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U sklopu diplomskog rada razvijena je metoda sinteze halogeniranih derivata marinoaziridina. Strukturni derivati 8a-8h pripravljeni su reakcijom različito supstituiranih N-tosil imina 7a-7h i akiralne 2-kinolinonske sulfonijeve soli 6 u prisustvu baze, kao smjese cis i trans izomera u dobrom iskorištenju. Ispitan je utjecaj baze, temperature i iminskog supstituenta na iskorištenje i dijastereoselektivnost reakcije. Uočeno je da baza nema bitan utjecaj na dijastereoselektivnost aziridinacije. Dijastereoselektivnost reakcije je različita i ovisna je o iminskom supstituentu. U većini slučajeva prevladava trans izomer, dok je neobična cis dijastereoselektivnost uočena kod derivata 8d. U drugom dijelu istraživanja ispitani su uvjeti odjeljivanja enantiomera novosintetiziranih spojeva na polisaharidnim kiralnim nepokretnim fazama temeljenim na derivatima amiloze i celuloze primjenom visokodjelotvorne tekućinske kromatografije. Chiral ART Cellulose SC nepokretna faza sa selektorom tris-(3,5-diklorfenilkarbamat) celulozom pokazala se najboljim izborom u odjeljivanju enantiomera, ali i u odjeljivanju cis i trans izomera. In this thesis, a method of synthesis of halogenated marinoaziridine derivatives was developed. Structural derivatives 8a-8h were prepared by reaction of variously substituted N-tosyl imines 7a-7h and achiral 2-quinolinone sulfonium salt 6 in the presence of a base, as a mixture of cis and trans isomers in good yield. The effect of base, temperature and imine substituent on the yield and diastereoselectivity of the reaction was investigated. It was observed that the base had no significant effect on the diastereoselectivity of aziridination. The diastereoselectivity of the reaction is different and depends on the imine substituent. In most cases, the trans isomer predominates, while unusual cis diastereoselectivity was observed in derivative 8d. In the second part of this research, the conditions of enantioseparation of newly synthesized compounds on polysaccharide chiral stationary phases based on amylose and cellulose derivatives were investigated using high performance liquid chromatography. Chiral ART Cellulose SC stationary phase with selector cellulose tris-(3,5-dichlorophenylcarbamate) proved to be the best choice in the enantioseparation, but also in the separation of cis and trans isomers. |
