Priprava para-supstituiranih N-aril-3-hidroksi-2-metilpiridin-4-onskih alfa-manozida s esterskom vezom na piridinonu

master's thesis

• Title (english): Preparation of para Substituted N-aryl-3-hydroxy-2-methylpyridin-4-one alpha-Mannosides with Ester Bond on Pyridinone Part
• Author: Antonija Rimac
• Mentor: Vesna Petrović Peroković (mentor)
• Committee member: Vesna Petrović Peroković (predsjednik povjerenstva)
• Committee member: Željka Soldin (član povjerenstva)
• Committee member: Sanda Rončević (član povjerenstva)
• Committee member: Ivana Biljan (član povjerenstva)
• Granter: University of Zagreb; Faculty of Science; (Department of Chemistry); Zagreb
• Defense date and country: 2017-12-18, Croatia
• Scientific / art field, discipline and subdiscipline: NATURAL SCIENCES; Chemistry

Abstract

U ovom diplomskom radu opisane su sinteze osnovnih prekursora za pripravu para
supstituiranih N-aril-3-hidroksi-2-metilpiridin-4-onskih α-D-manozida s esterskom vezom na
piridinonu. Piridinonski prekursori 1-4 priređeni su izravnim postupkom iz maltola i anilina
ili p-supstituiranih derivata anilina (p-metil-, p-metoksi- i p-nitroanilina) uz dodatak kiselog
katalizatora (p-TsOH) zagrijavanjem u zatvorenoj staklenoj cijevi. Manozna podjedinica 2-
(2',3',4',6'-tetra-O-acetil-α-D-manopiranoziloksi)octena kiselina, spoj 8, priređena je u
nekoliko koraka iz polazne D-manoze. Ispitane su mogućnosti esterifikacije manozilirane
octene kiseline 8 s odabranim piridinonskim alkoholom, spojem 2, uz karbodiimidne reagense
(EDC×HCl, DCC) i nukleofilne katalizatore (DMAP, HOBt). U reakcijama spojeva 2 i 8 uz
DCC i DCC/DMAP nastaje u tragovima acetilirani produkt 9, 2-metil-1-(p-metilfenil)piridin-
4-on-3-il-2-(2',3',4',6'-tetra-O-acetil-α-D-manopiranoziloksi)acetat, čija je struktura potvrđena
spektrometrijom masa. Reakcijom istih spojeva uz EDC×HCl/DMAP ili EDC×HCl/HOBt
nastao je neželjeni produkt, spoj 10, metil-2-(2',3',4',6'-tetra-O-acetil-α-Dmanopiranoziloksi)
acetat.
Strukture svih priređenih spojeva određene su spektroskopijom NMR (1H i 13C) i/ili
spektrometrijom masa (MS).

Abstract (english)

The syntheses of the main precursors needed for the preparation of the para substituted N-aryl
3-hydroxy-2-methylpyridin-4-one α-D-mannosides with the ester bond on the pyridinone part
were described in this diploma thesis. Pyridinone derivatives 1-4 were prepared first using
direct approach from maltol and aniline or p-substituted aniline derivatives (p-methyl-, pmethoxy-
and p-nitroaniline) with the addition of the acid catalyst (p-TsOH) in an autoclave.
Mannose subunit 2-(2',3',4',6'-tetra-O-acetyl-α-D-mannopyranosyloxy)acetic acid, compound
8, was prepared in several steps from D-mannose. The esterification of mannosylated acetic
acid 8 with the selected pyridinone alcohol, compound 2, was explored through several
synthetic pathways using carbodiimide reagents (EDC×HCl, DCC) and nucleophilic catalysts
(DMAP, HOBt). An unwanted byproduct, compound 10, methyl 2-(2',3',4',6'-tetra-O-acetyl-
α-D-mannopyranosyloxy)acetate, has formed in the reactions of derivatives 2 and 8 with
EDC×HCl/DMAP or EDC×HCl/HOBt as reagents.
Structures of all prepared compounds were determined using NMR spectroscopy (1H i
13C) and/or mass spectrometry (MS).

• Keywords: N-aril-3-hidroksi-2-metilpiridin-4-oni; esterifikacija; manozilirana octena kiselina; piridinonski α-D-manokonjugati
• Keywords (english): N-aryl 3-hydroxy-2-methylpyridin-4-ones; esterification; mannosylated acetic acid; pyridinone -D-mannoconjugates
• Language: croatian
• URN:NBN: urn:nbn:hr:217:338230
• Study programme: Title: Graduate university studies in chemistry; specializations in: Research programme; Course: Research programme; Study programme type: university; Study level: graduate; Academic / professional title: magistar/magistra kemije (magistar/magistra kemije)
• Type of resource: Text
• File origin: Born digital
• Access conditions: Open access; Embargo expiration date: 2019-12-20
• Created on: 2018-01-09 11:18:20