Priprava novih aneliranih tiofenskih biciklo[3.2.1]oktadienskih derivata

master's thesis

• Title (english): Preparation of new anelated thiophene bicyclo[3.2.1]octadiene derivatives
• Author: Mirela Pašičko
• Mentor: Dragana Vuk (mentor)
• Committee member: Dragana Vuk (predsjednik povjerenstva)
• Committee member: Irena Škorić (član povjerenstva)
• Committee member: Ljerka Kratofil Krehula (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2018-07-11, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry; Organic Chemistry

Abstract

U svrhu sinteze novih policikličkih derivata biciklo[3.2.1]oktadienskih sustava fuzioniranih s tiofenskom jezgrom, provedene su fotokemijske ciklizacije i aldolne kondenzacije na tieno-benzobiciklo[3.2.1]oktadienskim derivatima. Početni supstrat 1 je jednostavno dobiven Vilsmeier-Haackovom reakcijom formiliranja 2,3-[3,2-b-tieno]-6,7-benzobiciklo[3.2.1]okta-2,6-diena. Iz nastalog karbaldehida Wittigovom reakcijom sintetizirani su novi p-metil- i p-metoksi- supstituirani stirilni tieno-benzobiciklo[3.2.1]oktadienski derivati 2 i 3 koji su podvrgnuti fotoreakcijama u smislu priprave novih policikličkih struktura fotokemijskom metodologijom. Fotokemijskom reakcijom spoja 2 potpuna konverzija postignuta je nakon 18 h, te je izoliran ciklizacijski produkt 4 u 23 %-tnom iskorištenju, dok je osvjetljavanjem spoja 3 izoliran produkt 5 u 37 %-tnom iskorištenju, također nakon 18 h. Provođenjem aldolne reakcije karbaldehida 1 s acetonom dobiven je spoj 6 koji predstavlja tieno-fuzionirani benzobiciklo[3.2.1]oktadienski sustav s proširenom konjugacijom. Svi polazni spojevi 1 - 3 kao i njihovi produkti 4 - 6 okarakterizirani su modernim spektroskopskim metodama (jednodimenzionalni i dvodimenzionalni NMR, UV).

Abstract (english)

In order to prepare novel polycyclic derivatives of bicyclo[3.2.1]octadiene systems fused with thiophene ring, photochemical cyclizations and aldol condensations were carried out. The starting substrate 1 was easily obtained by Vilsmeier-Haack’s formylation reaction of 2,3-[3,2-b-thieno]-6,7-benzobicyclo[3.2.1]octa-2,6-diene. From the obtained carbaldehyde, novel p-methyl- and p-methoxy- substituted styryl thieno-benzobicyclo[3.2.1]octadiene derivatives 2 and 3 were formed by Wittig's reaction and underwent photochemical reactions in terms of obtaining new polycyclic structures. Full conversion of photochemical reaction of compound 2 was achieved after 18 h and the cyclization product 4 has been isolated with the yield of 23 %, while after the irradiation of compound 3 the product 5 was isolated in 37 % yield, also after 18 h. By carrying out aldol reaction of carbaldehyde 1 with acetone, product 6 was obtained which represents thieno-fused benzobicyclo[3.2.1]octadiene system with extended conjugation. The structure of the starting compounds 1 – 3 as well as of their products 4 – 6 were characterized by modern spectroscopic methods (one and two dimensional NMR, UV).

• Keywords: tiofen; benzobiciklo [3.2.1] oktadieni; fotokemija; aldolna reakcija; Vilsmeier-Haackova reakcija
• Keywords (english): tiophene; benzobicyclo [3.2.1] octadienes; photochemistry; aldol reaction; Vilsmeier-Haack reaction
• Language: croatian
• URN:NBN: urn:nbn:hr:149:573008
• Study programme: Title: Applied Chemistry - Graduate study; specializations in: Environmental chemistry and green technologies, Advanced materials and technologies, Applied organic chemistry; Course: Applied organic chemistry; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra primijenjene kemije (magistar/magistra primijenjene kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access
• Created on: 2020-06-02 11:34:03