| Abstract | U cilju proučavanja utjecaja heterocikličke jezgre kao supstituenta na fotokemijsko ponašanje konjugiranih butadienskih sustava, Wittigovom reakcijom sintetizirani su novi piridinski derivati butadiena 3-[4-(2-vinilfenil)buta-1,3-dienil]piridin (1) i 4-[4-(2-vinilfenil)buta-1,3-dienil]piridina (2) kao smjese geometrijskih izomera. Iz smjesa geometrijskih izomera uspješno su izolirani cis,trans-1 i trans,trans-1 te cis,trans-2 i trans,trans-2. Novosintetizirani derivati 1 i 2 podvrgnuti su fotokemijskim reakcijama na 300 i 350nm u smislu priprave novih bicikličkih struktura fotokemijskom metodologijom. Početni spojevi pokazali su različito fotokemijsko ponašanje. Fotoreakcija spoja 1 dovodi do stvaranja bicikličkog produkta rel-3-[(9S)-triciklo[6.3.1.02,7]dodeka-2,4,6,10-tetraen-9-il]piridina (rel-(9S)-7), dok osvjetljavanjem spoja 2 dolazi do stvaranja intramolekulskom cikloadicijom većinskog bicikličkog rel-4-[(9S)-triciklo[6.3.1.02,7]dodeka-2,4,6,10-tetraen-9-il]piridina (rel-(9S)-8) i manjinskog tricikličkog produkta rel-4-[(10S)-tetraciklo[7.2.1.02,11.03,8]dodeka-3,5,7-trien-10-il]piridina (rel-(10S)-9). Polazni spojevi 1 i 2 kao i njihovi fotoprodukti okarakterizirani su modernim spektroskopskim metodama (jednodimenzionalni i dvodimenzionalni NMR, UV, IR i MS). Novi potencijalni farmakološko interesantni spojevi dobiveni su jednostavnim pristupom koristeći svjetlo kao reagens i pogodni su za daljnje transformacije i funkcionalizacije. |
| Abstract (english) | In order to study the influence of heterocyclic nuclei as substituents on the photochemical behavior of the conjugated butadiene systems, new butadiene derivatives 3-[4-(2-vinylphenyl)buta-1,3-dienyl]pyridine (1) and 4-[4-(2-vinylphenyl)buta-1,3-dienyl]pyridine (2) with pyridine were synthesized by Wittig reaction as a mixture of geometric isomers. From a mixture of geometric isomers we isolated both isomers cis,trans-1, trans,trans-1 and cis,trans-2 and trans,trans-2. The newly synthesized derivatives 1 i 2 undergo photochemical reactions at 300 and 350 nm to give new bicyclic structures by photochemical cycloaddition. The initial compounds display diverse photochemical behavior. Photoreaction of compound 1 leads to the formation of the bicyclic product rel-3-[(9S) tricyclo[6.3.1.02,7]dodeca-2,4,6,10-tetraen-9-yl]pyridine (rel-(9S)-7), while illuminating the compound 2 leads to major bicyclic product rel-4-[(9S)-tricyclo[6.3.1.02,7]dodeca-2,4,6,10-tetraen-9-yl]pyridine (rel-(9S)-8) and as a minor product a tricyclic product, rel-4-[(10S)-tetracyclo[7.2.1.02,11.03,8]dodeca-3,5,7-trien-10-yl]pyridine (rel-(10S)-9) is gained by intramolecular cycloaddition. The structure of starting compounds 1 i 2 as well as their photoproducts 7-9 were characterized by modern spectroscopic methods (one and two dimensional NMR, UV, IR and MS). New potential pharmacologically interesting compounds were obtained by utilizing light, as a clean and accessible reagent, which are suitable for further transformation and functionalizations. |
