Abstract
THE mechanism of benzidine formation from hydrazobenzene has been the subject of incessant consideration1. Kinetic study2 has shown the reaction to be bimolecular in respect of acid participation, but the idea3 that this involves initial formation of a doubly charged cation from such a weak base as hydrazobenzene is totally unacceptable. The singly charged cation, like other ammonium ions, would be in equilibrium with aniline and the nitrogenous anion, associated with it by a π bond4, were it not that para-substitution ensues. Finally, the quinonoid substituent is rendered aromatic by action of the second molecule of acid, or, alternatively5 to a subordinate extent, by a suitably constituted hydrazo-compound if such be present.
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Shiner, H. J., and Chamneux, J. T., J. Org. Chem., 32, 901 (1967). Banthorpe, D. V., Cooper, A., and Ingold, C. K., Nature, 216, 232 (1967).
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KENNER, J. Benzidine Rearrangement. Nature 219, 153 (1968). https://doi.org/10.1038/219153a0
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DOI: https://doi.org/10.1038/219153a0
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