Influence of different amino substituents in position 1 and 4 on spectroscopic and acid base properties of 9,10-anthraquinone moiety

A series of novel 1-amino and 1,4-diamino-9,10-anthraquinones, substituted with different alkyl groups, were synthesized as the result of alkylation with amino substituents. All the obtained aminoanthraquinone derivatives were characterized by NMR, IR spectroscopy and mass spectrometry. The spectroscopic properties of these compounds were determined by using UV–Vis spectroscopy in acetonitrile, and in the mixture of acetonitrile and methanol at different pH ranges. The effects of various substituents present in the newly developed anthraquinone derivatives and their ability to form hydrogen bonds between the carbonyl oxygen atom of anthraquinone moiety and nitrogen atom of N–H group in 1-aminoanthraquinone (1-AAQ) and 1,4-diaminoanthraquinone (1,4-DAAQ) were studied. Additionally, the effects of hydrogen bond formation between O–H group in hydroxyethylamino substituent and the carbonyl oxygen atom of anthraquinone were investigated.The spectroscopic behavior of the studied derivatives strongly depended on the solvent–solute interactions and the nature of solvent. The values of pKa for the new anthraquinones were determined by the combined potentiometric and spectrophotometric titration methods.

Graphical abstractFigure optionsDownload full-size imageDownload as PowerPoint slideHighlights► The number of amino substituents directly affects the basicity of the examined compounds. ► 1,4-diamino-substituted compounds have higher pKa value than monosubstituted derivatives. ► Two amino substituents present in position 1 and 4 cause vibrational overtones.