Synthesis and reactions of perylenecarboxylic acid derivatives. VI. Sulfonation of 3, 4-perylenedicarboximide

Abstract

The sulfonation of 3, 4-perylenedicarboximide (1) with sulfuric acid has been studied. The position of the sulfo group in the monosulfonated product (2) obtained at 100 °C has been discussed on the basis of the NMR and IR spectra of 2 and the related compounds, and has been confirmed to be the 9-sulfoperylene-3, 4-dicarboximide. The localized treatment of 1 by Hückel and Pople MO calculations confirmed substitution at the 9-position. Paper chromatographic analysis indicated that the reaction product was only 2 in the temperature range 60-120 °C, and the reaction rate was determined spectroscopically. The maximum formation of 2 was approximatedly 97% at 100 °C. The rate of reaction was found to be a pseudo first order process and the activation energy found to be 19.5 kcal/mol.