Ferrocén-szubsztituált heterociklusok és származékaik szintézise, szerkezetigazolása és komplex spektroszkópiai vizsgálata = Synthesis, structure determination and complex spectroscopic study of ferrocene-substituted heterocycles and their derivatives

Uj, mono- es poliheterociklusokkal egyszeresen es tobbszorosen szubsztitualt ferrocenszarmazekokat allitottunk elő. Szerkezetuket komplex nagyműszeres vizsgalatokkal (IR, MS, rontgendiffrakcio, multinuklearis NMR) deritettuk fel. Etil-azido-ferrocenilakrilatbol es iminofoszforanjabol uj ferrocentartalmu 1,2,3-triazolt, aminobutadient, oxazolont es imidazolont szintetizaltunk. Acetilferrocenből es 1,1’-diacetilferrocenből 1-[piridazin-3(2H)-on-6-il]ferrocent es 1,1’-bisz[piridazin-3(2H)-on-6-il]ferrocent, ebből fazistranszfer dialkilezessel es diallilszarmazekanak metatezisevel uj ferrocenofanokat allitottunk elő. Biologiai vizsgalatok celjaira, ferrocent es aromas/heteroaromas gyűrűt tartalmazo kalkonok, ezekből pirazolin/pirazol-, szteroid-, glikozid- es oligopeptid szarmazekok keszultek. 1,1’-Diacilferrocenekből hidrazinnal diaza-butadien lancokat es ket ferrocent tartalmazo makro-ciklusokat, esetenkent ezek mono- es dipalladol komplexeit szintetizaltuk. A formil- es acetilferrocen tioszemikarbazonjabol ferrocenszubsztitualt 1,3-tiazinonokat, tiazolokat, tiazolonokat, pirimidonokat es imidazolonokat izolaltunk. Előallitottuk 1,1’-diacilferrocenek aril- es heteroaril-szubsztitualt mono- es dihidrazonjait es tanulmanyoztuk reakciokeszseguket 1,3-dipolaris cikloaddiciokban. A kiserleti munka soran tapasztalt szerkezet-reaktivitas osszefuggeseket es molekuladinamikai tulajdonsagokat DFT szamitasokkal ertelmeztuk. | We prepared novel ferrocenes (Fc) substituted by mono- and polyheterocycles. Their structure was elucidated by complex high-performance instrumental methods (IR, MS, X-ray, multinuclear NMR). By multistep reactions, ethyl-azido-Fc-acrylate and its iminophosphorane were transformed into novel Fc-containing 1,2,3-triazole, aminobutadiene, oxazolone and imidazolone derivatives. Starting from 1-acetyl- and 1,1’-diacetyl-Fc we synthesized 1-[pyridazin-3(2H)-one-6-yl]ferrocene and 1,1’-bis[pyridazin-3(2H)-one-6-yl]ferrocene, phase-transfer alkylation and metathesis of diallyl derivative of the latter afforded new ferrocenophanes. On purpose to biological investigations numerous chalcones with ferrocene and aryl/hetaryl motifs and their novel pyrazoline/pyrazole-, steroide-, glycoside- or oligopeptide derivatives were prepared. Reactions of 1,1’-diacylferrocenes with hydrazine resulted in macrocycles containing diazabutadiene chains and two ferrocene units, occasionally their mono- and dipalladol complexes were synthesized. Thiosemicarbazones, obtained from formyl- and acetylferrocene, were converted into Fc-substituted 1,3-thiazinones, thiazoles, thiazolones, pyrimidones and imidazolones. We prepared aryl/hetaryl-substituted mono- and dihydrazones of some 1,1’-diacylferrocenes and studied their reactivity in 1,3-dipolar cycloadditions. The experimentally observed structure-reactivity relationship and molecular dynamics were interpreted by DFT calculations.