74849-14-2Relevant academic research and scientific papers
Pathways for the Decomposition of Alkylaryltriazenes in Aqueous Solution
Jones, Caroline C.,Kelly, Migel A.,Sinnott, Michael L.,Smith, Paul J.,Tzotzos, George T.
, p. 1655 - 1664 (2007/10/02)
Primary alkylaryltriazenes give solvent-equilibrated alkenediazonium ions and anilines in aqueous solution at 25 deg C by two processes.The first, an A-SE2(N) reaction, involves immobilisation of a molecule of catalysing acid, and a transition state in which the proton is essentially completely transferred and little breakage of the N-N bond has occurred.The structure of this transition state varies with the strength of the catalysing acid and the pKa of the liberated aniline in a way interpretable in terms of a More O'Ferrall-Jencks diagram.The second process is the departure of aniline anion without acid assistance.The first process is governed by positive, the second by negative, βlg values.
Substituent Effects on Tautomerisation Constants of Alkylaryltriazenes
Kelly, Miguel A.,Murray, Martin,Sinnott, Michael L.
, p. 1649 - 1654 (2007/10/02)
Both tautomers of propyl-p-nitrophenyl-, -p-cyanophenyl-, -3,5-dichlorophenyl-, and -p-chlorophenyl-triazenes are directly observable by 1H n.m.r. at 200 MHz in CD3CN at 25 deg C.In addition, lower temperature studies enable the two tautomers of propyl-p-methylphenyl- and -p-methoxyphenyl-triazenes to be quantitated.At -45 deg C rotamers about the N-N bond of the conjugated tautomers are also separately observable. 13C N.m.r. studies of the p-nitro- and p-chloro-compounds suggest tautomerisation involves the less abundant rotamer of the conjugated tautomer and the unconjugated tautomer.The position of equilibrium at 25 deg C is described by log (/) = (0.67 +/- 0.13) - (0.31 +/- 0.04)pKa (ArNH3+). 13C, as well as 1H n.m.r. studies indicate that change of solvent to (CD3)2SO, CD3CN-(CD3)2SO, or CD3CN-(CD3)2SO-H2O has little effect.Neither, in the p-nitrophenyl case, does change of the propyl group for benzyl.
