Synthesis and Spectroscopic Study <strong>of</strong> Benzanthrone 3-N-Derivatives asNew Highly Fluorescent DyesE.M.Kirilova 1 , A.I.Puchk<strong>in</strong> 1 , I.D.Ivanova 2 , A.Ruža 1 , G.K.Kirilov, N.Orlova 21 Chemistry Department, Daugavpils University, 13 Vienibas str., LV-5401, Daugavpils(Latvia);2 Faculty <strong>of</strong> Chemistry, University <strong>of</strong> Latvia, 48 Valdemara str., LV-1013, Riga (Latvia).e-mail: elena.kirilova@<strong>in</strong>box.lvToday many techniques use fluorescent dyes for the labell<strong>in</strong>g <strong>of</strong> biological objects. Newpractical uses call for the synthesis <strong>of</strong> new fluorescent probes with improved properties. Inpresent work, we have synthesized a number <strong>of</strong> 3-am<strong>in</strong>obenzanthrone N-derivatives –substituted am<strong>in</strong>es, im<strong>in</strong>es and amid<strong>in</strong>es, obta<strong>in</strong><strong>in</strong>g highly fluorescent compounds [1].Synthesized dyes are the analogues <strong>of</strong> cell membrane hydrophobic probe – 3-methoxybenzanthrone,but new derivatives are long-wavelength light-emitt<strong>in</strong>g fluorescent dyes.YNR 1R 2YXOIIYNRNR 1R 2OIOIIIYNROIVThe spectral behaviour <strong>of</strong> the obta<strong>in</strong>ed dyes was <strong>in</strong>vestigated. We have studied thespectral properties <strong>of</strong> prepared derivatives – absorption and fluorescence spectra <strong>in</strong>various solvents. For obta<strong>in</strong>ed dyes large Stokes shift values (about 100 nm) are observed,excitation maxima <strong>of</strong> the dyes are located near 500 nm and emission maxima near 650nm. In addition these compounds are showed strong fluorescent solvatochromism.It was found that many <strong>of</strong> synthesized compounds are quite sensitive to the surround<strong>in</strong>genvironments and are potential fluorescent probes for screen<strong>in</strong>g structural and functionalalterations <strong>of</strong> cell membranes.- 8 -
Synthesis and Crystal Structure <strong>of</strong> Novel Amid<strong>in</strong>o Derivatives <strong>of</strong>BenzanthroneE.M.Kirilova 1 , I.D.Ivanova 2 , A.I.Puchk<strong>in</strong> 1 , S.V.Belyakov 31 Chemistry Department, Daugavpils University, 13 Vienibas str., LV-5401, Daugavpils(Latvia);2 Faculty <strong>of</strong> Chemistry, University <strong>of</strong> Latvia, 48 Valdemara str., LV-1013, Riga (Latvia);3 Latvian Institute <strong>of</strong> Organic Synthesis, Riga, Latvia.e-mail: elena.kirilova@<strong>in</strong>box.lvToday many techniques use fluorescent dyes for the label<strong>in</strong>g <strong>of</strong> biological objects [1].Practical applications uses call for the synthesis <strong>of</strong> new fluorescent compounds withimproved properties for a specific requirement. In this connection the <strong>in</strong>tensive<strong>in</strong>vestigations for preparation <strong>of</strong> new fluorescent probes now have developed.In our previous <strong>in</strong>vestigations were synthesized a number <strong>of</strong> benzanthrone N-conta<strong>in</strong><strong>in</strong>gderivatives, obta<strong>in</strong><strong>in</strong>g highly fluorescent compounds [2, 3]. Synthesized dyes are sensitivelong-wavelength light-emitt<strong>in</strong>g fluorescent dyes, which have high photostability and lowcytotoxicity. It has been shown that some <strong>of</strong> obta<strong>in</strong>ed compounds are potential fluorescentprobes for screen<strong>in</strong>g structural and functional alterations <strong>of</strong> cell membranes and forestimation <strong>of</strong> the immune state [2].The aim <strong>of</strong> this work was the modification <strong>of</strong> some <strong>of</strong> benzanthrone derivatives (I, III) by<strong>in</strong>clud<strong>in</strong>g new substituents <strong>in</strong> chromophoric system <strong>in</strong> order to f<strong>in</strong>d potential fluorescentprobes with large lum<strong>in</strong>escence <strong>in</strong>tensity and high stability. Here we present the synthesis<strong>of</strong> several new benzanthrone derivatives (II, IV) with amid<strong>in</strong>e group:NH 2NRNR 1R 2OIOIIBrBrN H 2OIIIRR 2R 1NNOIVSynthesized derivatives have bright from yellow to red fluorescence <strong>in</strong> <strong>organic</strong> solventsand solid state. The structure <strong>of</strong> obta<strong>in</strong>ed compounds was confirmed by NMR and IRspectroscopy. In addition thermal analysis and crystal structures <strong>of</strong> studied compoundshave been <strong>in</strong>vestigated.1. Kirilova, E. M; Kaln<strong>in</strong>a, I; Kirilov, G. K; Meirovics, I. J. Fluoresc 2008, 18 (3-4), 645-648.2. Kirilova, E. M; Belyakov, S. V; Kaln<strong>in</strong>a, I. Topics <strong>in</strong> Chemistry & Materials Science, S<strong>of</strong>ia:Heron Press (ed: G. Vayssilov, R. Nikolova) 2009, 3, 19-28.3. Gorbenko, G.; Trusova, V.; Kirilova, E.; Kirilov, G.; Kaln<strong>in</strong>a, I.; Vasilev, A.; Kaloyanova, S.;Deligeorgiev, T. Chem. Phys. Lett, 2010, 495, 275–279.- 9 -