Spectral and Acid−Base Features of 3,7-Dihydroxy-2,8-diphenyl-4H,6H-pyrano[3,2-g]chromene-4,6-dione (Diflavonol)A Potential Probe for Monitoring the Properties of Liquid Phases

• Published in: Journal of organic chemistry Vol. 68; no. 15; pp. 5860 - 5869
• Main Authors: Roshal, A. D, Moroz, V. I, Pivovarenko, V. G, Wróblewska, A, Błażejowski, J
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 25.07.2003
• Subjects: Chemistry; Exact sciences and technology; Heterocyclic compounds; Heterocyclic compounds with o, s, se, te hetero atom and condensed derivatives; Organic chemistry; Preparations and properties; Solvent effect; Theoretical study; Alcohol; Dissociation constant; Ground state; Acidity; Liquid phase; Tautomer; Tricyclic compound; Oxygen heterocycle; Ketone; Fluorescence spectrometry; Absorption spectrometry; Thermodynamics; Emission spectrometry; Density functional method; Aromatic compound; Alkalinity; AM1 method; Excited state
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo034200f

Diflavonol is a molecule that can exist in neutral or anionic form and in several tautomeric forms in ground and excited states. Absorption and emission spectroscopy combined with theoretical calculations have shown that only one tautomer of neutral diflavonol exists in the ground state, but two exist in the excited state. In the latter case, one is the tautomer originating from the ground state tautomer, which exists in strongly protic solvents, the other is the phototautomer occurring in weakly protic or aprotic solvents as a result of the intramolecular transfer of one proton. The OH groups present in diflavonol and involved in weak intramolecular hydrogen bonds exhibit a proton-donating ability reflected by the experimental values of acidity constants or theoretical enthalpies and free energies of proton detachment. The electronically excited molecule is a relatively strong acid when it loses one proton. With increasing basicity of the medium, monoanionic and dianionic forms occur which exhibit spectral characteristics and an emission ability different from those of neutral diflavonol. These interesting features of diflavonol open up possibilities for the analytical use of the compound and its application as a spectral probe sensitive to the properties of liquid phases.