Sinteza konjugata heterocikla i ferocena i njihovih metalnih kompleksa

master's thesis

• Title (english): Synthesis of heterocycle and ferrocene conjugates and their metal complexes
• Author: Silvio Jakopec
• Mentor: Silvana Raić-Malić (mentor)
• Mentor: Srećko Kirin (komentor)
• Committee member: Silvana Raić-Malić (predsjednik povjerenstva)
• Committee member: Silvija Maračić (član povjerenstva)
• Committee member: Srećko Kirin (član povjerenstva)
• Granter: University of Zagreb; Faculty of Chemical Engineering and Technology; Zagreb
• Defense date and country: 2020-07-03, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

Ferocen pripada skupini metalocena te predstavlja značajan farmakofor u medicinskoj kemiji, a njegovi su derivati važni ligandi u koordinacijskoj kemiji. U ovom radu opisana je sinteza novih mono- i bis-ferocenskih derivata aromatskih amina s 1,2,3-triazolnom premosnicom te njihovih metalnih kompleksa. Mono- i bis-propargilirani terminalni alkini (1–3) dobiveni su alkiliranjem 2,2'-dipiridilamina, anilina i 2-aminobenzotiazola s propargil-bromidom u bazičnom mediju, dok su azidni prekursori za klik reakcije 1-azidometilferocen (4), 1-azidoferocen (5) i 1-azidoetilferocen (6) pripravljeni iz odgovarajućih derivata ferocena s natrijevim azidom. Ciljani konjugati ferocena i heterocikla (7–9) sintetizirani su regioselektivnom 1,3-dipolarnom cikloadicijom propargiliranih aromatskih amina (1–3) i ferocenskih azida (4–6). Konjugati ferocena i heterocikla korišteni su kao ligandi u sintezi kompleksa s metalima Zn(II) i Cu(II). Strukture novosintetiziranih derivata potvrđene su spektroskopijom 1H i 13C NMR. Spektroskopska svojstva dobivenih kompleksa istražena su spektroskopijom NMR, UV-Vis i IR. Kristalna struktura Cu(II) kompleksa konjugata ferocena i 2,2'-dipiridilamina povezanih 1,2,3-triazolnom premosnicom određena je difrakcijom X-zraka na monokristalu.

Abstract (english)

Ferrocene belongs to the group of metallocenes and represents a significant pharmacophore in medicinal chemistry along with its derivatives being important ligands in coordination chemistry. In this work, novel mono- and bis-ferrocenyl derivatives connected to aromatic amine through 1,2,3-triazolyl linker and their metal complexes were prepared. Mono- and bis-propargylated terminal alkynes (1–3) were obtained by reaction of 2,2'-dipyridylamine, aniline and 2-aminobenzothiazole with propargyl bromide in a basic media while azide precursors for the „click“ reaction of 1-azidomethylferocene (4), 1-azidoferocene (5) and 1-azidoethylferocene (6) were prepared from corresponding ferrocene derivatives and sodum azide. Conjugates of ferrocene and heterocycles (7–9) were prepared by the Huisgen 1,3-dipolar cycloaddition of propargylated aromatic amines (1–3) and ferrocene azides (4–6). The reactions were performed using copper(II) acetate in methanol as a source of Cu(I) ionsConjugates of ferrocene and heterocycles were used as ligands in the synthesis of Zn(II) and Cu(II) metal complexes. The structures of the newly synthesized derivatives were confirmed by 1H and 13C NMR spectroscopy. The spectroscopic properties of the obtained complexes were investigated by NMR, UV-Vis and IR spectroscopy. The crystal structure of the Cu(II) complex of ferrocene and 2,2'-dipyridylamine conjugates linked by a 1,2,3-triazole was determined by single-crystal X-ray diffraction.

• Keywords: ferocen; 1 3-dipolarna cikloadicija; metalni kompleksi; 1 2 3-triazol
• Keywords (english): ferrocene; 1 3-dipolar cycloaddition; metal complexes; 1 2 3-triazole
• Language: croatian
• URN:NBN: urn:nbn:hr:149:185478
• Project: Number: KK.01.1.1.04.0013; Title: Inovativna rješenja u katalitičkim proizvodnim procesima za potrebe farmaceutske industrije; Acronym: CAT PHARMA; Leader: Srećko Kirin; Jurisdiction: eu; Funder: EC; Funding stream: EFRR
• 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; Embargo expiration date: 2021-07-01
• Created on: 2022-03-03 10:56:14