pH-Dependent Photoinduced Interconversion of Furocoumaric and Furocoumarinic Acids.
Photo-controlled or photo-regulated molecules, especially biologically active and operating in physiological conditions, are in steady demand. Herein, furocoumaric and furocoumarinic acids being (Z/E)-isomers relative to each other were obtained in two stages starting from psoralen: the alkaline solvolysis of psoralen led to furocoumaric acid, which was further Z → E photoisomerized (365 nm) to furocoumarinic acid. The kinetics of Z → E photoisomerization was monitored by HPLC and UV-vis spectrophotometry. Photophysical characteristics in the aqueous phase for both acids, as well as the reversibility of (Z/E) photoisomerization process, were also assessed. Furocoumarinic acid was found to be visibly fluorescent at pH 2.0-12.0, with the maxima of fluorescence emission spectra being pH-dependent. The reverse E → Z photoisomerization predicted by quantum chemistry calculations as energetically favorable for the monoanionic form of furocoumarinic acid was proved in the experiment while being complicated by pyrone ring closure back to psoralen in acidic and neutral conditions. The preparative synthesis of furocoumarinic acid outlined in this work is particularly valuable in view of a wide range of pharmacological effects previously predicted for this compound.
['Skarga|Vladislav V|VV|', 'Matrosov|Anton A|AA|', 'Nichugovskiy|Artemiy I|AI|0000-0003-2523-2054', 'Negrebetsky|Vadim V|VV|', 'Maslov|Mikhail A|MA|0000-0002-5372-1325', 'Boldyrev|Ivan A|IA|', 'Malakhov|Mikhail V|MV|']
D005363:Ficusin D005453:Fluorescence D011564:Furocoumarins D006863:Hydrogen-Ion Concentration D007536:Isomerism D008027:Light D008968:Molecular Conformation D011753:Pyrones D013056:Spectrophotometry, Ultraviolet
furocoumarinic acid furocoumarins psoralens furocoumaric acid fluorescence quantum chemistry calculations (E → Z)-photoisomerization (Z → E)-photoisomerization UV irradiation pH dependence photoproducts photoswitch