Funkcionalizacija heterocikličkih benzobiciklo[3.2.1]oktadienskih sustava

master's thesis

• Title (english): Functionalization of heterocyclic benzobicyclo[3.2.1]octadiene systems
• Author: Matej Lukač
• Mentor: Dragana Vuk (mentor)
• Committee member: Dragana Vuk (predsjednik povjerenstva)
• Committee member: Irena Škorić (član povjerenstva)
• Committee member: Danijela Ašperger (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2018-11-30, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry; Organic Chemistry

Abstract

Fotokatalitičke oksigenacije predstavljaju tip homogene fotokatalitičke reakcije pomoću kojih se molekularni kisik na vrlo jednostavan način uz pomoć svjetlosti ugrađuje u produkte. U ovome radu ispitan je utjecaj naboja Mn(III) porfirina, koncentracije kisika te položaja heteroatoma u prstenu na tijek i mehanizam reakcija fotokatalitičke oksigenacije na tiofenskim derivatima koji sadrže biciklo[3.2.1]oktadiensku strukturu, koja je kostur brojnih važnih biološki aktivnih prirodnih spojeva i njihovih metabolita. Reakcije fotokatalitičke oksigenacije provedene su osvjetljavanjem u smjesi aceton-voda (50:50) uz anionski ili kationski manganov(III) porfirin kao katalizator, čime se izbjegla upotreba toksičnih otapala, te propuhivanjem kisikom ili zrakom pri pH 10. Početni prekursori 1 i 2 dobiveni su Wittigovom reakcijom iz difosfonijeve soli i odgovarajućeg aldehida, nakon čega su podvrgnuti fotokemijskoj reakciji. Fotokemijskom reakcijom sintetizirani su biciklički tiofenski sustavi 3 i 4, s različitim položajem heteroatoma u prstenu. Spojevi 3 i 4 podvrgnuti su zatim reakciji fotokatalitičke oksigenacije čime je dobiven niz oksigeniranih fotoprodukata: hidroksida, hidroperoksida i ketona, koji su u potpunosti spektroskopski okarakterizirani.

Abstract (english)

Photocatalytic oxygenation reactions are a type of homogeneous photocatalytic reactions in which molecular oxygen is incorporated into products. In this work, impact of Mn(III) porphyrin catalyst, oxygen concentration and position of heteroatom on the course and mechanism of the photocatalytic oxygenation reactions was investigated. Reactions were performed on the thiophene derivatives containing the bicyclo[3.2.1]octadiene moiety, which is the skeleton of many important biologically active natural compounds and their metabolites. Photocatalytic oxygenations were conducted in the presence of anionic or cationic manganese porphyrin as a catalyst, at pH 10 in oxygen- or air-saturated system. Initial precursors 1 and 2 were obtained by Wittig reaction from diphosphonic salt and the corresponding aldehyde, followed by photochemical reaction. Irradiation of starting compounds 1 and 2 gave bicyclic thiophene systems 3 and 4. Compounds 3 and 4 are then subjected to photocatalytic oxygenation reaction, resulting with a series of oxygenated photoproducts: hydroxides, hydroperoxides and ketones, which were completely spectroscopic characterized.

• Keywords: fotokataliza; benzobiciklo[3.2.1]oktadien; fotokatalitička oksigenacija; Mn(III) porfirini
• Keywords (english): photocatalysis; benzobicyclo[3.2.1]octadienes; photocatalytic oxygenation; Mn(III) porphyrins
• Language: croatian
• URN:NBN: urn:nbn:hr:149:898437
• Study programme: Title: Chemical Engineering - Graduate study; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra inženjer/inženjerka kemijskog inženjerstva (magistar/magistra inženjer/inženjerka kemijskog inženjerstva)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2022-02-23 12:22:56