Aromatic nucleophilic substitution. XVI. Stopped-flow kinetics of formation and decomposition of 1,3- and 1,1-disubstituted anionic .SIGMA. complexes in reactions of 1-dimethylamino-2,4-dinitronaphthalene with potassium alkoxides in dimethyl sulfoxide-alc

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概要

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• Reactions of 1-dimethylamino-2,4-dinitronaphthalene with potassium methoxide or ethoxide were carried out in DMSO–CH<SUB>3</SUB>OH or DMSO–C<SUB>2</SUB>H<SUB>5</SUB>OH (90:10 v/v), respectively, where the 1,3-disubstituted anionic σ complexes were first rapidly formed, undergoing isomerizations to the 1,1-disubstituted anionic σ complexes. Rates and activation parameters were determined by kinetic studies using stopped-flow and conventional spectrophotometers. The rate constant (25 °C) for the formation of 1,3-disubstituted one in DMSO–CH<SUB>3</SUB>OH is about half that in DMSO–C<SUB>2</SUB>H<SUB>5</SUB>OH, whereas the rate constant (25 °C) for its decomposition is more than twice that in DMSO–C<SUB>2</SUB>H<SUB>5</SUB>OH. The apparent pseudo-first-order rate constant for the formation of 1,1-disubstituted anionic σ complex in DMSO–CH<SUB>3</SUB>OH depends upon the methoxide ion concentration, whereas that in DMSO–C<SUB>2</SUB>H<SUB>5</SUB>OH is almost independent of the ethoxide ion concentration. The mechanism is discussed on the basis of activation parameters.

• 公益社団法人 日本化学会の論文

著者

• Sekiguchi Shizen

  Department of Chemistry, Faculty of Engineering, Gunma University

• Tomoto Noboru

  Department of Chemistry, Miyazaki University

• Takei Toshio

  Department of Applied Chemistry, College of Engineering, University of Osaka Prefecture

• Tone Noboru

  Department of Synthetic Chemistry, Gunma University

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