20.500.12556/RUL-175991 Nove pretvorbe 3-azido-1-ciano-4-okso-4H-kinolizina in 3-azido-4-okso-4H-pirido[1,2-a]pirimidina Novel transformations of 3-azido-1-cyano-4-oxo-4H-quinolizine and 3-azido-4-oxo-4H-pyrido[1,2-a]pyrimidine V magistrskem delu smo najprej sintetizirali sedem 3-benzamido-substituiranih pirido[1,2-a]pirimidinonov, kinolizinonov in pirimido[1,2-b]piradizinonov. N-(1-Ciano-4-okso-4H-kinolizin-3-il)benzamid in N-(4-okso-4H-pirido[1,2-a]pirimidin-3-il)benzamid smo v naslednjem koraku hidrolizirali in dobljena amina nato nitrozirali ter v zadnjem koraku diazonijevi soli z natrijevim azidom pretvorili v 3-azido-1-ciano-4H-kinolizin-4-on in 3-azido-4H-pirido[1,2-a]pirimidin-4-on. Z dobljenima azidoma smo preučevali z bakrom katalizirane cikloadicije na terminalne alkine in nekatalizirano cikloadicijo na napeti ciklooktinski derivat. S temi cikloadicijami smo pod optimiziranimi pogoji sintetizirali deset novih spojin, ki smo jih nato okarakterizirali glede na njihovo strukturo in optične lastnosti. S 3-azido-4H-pirido[1,2-a]pirimidin-4-onom smo izvedli tudi fotokemijske pretvorbe, kjer pa smo lahko potrdili le nastanek produkta med azidom in tetrahidrofuranom. Prav tako smo lahko predlagali nov, ustreznejši in eksperimentalno podprt mehanizem termične pretvorbe azidov. Predlagani mehanizem je ustrezen tudi pri fotokemijskih pretvorbah, saj pretvorbe ne glede na način aktivacije najverjetneje potekajo preko skupnega nitrenskega intermediata. Na koncu smo z reakcijo 3-benzamido-9-propargiloksi-4H-pirido[1,2-a]pirimidona z 1,2-bis(2-azidoetoksi)etanom sintetizirali ustrezni bis-cikloadukt kot prekurzor homobifunkcionalnega fluorescenčnega označevalca. In this master's thesis, we first synthesized seven 3-benzamido-substituted pyrido[1,2-a]pyrimidinones, quinolizinones, and pyrimido[1,2-b]pyrazinones. In the next step, N-(1-cyano-4-oxo-4H-quinolizin-3-yl)benzamide and N-(4-oxo-4H-pyrido[1,2-a]pyrimidin-3-yl)benzamide were hydrolyzed and the obtained amines were converted into the corresponding azides via nitrosation. Next, copper-catalyzed cycloadditions of title azides to terminal alkynes and a strain-promoted cycloaddition to a cyclooctyne derivative were studied. Ten novel compounds were synthesized using these two cycloaddition reactions under optimized conditions. All novel compounds were characterized in terms of their structure and optical properties. Photochemical reactions of 3-azido-4H-pyrido[1,2-a]pyrimidin-4-one were also performed, however, only the formation of a product formed in the reaction of azide with tetrahydrofuran could be determined. We also proposed a new, more adequate and experimentally supported mechanism of thermal transformation of title azides. The proposed mechanism of thermal transformation is also amenable to photochemical reactions, as nitrene is most likely formed as a central intermediate regardless of the mode of activation (thermal or photochemical). Finally, by reacting 3-benzamido-9-propargyloxy-4H-pyrido[1,2-a]pyrimidin-4-one with 1,2-bis(2-azidoethoxy)ethane, the corresponding bis-cycloadduct was synthesized as a precursor of a homobifunctional fluorescent marker. fluorescenčni (aza)kinolizini optične lastnosti biokonjugacija "klik kemija" fotokemijske in termične reakcije fluorescent (aza)quinolizines optical properties bioconjugation "click chemistry" photochemical and thermal reactions true false false Slovenski jezik Angleški jezik Magistrsko delo/naloga 2025-11-17 13:00:03 2025-11-17 13:00:10 2025-12-04 12:22:06 0000-00-00 00:00:00 2025 0 0 0000-00-00 NiDoloceno NiDoloceno NiDoloceno 0000-00-00 0000-00-00 0000-00-00 25523 259983363 Humar_Tadej_-_Nove_pretvorbe_3-azido-1-ciano-4-okso-4H-kinolizina_in_3-azido-4-okso-4H-pirido[1,.pdf Humar_Tadej_-_Nove_pretvorbe_3-azido-1-ciano-4-okso-4H-kinolizina_in_3-azido-4-okso-4H-pirido[1,.pdf 1 0D4CFFD0917B6C501F5FF6F5CF60102C d7ad329aae6d89176547ca5a232b66f697ceece661569c7bec50a73fc0486222 a0d3184d-c3ac-11f0-9328-0050569b8976 https://repozitorij.uni-lj.si/Dokument.php?lang=slv&id=222000 Fakulteta za kemijo in kemijsko tehnologijo 0 0 0