| dc.contributor.advisor | Stevanović, Dragana | |
| dc.contributor.other | Ilić Komatina, Danijela S. | |
| dc.contributor.other | Damljanović, Ivan | |
| dc.contributor.other | Joksović, Milan | |
| dc.creator | Minić, Aleksandra | |
| dc.date.accessioned | 2020-10-24T12:30:57Z | |
| dc.date.available | 2020-10-24T12:30:57Z | |
| dc.date.issued | 2019-04-24 | |
| dc.identifier.uri | http://eteze.kg.ac.rs/application/showtheses?thesesId=7410 | |
| dc.identifier.uri | https://fedorakg.kg.ac.rs/fedora/get/o:1243/bdef:Content/download | |
| dc.identifier.uri | https://nardus.mpn.gov.rs/handle/123456789/17534 | |
| dc.description | Izvod:
U okviru ovog rada ispitan je sintetički potencijal 3-(arilamino)-1-
ferocenilpropan-1-ona kao prekursora u sintezi novih heterocikličnih derivata
ferocena. Istraživanja tokom izrade ove disertacije obuhvatila su sintezu polaznih
supstrata (odgovarajućih Manihovih baza) i razvoj metodologija za njihovu
sintetičku transformaciju do odgovarajućih heterocikličnih sistema. Za sintezu
3-(arilamino)-1-ferocenilpropan-1-ona 194 korišćena je jednostavna metoda, koja je
prethodno razvijena u našoj laboratoriji [7]. Pomenuti protokol obuhvata azaMajklovu reakciju akriloilferocena (200) (dobijenog Fridel-Kraftsovim
acilovanjem) kao Majklovog akceptora i aromatičnih amina (supstituisanih anilina)
kao donora. Reakcija se izvodila u ultrazvučnoj kadi, primenom gline −
montmorilonita K-10 kao katalizatora i bez prisustva rastvarača. Odgovarajući
β-aminoketoni 194 dobijeni su u visokim prinosima (do 88%). Spektralni podaci za
Manihove baze 194a-j su u skladu sa literaturnim podacima [6, 7], dok su
novosintetisana jedinjenja 194k-ć (pripremljena za potrebe ove disertacije) u
potpunosti okarakterisana standardnim spektroskopskim metodama.
3-(Arilamino)-1-ferocenilpropan-1-oni 194 su prepoznati kao pogodni polazni
supstrati za dobijanje složenih acikličnih sistema i heterocikličnih jedinjenja
koja sadrže ferocensko jezgro zahvaljujući hemijskim osobinama prisutne karbonilne
i amino-grupe. Stoga, u ovom radu su razvijene i detaljno opisane sintetičke metode
za pripremu derivata ferocena polazeći od odgovarajućih β-aminoketona 194, a sa
ciljem zatvaranja heterocikličnih prstenova:
• 1-Aril-3-fenil-4-feroceniltetrahidropirimidin-2(1H)-ona;
• 4-Ferocenil-1,2,3,4-tetrahidrohinolina;
• 4-Ferocenilhinolina;
• 3-Aril-N-fenil-6-ferocenil-1,3-tiazinan-2-imina.
Sinteza prve serije jedinjenja – ferocenskih derivata pirimidin-2(1N)-ona
planirana je intramolekulskom ciklizacijom odgovarajućih acikličnih 1,3-ketourea
– 1-aril-3-fenil-1-(3-ferocenil-3-oksopropil)urea 201. Stoga je osmišnjena i
izvedena njihova sinteza. 1,3-Ketouree 201 su dobijene primenom efikasnog i
jednostavnog protokola uz upotrebu jednostavne opreme. Ovaj protokol se zasnivao na
reakciji između odgovarajućih 1,3-aminoketona 194 i fenil-izocijanata (reakcija je
potpomognuta ultrazvučnom iradijacijom). Uspešno su optimizovani reakcioni
uslovi i ciljana jedinjenja 201 dobijena su u visokim prinosima (do 99%). Kako o ovoj
grupi jedinjenja nisu pronađeni podaci u literaturi, njihovoj strukturnoj
karakterizaciji je posvećena posebna pažnja. Novosintetisana jedinjenja su izolovana
i detaljno okarakterisana fizičkim i spektroskopskim podacima (tačke topljenja,
mikroanaliza, IR, 1H i 13C NMR), a čak tri jedinjenja (201v, 201g i 201j) su bila
podesna za rendgensku strukturnu analizu, pa im je na taj način nedvosmisleno
potvrđena struktura. Redoks osobine svih ferocenskih derivata 1,3-ketourea 201
ispitane su tehnikom ciklične voltametrije. Nađeno je da u prozoru potencijala od
0,000-1,300 V jedinu elektroforu u njihovoj strukturi predstavlja ferocensko jezgro.
1,3-Ketouree 201a-t pokazuju samo jedan oksidacioni (na 0,839-0,928 V) i jedan
redukcioni talas (na 0,693-0,754 V) koji su na znatno višem potencijalu od vrednosti
potencijala za nesupstituisani ferocen. Ovako elektrohemijsko ponašanje se
pripisuje uticaju elektron-privlačne karbonilne grupe koja je direktno vezana za
ferocenil-grupu. Takođe, elektrohemijska merenja su pokazala da je redoks proces
kontrolisan difuzijom i ukazala na kvazi-reverzibilnu prirodu sistema.
Ferocenski derivati 1,3-ketouree 201 prepoznati su kao pogodni sintetički
intermedijeri za intramolekulsku ciklizaciju i građenje pirimidin-2(1N)-onskog
prstena. Nažalost, svi pokušaji da se ostvari sinteza heterocikličnih derivata 202
polazeći od 201 bili su neuspešni, zbog čega je izabran alternativni pristup. | sr |
| dc.description | Summary:
Within this study, the synthetic potential of 3-(arylamino)-1-ferrocenylpropan-1-ones as
suitable precursors for the synthesis of novel ferrocene-containing heterocyclic compounds
was evaluated. This research included the synthesis of the starting substrates (corresponding
Mannich bases) and the development of new methodologies for their further transformation
to the corresponding heterocyclic systems. The synthesis of 3-(arylamino)-1-
ferrocenylpropan-1-ones was achieved using an elegant and simple method, which was
previously developed in our laboratory [7]. This protocol included aza-Michael reaction of
acryloylferrocene (200) and aromatic amines (substituted anilines). Moreover, Michael
acceptor – acryloylferrocene (200) was obtained by the Friedel-Crafts’ acylation. This
reaction was performed in an ultrasonic bath without the presence of solvent using clay –
montmorillonite K-10 as a catalyst. The β-aminoketones 194 were synthesized in high yields
(up to 88%). Spectral data for Mannich bases 194а-ј were in accordance with the literature
data [6, 7], while the newly synthesized compounds 194к-ћ (prepared for the purposes of this
dissertation) were fully characterized by the standard spectroscopic methods.
Due to the chemical properties of the carbonyl and amino group, 3-(arylamino)-1-
ferrocenylpropan-1-ones 194 were recognized as suitable starting substrates for the
preparation of ferrocene-containing acyclic and heterocyclic systems. Therefore, synthetic
transformation of corresponding β-aminoketones 194 in novel ferrocene-containing
heterocyclic systems are performed and include:
• 1-Aryl-3-phenyl-4-ferrocenyltetrahydropyrimidin-2(1H)-ones;
• 4-Ferrocenyl-1,2,3,4-tetrahydroquinolines;
• 4-Ferrocenylquinolines;
• 3-Aryl-N-phenyl-6-ferrocenyl-1,3-thiazinan-2-imines.
Synthesis of feroccene-containing pyrimidin-2(1H)-ones was planned by intramolecular
cyclization of the corresponding acyclic 1,3-ketoureas 201. Thus, the first task was
optimization of reaction conditions for the synthesis of 1-aryl-3-phenyl-1-(3-ferrocenyl-3-
oxopropyl)ureas 201. The 1,3-ketoureas 201 were obtained using an efficient and simple
protocol with the usage of simple equipment. This protocol was based on the reaction
between the corresponding 1,3-aminoketones 194 and phenyl isocyanate (the reaction was
prompted by ultrasound irradiation). The reaction conditions were successfully optimized,
and the compounds 201 were synthesized in the high yields (up to 99%). Since, there is no
literature data for this class of compounds, a special attention was given to their structural
characterization. The newly synthesized products were isolated pure and thoroughly
characterized by the physical and spectroscopic data (melting points, microanalysis, IR, 1H
and 13C NMR). Additionally, the structures of compounds 201в, 201г and 201ј were
unambiguously confirmed by the X-ray analysis. The redox properties for all novel
ferrocene-containing 1,3-ketoureas 201 were evaluated by the cyclic voltammetry technique.
It was found that all 1,3-ketoureas 201 exhibit a reversible one-electron redox process at the
similar potential (oxidation waves appear at 0.839–0.928 V and the reduction ones at 0.693–
0.745 V) attributed to the ferrocene core. These potentials are considerably more positive
than the one of the unsubstituted ferrocene, as a consequence of the presence of an electronwithdrawing carbonyl group. Both, anodic and cathodic peak currents are proportional to the
square root of the scan rate, and their ratio is independent of the scan rate, indicating a
diffusion-controlled process. Moreover, the difference between the oxidation and reduction
maxima was around 0.156 V, which confirms the quasi reversible nature of the system. | en |
| dc.format | application/pdf | |
| dc.language | sr | |
| dc.publisher | Универзитет у Крагујевцу, Природно-математички факултет | sr |
| dc.relation | info:eu-repo/grantAgreement/MESTD/Basic Research (BR or ON)/172034/RS// | |
| dc.rights | openAccess | en |
| dc.rights.uri | https://creativecommons.org/licenses/by-nc-sa/4.0/ | |
| dc.source | Универзитет у Крагујевцу | sr |
| dc.title | 3-(Arilamino)-1-ferocenilpropan-1-oni kao prekursori u sintezi novih heterocikličnih derivata ferocena | sr |
| dc.type | doctoralThesis | en |
| dc.rights.license | BY-NC-SA | |
| dc.identifier.fulltext | https://nardus.mpn.gov.rs/bitstream/id/66141/Izvestaj_Aleksandra_Minic_PMF.pdf | |
| dc.identifier.fulltext | https://nardus.mpn.gov.rs/bitstream/id/66140/Disertacija.pdf | |
| dc.identifier.rcub | https://hdl.handle.net/21.15107/rcub_nardus_17534 | |
