Mehanokemijska sinteza bakrovih tereftalata i njihova primjena kao katalizatora u Friedländerovoj reakciji

master's thesis

• Title (english): Mechanochemical synthesis of copper terephthalates as catalysts for the Friedländer reaction
• Author: Nika Rožić
• Mentor: Vjekoslav Štrukil (mentor)
• Committee member: Vesna Petrović Peroković (predsjednik povjerenstva)
• Committee member: Mirta Rubčić (član povjerenstva)
• Committee member: Davor Kovačević (član povjerenstva)
• Committee member: Ines Primožič (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2021-02-17, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Metalo-organske mreže su porozni materijali koji pripadaju skupini koordinacijskih polimera te se sastoje od metalnih atoma ili klustera i organskih liganada. Dimetilformamidni solvat bakrovog(II) tereftalata, kao primjer katalitički aktivne metalo-organske mreže, je sintetiziran mehanokemijskom metodom pri čemu je dobiveni produkt identičan produktu solvotermalne sinteze. Također su sintetizirani slojeviti dvostruki hidroksidi bakra(II) s tereftalatnim i 2,3,5,6-tetrafluortereftalatnim premosnim anionima otopinskom, mehanokemijskom i hidrotermalnom metodom. Svim pripravljenim spojevima je ispitana katalitička aktivnost u modelnoj reakciji između 2-aminobenzilnog alkohola i acetofenona, zvanoj modificirana Friedländerova sinteza. Slojeviti bakrov(II) hidroksid, kao najučinkovitiji katalizator, upotrijebljen je zatim u pripravi raznih derivata kinolina polazeći iz 2-aminobenzilnog alkohola i različito supstituiranih aromatskih ketona. Spektroskopijom NMR istražen je mehanizam modelne reakcije, a također je predložen i mehanizam oksidacije alkohola do aldehida katalizirane bakrovim katalizatorom.

Abstract (english)

Metal-organic frameworks (MOF) are porous materials consisting of metal ions or clusters and organic ligands. A dimethylformamide solvate of copper(II) terepththalate, as the catalytically active MOF, was synthesized by mechanochemical ball milling, resulting in the product identical to the one prepared by a solvothermal synthesis. Also, layered copper(II) double hydroxides with terephthalate and 2,3,5,6-tetrafluoroterephthalate bridging anions were prepared by solution, mechanochemical and hydrothermal syntheses. The synthesized products were assessed for their catalytic activity in a model modified Friedländer reaction between 2-aminobenzyl alcohol and acetophenone. The layered copper double hydroxide terephthalate as the most efficient catalyst, was used in the synthesis of several quinoline derivatives starting from 2-aminobenzyl alcohol and various aromatic ketones. Finally, the mechanism of the model reaction has been probed by NMR spectroscopy, while the mechanism of alcohol oxidation, catalysed by the copper catalyst, has also been proposed.

• Keywords: Friedländerova reakcija; kinolini; mehanokemija; metalo-organske mreže
• Keywords (english): Friedländer reaction; mechanochemistry; metal-organic frameworks; quinolines
• Language: croatian
• URN:NBN: urn:nbn:hr:217:948808
• Project: Number: IP-2018-01-3298; Title: Cikloadicijske strategije prema policikličkim gvanidinima; Acronym: CycloGu; Leader: Davor Margetić; Jurisdiction: Croatia; Funder: HRZZ; Funding stream: IP
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2023-02-17
• Created on: 2021-03-09 13:34:07