Title 1,3-Dipolarna cikloadicija na tetra- i tripiridilporfirine
Title (english) 1,3-Dipolar cycloaddition reactions of tetra- and tripyridylporphyrins
Author Magdalena Vincetić
Mentor Nela Malatesti (mentor)
Committee member Jasminka Giacometti (predsjednik povjerenstva)
Committee member Duško Čakara (član povjerenstva)
Committee member Nela Malatesti (član povjerenstva)
Granter University of Rijeka (Faculty of Biotechnology and Drug Development) Rijeka
Defense date and country 2018-10-25, Croatia
Scientific / art field, discipline and subdiscipline BIOTECHNICAL SCIENCES Biotechnology
Abstract 1,3-dipolarna cikloadicija jedna je od najvažnijih metoda u organskoj kemiji za sintezu peteročlanih prstena. Ovdje dolazi do reakcije između vrste zwitterionske rezonantne strukture, odnosno 1,3-dipola i spoja koji u svojoj strukturi ima višestruku vezu, odnosno dipolarofila. Jedna vrsta 1,3-dipola alilnog tipa su azometinski ilidi. Porfirini u 1,3-dipolarnoj cikloadiciji mogu sudjelovati kao dipolarofili i reagirati s azometinskim ilidima gdje nastaju klorini i bakterioklorini.
U ovom radu su Adler-Longo metodom sintetizirani 5,10,15,20-tetrakis(3-piridil)porfirin i 5-(4-acetamidofenil)-10,15,20-tris(3-piridil)porfirin te su dalje korišteni u reakcijama 1,3-dipolarne cikloadicije. Sinteze su provedene konvencionalnim putem i u mikrovalnim uvjetima. Oba porfirina su korištena za reakcije s dva različita azometinska ilida generirana in situ iz sarkozina i paraformaldehida te iz sarkozina i benzaldehida.
Reakcijom 1,3-dipolarne cikloadicije sintetiziran je novi spoj, monocikloadukt (klorin) 5,10,15,20-tetrakis(3-piridil)porfirina. Azometinski ilid je u ovoj reakciji generiran iz sarkozina i paraformaldehida, a reakcija je provedena konvencionalnim putem. Struktura monocikloadukta je potvrđena 1H i 13C NMR te UV/vis spektroskopijom. Apsorpcijski spektar novosintetiziranog monocikloadukta odgovara apsorpcijskom spektru karakterističnom za klorine. Novi monocikloadukt je okarakteriziran i fluorescencijskim spektrom. Produkti dobiveni u svim ostalim reakcijama provedenim konvencionalnim putem i u mikrovalnim uvjetima nisu izolirani kao čisti spojevi te struktura ovih spojeva nije mogla biti potvrđena NMR spektroskopijom.
Abstract (english) 1,3-dipolar cycloaddition is one of the most important methods in organic chemistry for the synthesis of five-membered rings. This is the reaction between species represented by zwitterionic resonance structures (1,3-dipole) and multiple bond system (dipolarophile). Azomethine ylides are allyl type 1,3-dipoles. Porphyrins can participate as dipolarophiles in 1,3-dipolar cycloaddition with azomethine ylides; chlorins and bacteriochlorins can be obtained as a result of this reaction.
In this work, 5,10,15,20-tetrakis(3-pyridyl)porphyrin and 5-(4-acetamidophenyl)-10,15,20-tris(3-pyridyl)porphyrin are synthesized using Adler-Longo method and used in 1,3-dipolar cycloaddition reactions. Syntheses were carried out using conventional methods and microwave irradiation. Both porphyrins were used in 1,3-dipolar cycloaddition with two different azomethine ylides generated in situ. One was generated from sarcosine and paraformaldehyde and the other from sarcosine and benzaldehyde.
1,3-dipolar cycloaddition reaction of 5,10,15,20-tetrakis(3-pyridyl)porphyrin and azomethine ylide afforded monocycloadduct (chlorin). Azomethine ylide was in that case generated from sarcosine and paraformaldehyde. The reaction was carried out using conventional method. The structure of monoaduct was confirmed by 1H i 13C NMR and UV/vis spectroscopy. The absorption spectrum of monoaduct is typical of a chlorin. New monoaduct was also analyzed by fluorescence spectroscopy. Products obtained from other performed reactions, conventional and microwave assisted, were not isolated pure, therefore the structures of these compounds could not be confirmed by NMR spectroscopy.
Keywords
1
3-dipolarna cikloadicija
azometinski ilid
porfirin
klorin
sinteza uz mikrovalno ozračivanje
Keywords (english)
1
3-dipolar cycloaddition
azomethine ylide
porphyrin
chlorin
microwave-assisted synthesis
Language croatian
URN:NBN urn:nbn:hr:193:399660
Study programme Title: Medicinal chemistry Study programme type: university Study level: graduate Academic / professional title: magistar/magistra medicinske kemije (magistar/magistra medicinske kemije)
Type of resource Text
File origin Born digital
Access conditions Open access Embargo expiration date: 2020-01-01
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Created on 2018-11-06 08:29:29