- The Rearragement of Aromatic Nitro Compounds. Part 1. The Reactions of Nitroanilines in Aqueous Sulphuric Acid
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A number of substituted 2-nitroanilines rearange in concentrated sulphuric acid at 110 deg C to yield products that appear to be derived from 1,3-migration of the 2-nitro-group.For 2,3-dinitroaniline, the rate of reaction is almost independent of acidity over the range 83-97percent sulphuric acid and the solvent isotope effect k(H2SO4)/k(D2SO4) is 1.3-1.9.Methyl and t-butyl groups, when present as additional substituents in 2,3-dinitroaniline, have only a small effect on the reaction rate but 3-methyl-2-nitroaniline reacts much more slowly than 2,3-dinitroaniline.These results are discussed in terms of a rate-determining migration of the 2-nitro group following protonation at the 2-position.
- Murphy, J. Timothy,Ridd, John H.
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p. 1767 - 1772
(2007/10/02)
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- Synthesis of Polynitro Compounds. Peroxydisulfuric Acid Oxidation of Polynitroarylamines to Polynitro Aromatics.
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Peroxydisulfuric acid in sulfuric acid solution, prepared by reaction of hydrogen peroxide with excess oleum or 100percent H2SO4, oxidizes primary polynitroarylamines and their N-acetamido derivatives to polynitro aromatics in good to excellent yields.The new procedure is illustrated by the synthesis of several new polynitro compounds, not preparable by known synthetic methods.Peroxytrifluoromethanesulfonic acid is comparably efficient for such oxidations.The scope and limitations of the new reaction have been examined and compared to other methods of synthesis of polynitro compounds.
- Nielsen, Arnold T.,Atkins, Ronald L.,Norris, William P.,Coon, Clifford L.,Sitzmann, Michael E.
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p. 2341 - 2347
(2007/10/02)
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