affected by changing the alkyl group.From these results a duality in mechanism is proposed; first, a simultaneous protonation and alkyl group expulsion to be the rate-determining step when R is tertiary, benzylic and possibly secondary.Secondly, a concerted mechanism for the protonation of nitrogen and cleavage of the N-R bond for primary alkyl groups.
Substituent Effects on 13C and 15N Chemical Shifts in Triazenes Studied by Principal Components Multivariate Data Analysis
Dunn, III, W.J.,Lins, C.,Kumar, G.,Manimaran, T.,Grigoras, S.,et al.
, p. 450 - 456 (2007/10/02)
Principal components analysis was applied to the 13C and 15N chemical shift data on a series of fifteen 1-(para-substituted-phenyl)-3-acetyl-3-methyltriazenes.It was found that the halogen-substituted triazenes formed a class, based on substituent effects, which was different from the remaining eleven triazenes.A one-component model described the halogen class, whereas a two-component model was necessary for a description of the second class.In the second class, substituent tended to cluster to form groups depending on their electronic character.
