Rearrangement mechanisms for azoxypyridines and azoxypyridine N-oxides in the 100% H2SO4 region — The Wallach rearrangement story comes full circle1

Buncel, Erwin; Sam-Rok Keum; Rajagopal, Srinivasan; Cox, Robin A.
August 2009
Canadian Journal of Chemistry;Aug2009, Vol. 87 Issue 8, p1127
Academic Journal
Kinetic studies of the Wallach rearrangements of four azoxypyridines, four azoxypyridine N-oxides, and one azoxypyridine N-methiodide have been carried out in the 100% H2SO4 acidity region. For all of the β-isomers in the study the reactions proceeded at a spectrally measurable rate, and the log observed rate constants were found to be linear functions of the log H3SO4+ concentration, as previously found for azoxybenzene itself, suggesting that the reaction mechanism for these substrates is the same as that previously deduced for axozybenzene, i.e., a general-acid-catalysis A-SE2 process. For the α-azoxypyridines no reaction could be observed at all. The two α-azoxypyridine N-oxides in the study did react, albeit very slowly, but for these two compounds the log observed rate constants were not linear functions of the log H3SO4+ concentration, but were instead found to be linear in the H0 acidity function, which is known for the 100% H2SO4 acidity region. It follows that the reaction mechanism for these α-isomers is a different one, presumably an A1 process. This mechanism was proposed back in 1963 for azoxybenzene, but has never actually been observed for any substrate before the work reported in this study. Thus, the Wallach rearrangement story can be said to have come full circle.


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