Naslov (srp)

Sinteza derivata 1H-tetrazol-5-amina i 1H- pirazol-5-ola katalizovana kompleksnim jedinjenjima paladijuma : doktorska disertacija

Autor

Nikolić, Andrea M., 1994-

Doprinosi

Gruden-Pavlović, Maja, 1970-
Vulović, Bojan Z., 1983-
Francuz, Jovana, 1982-
Opsenica, Igor, 1977-
Ajdačić, Vladimir, 1991-
Milić, Dragana, 1967-

Opis (eng)

Palladium catalyzed C–N bond formation is a very significant reaction in medicinal chemistry andpharmaceutical industry. Considering the importance of N,1-disubstituted-1H-tetrazol-5-amines inthe industry of explosives and pharmaceuticals, medicinal chemistry and photochemistry, one of thegoals set for this doctoral dissertation was the development of a new method for the synthesis of Naryl-1-substituted-1H-tetrazol-5-amines based on the N-arylation reaction of 1-substituted-1Htetrazol-5-amines catalyzed by palladium complexes. Even though the reactivity of tetrazol-5-amines in this reaction can be considered to be reduced, optimized reaction conditions weredetermined and 23 N-aryl-1-substituted-1H-tetrazol-5-amine derivatives were synthesized. Duringthe synthesis of N,1-diaryl-1H-tetrazol-5-amines, under the previously optimized reactionconditions, Dimroth rearrangement of the N-arylation reaction products was observed. By loweringthe reaction temperature from 105 ºC to 35 ºC, 19 N,1-diaryl-1H-tetrazol-5-amines were obtainedwhile the rearrangement reaction did not occur. Reaction parameters, the relationship between thestructure and the reaction outcome, as well as the mechanism of Dimroth rearrangement weredetermined with experimental and in silico methods. Additionally, the reaction was applied for thesynthesis of new N,1-diaryl-1H-tetrazol-5-amine derivatives. A method for the synthesis of hybridmolecules containing two privileged fragments, 3-(trifluoromethyl)-1H-pyrazole and isochromene,was developed in the last segment of this dissertation. Nine hybrid derivatives and one sulfuranalogue were obtained by applying a one-pot two-step method. Rare 13C–19F through-spacecoupling was observed in all 13C NMR spectra of the hybrid molecules.

Opis (srp)

Formiranje C–N veze katalizovano kompleksnim jedinjenjima paladijuma predstavlja veomaznačajnu reakciju u medicinskoj hemiji i farmaceutskoj industiji. Imajući u vidu značaj N,1-disupstituisanih-1H-tetrazol-5-amina u farmaceutskoj industiji, industriji eksploziva, medicinskojhemiji i fotohemiji, kao jedan od ciljeva ove doktorske disertacije postavljen je razvoj nove metodeza sintezu N-aril-1-supstituisanih-1H-tetrazol-5-amina zasnovane na reakciji N-arilovanja 1-supstituisanih-1H-tetrazol-5-amina katalizovanoj kompleksnim jedinjenjima paladijuma. Iako setetrazol-5-amin može smatrati manje reaktivnim sistemom za ovu reakciju, pronađeni su optimalnireakcioni uslovi i sintetisana su 23 derivata N-aril-1-alkil-1H-tetrazol-5-amina. Ustanovljeno je daprilikom sinteze N,1-diaril-1H-tetrazol-5-amina, primenom prethodno optimizovanih reakcionihuslova, dolazi i do reakcije Dimroth-ovog premeštanja proizvoda N-arilovanja. Snižavanjemreakcione temperature sa 105 ºC na 35 ºC, sintetisano je novih 19 derivata N,1-diaril-1H-tetrazol-5-amina, pri čemu reakcija premeštanja nije opažena. Primenom eksperimentalnih i in silico metodaodređeni su reakcioni parametri, uticaj strukture na ishod reakcije i mehanizam reakcije Dimrothovog premeštanja N,1-diaril-1H-tetrazol-5-amina. U nastavku istraživanja reakcija je primenjena usintezi novih derivata N,1-diaril-1H-tetrazol-5-amina. U poslednjem segmentu ove disertacijerazvijena je metoda za sintezu hibridnih molekula koji sadrže fragmente privilegovanih struktura, 3-(trifluormetil)-1H-pirazola i izohromena. Primenom sinteze u dva koraka u jednom sudu sintetisanoje devet derivata kao i jedan analog hibridnih molekula sa sumporom. Analizom 13C NMR spektarahibridnih molekula uočena je pojava 13C–19F sprezanja kroz prostor.

Opis (srp)

Hemija - Organska hemija / Chemistry - Organic chemistry Datum odbrane: 01.06.2022.

Jezik

srpski

Datum

2022

Licenca

Ovo delo je licencirano pod uslovima licence
Creative Commons CC BY-NC-ND 3.0 AT - Creative Commons Autorstvo - Nekomercijalno - Bez prerada 3.0 Austria License.

http://creativecommons.org/licenses/by-nc-nd/3.0/at/legalcode

Predmet

OSNO - Opšta sistematizacija naučnih oblasti, Heterociklična jedinjenja

tetrazol-5-amine, heterocyclic compounds, palladium, pyrazole, hybrid molecules, isochromene, N-arylation, C–H arylation, Dimroth rearrangement

OSNO - Opšta sistematizacija naučnih oblasti, Heterociklična jedinjenja

tetrazol-5-amin, heterociklična jedinjenja, paladijum, pirazol, hibridni molekuli, izohromen, N-arilovanje, C–H arilovanje, Dimroth-ovo premeštanje