Kiralni reagent za elektrofilno fluoriranje s kininskim derivatom na poliHIPE nosilcu

Markovič, Aleksander Saša (author), Iskra, Jernej (mentor), Krajnc, Peter (comentor)

Pripravil sem polimerne pene s polimerizacijo emulzij z visokim deležem notranje faze, na osnovi 4-vinilbenzil klorida (VBC) in divinil benzena (DVB) ter v ogrodje polimera vgradil kinin, tako s post-polimerizacijsko modifikacijo hiperzamreženega poliHIPE, s substitucijo prostih klorovih atomov na polimernem ogrodju z deprotoniranim kininom. Kot s pripravo etrskega monomera iz VBC in kinina. Kiralno ogrodje kinina je služilo za nadaljnjo pripravo kiralnega elektrofilnega fluorirnega reagenta. Sintetizirane polimere sem očistil s Soxhlet ekstrakcijo ter jih kemijsko karakteriziral s FTIR spektroskopijo in elementno analizo. Nadalje sem s sorpcijo dušika in vrstično elektronsko mikroskopijo preveril tudi morfološke lastnosti materialov. Nato sem na dušik v kininskem bicikličnem fragmentu prenesel fluor s SelectfluorTM. Po potrditvi uspešnega prenosa z jodometrično titracijo sem polimer uporabil za elektrofilno fluoriranje 1,3-dikarbonilnih spojin, na osnovi 1,3-difenilpropan-1,3-diona in etil 2 oksopiperidin-3-karboksilata, ki sem jih karakteriziral z 1H in 19F NMR ter določil enenatiomerni presežek s kiralnim HPLC-jem oz. diastereoizomerni presežek iz kemijskih premikov v 19F NMR spektru.

• Language: Slovenian
• Keywords: Elektrofilno fluoriranje, poliHIPE, kinin, kiralni HPLC
• Work type: Master's thesis/paper
• Typology: 2.09 - Master's Thesis
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Year: 2023
• PID: 20.500.12556/RUL-150573
• COBISS.SI-ID: 172477443
• Publication date in RUL: 20.09.2023

MARKOVIČ, Aleksander Saša, 2023, Kiralni reagent za elektrofilno fluoriranje s kininskim derivatom na poliHIPE nosilcu [online]. Master’s thesis. [Accessed 23 April 2025]. Retrieved from: https://repozitorij.uni-lj.si/IzpisGradiva.php?lang=eng&id=150573

Secondary language

• Language: English
• Title: Chiral reagent for electrophilic fluorination with polyHIPE supported quinine derivative

Abstract

Polymer foams with high internal phase were prepared based on 4-vinylbenzyl chloride (VBC) and divinyl benzene (DVB), where quinine was integrated into the polymer framework, with a post-polymerisation modification of hypercrosslinked polyHIPE by substitution of free chlorine atoms with deprotonated quinine. As well as by ether monomer synthesis, which was prepared from VBC and quinine, where the chiral framework of quinine served later for synthesising a chiral electrophilic fluorinating agent. Synthesised polymers were purified by Soxhlet extraction, and their chemical composition was analyzed by FTIR spectroscopy and elemental analysis. Furthermore, the morphological properties of the materials were analyzed by nitrogen sorption and scanning electron microscopy. Afterwards, the quinine bicyclic moiety's nitrogen was fluorinated with SelectfluorTM. When the success of fluorine transfer was determined by iodometric titration, the polymer materials were further used for electrophilic fluorination of 1,3 dicarbonyl substrates based on 1,3-diphenylpropane-1,3-dione and ethyl 2 oxo-3-piperidine carboxylate which were then characterized by 1H and 19F NMR and chiral HPLC to determine the enantiomeric excess or the diastereomeric excess by the chemical shifts in 19F NMR spectra.

• Keywords: Electrophilic fluorination, polyHIPE, quinine, chiral HPLC