Sinteza novih biciklo[3.2.1]oktadienskih derivata fuzioniranih s tiofenskim prstenom

master's thesis

• Title (english): Synthesis of new bicyclo[3.2.1]octadiene derivatives fused with thiophene ring
• Author: Iva Horvat
• Mentor: Dragana Vuk (mentor)
• Committee member: Dragana Vuk (predsjednik povjerenstva)
• Committee member: Irena Škorić (član povjerenstva)
• Committee member: Šime Ukić (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2018-07-12, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry; Organic Chemistry

Abstract

U ovom radu provest će se funkcionalizacija biciklo[3.2.1]oktadienskog sustava fuzioniranog s tiofenskom jezgorm. Formiliranjem tiofenske jezgre dobiveni aldehid III podvrgnut je Wittigovoj reakciji da bi se dobili 2-tienilni sustavi 1 i 2 koji su zatim fotokemijski ciklizirani. Očekivano je dobivanje novih složenih policikličkih struktura ovisno o elektronskom utjecaju metilne i cijano skupine kao supstituenta. Fotokemijska reakcija metil-supstituiranog spoja 1 dovodi do nastanka ciklizacijskog produkta 3. Međutim, osvjetljavanjem spoja 2 ne dolazi do reakcije, te je izoliran samo početni spoj. Kako bi se ispitao utjecaj položaja heteroatoma na reakcijski mehanizam provela se i sinteza na 3-tienilnom sustavu. Provođenjem fotokemijske reakcije dobiven je biciklički derivat V koji reakcijom Vilsmeier-Haack-ovog formiliranja daje aldehid 4. Novosintetizirani spoj 4 podvrgnut je Wittigovoj reakciji u smislu priprave novih aneliranih sustava. Dobiveni produkt 5 izoliran je u 46 %-tnom iskorištenju te je podvrgnut fotokemijskoj ciklizaciji. Nakon 5 sati dobiven je ciklizacijski produkt 6 u iskorištenju od 28 %. Svi priređeni spojevi 1-6 okarakterizirani su modernim spektroskopskim metodama (1H NMR, 13C NMR, UV, IR).

Abstract (english)

In this work, functionalization of bicyclo[3.2.1]octadiene system fused with thiophene ring will be carried out. Aldehyde III obtained by Vilsmeier-Haack's formylation reaction of thiophene ring, underwent Wittig's reaction in terms of obtaining 2-thienyl systems 1 and 2, which were then photochemically cyclizated. Getting the new complex polycyclic structures depending on the electronic effects of methyl and cyano groups as substituents in the molecule was expected. Photochemical reaction of methyl-substituted compound 1 leads to the cyclization product 3. On the other hand, by illuminating the compound 2, no reaction was observed and only the starting compound was isolated. In order to examine the influence of the position of heteroatom on reaction mechanism, synthesis on 3-thienyl system was carried out. Bicyclic derivative V was obtained by photochemical reaction and then underwent formylation reaction. The new synthesized compound 4 underwent Wittig’s reaction in terms of obtaining new anelated systems. Obtained product 5 was isolated in 46 % yield and then underwent photochemical cyclization. After 5 h, cyclization product 6 was obtained with the yield of 28 %. All obtained compounds 1-6 were characterized by modern spectroscopic methods (1H NMR, 13C NMR, UV, IR).

• Keywords: tiofen; fotokemija; biciklo[3.2.1]oktadienska struktura; Wittigova reakcija; Vilsmeier-Haack-ova reakcija
• Keywords (english): thiophene; photochemistry; bicyclo[3.2.1]octadiene structure; Wittig reaction; Vilsmeier-Haack reaction
• Language: croatian
• URN:NBN: urn:nbn:hr:149:109620
• 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: 2020-06-04 12:27:09