Synthesis of 2,8‐Disubstituted 1,3,7,9‐Tetraazaperylenes and Radiochromism of Their Dichloromethane Solutions

Abstract Nucleophilic aromatic substitution of chlorine in the 1,3,7,9‐tetraazaperylenes core was investigated as a simple approach to the synthesis of various 2,8‐disubstituted 1,3,7,9‐tetraazaperylenes. Functionalization of 1,3,7,9‐tetraazaperylenes core was achieved through the introduction of different substituents such as phenoxy, alkoxy, dialkylamino, morpholino, ethanolamino, and phenylamino groups. A one‐step dichloro‐substitution protocol was developed for the isolation of 1,3,7,9‐tetraazaperylenes containing two identical substituents. Two‐step procedures involving isolation of the monoaminated derivative and its subsequent reaction with O‐ or N‐nucleophiles were used to synthesize 1,3,7,9‐tetraazaperylenes with two different substituents. The structure of the substituents in 1,3,7,9‐tetraazaperylenes significantly affects UV–vis spectra of their solutions. Moreover, dichloromethane solutions of N,N,N,N ‐tetrabutyl‐1,3,7,9‐tetraazaperylene‐2,8‐diamine exhibit properties of colorimetric sensors of both proton concentration and γ‐irradiation with an operating range of 10–50 Gy.