Abstract
THE methanolysis of 2,4-dinitrophenyl p-toluene sulphonate has been investigated, in continuance of a series of investigations of the methanolysis of nitrophenyl esters1,2 both under initially neutral conditions and in the presence of tertiary bases, namely, pyridine and its methyl derivatives. In the cases of picryl acetate1 and 2,4-dinitrophenyl acetate2 both the neutral and base-catalysed reactions show acyl–oxygen fission: . In the case of picryl benzoate1 under initially neutral conditions, along with acyl–oxygen fission (1), there also occurred some aryloxygen fission (2): Reaction (2) did not, however, occur in the presence of tertiary bases. The order of the catalytic constants () are in each case > > > , whereas the basic strengths are in the order 2,4,6-collidine > 2,6-lutidine > 2-picoline > pyridine. Thus specific and general base catalysis are ruled out. The mechanism is thus nucleophilic catalysis.
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KIRKIEN-KONASIEWICZ, A., SAMMY, G. & MACCOLL, A. Methanolysis of 2,4-Dinitrophenyl p-Toluene Sulphonate. Nature 203, 637 (1964). https://doi.org/10.1038/203637a0
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DOI: https://doi.org/10.1038/203637a0
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