Sinteza imobilizirane 4-aminobenzojske kisline in njena uporaba v pripravi imobiliziranih Cu(II)-enaminon katalizatorjev

Jarc Rydzi, Matej (author), Svete, Jurij (mentor)

V tem diplomskem delu sem raziskoval imobilizirane baker enaminon katalizatorje, vezane na aminopropil silikagel, kjer je 4-aminobenzojska kislina služila kot povezava med silikagelom in enaminonom. Uspešno sem s funkcionaliziranega silikagela 1 in 1' s hidroksilaminom odcepil enaminon, da sem pridobil imobilizirano 4-aminobenzojsko kislino s prostim aminskim fragmentom 2, kar sem potrdil z IR spektroskopijo. Ta reakcija poteka tako, da hidroksilamin povzroči ciklizacijo enaminona, kar povzroči njegov odcep od nosilca. Strukturo heterocikličnega stranskega produkta sem dokazal z NMR spektroskopijo. Na prosto aminsko skupino sem želel vezati nov enaminon, da bi nastali novi imobilizirani enaminoni 4a–c, a ta reakcija ni bila uspešna niti pod ostrejšimi pogoji. Zato sem na izhodno spojino 1 koordiniral Cu(II) ione, da sem pridobil katalizator 5. Nastali katalizator sem uporabil v modelni reakciji za sintezo bicikličnega pirazolidinona, metil 6,7-dihidro-7,7-dimetil-1-(3,4,5-trimetoksifenil)-5-okso-1H,5H-pirazolo[1,2-a]pirazol-2-karboksilata (9). Njegov nastanek in učinkovitost katalizatorja sem dokazal z NMR spektroskopijo.

• Language: Slovenian
• Keywords: 4-aminobenzojska kislina, enaminon, bakrov katalizator, biciklični pirazolidinoni
• Work type: Bachelor thesis/paper
• Typology: 2.11 - Undergraduate Thesis
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Year: 2021
• PID: 20.500.12556/RUL-129227
• COBISS.SI-ID: 75983107
• Publication date in RUL: 30.08.2021

Secondary language

• Language: English
• Title: Synthesis of immobilised 4-aminobenzoic acid and its use in preparation of immobilised Cu(II)-enaminone catalysts

Abstract

In this diploma thesis, I have researched immobilised copper-enaminone catalyst, bound onto aminopropyl silica gel, where 4-aminobenzoic acid served as a linker between the silica gel and the enaminone. The enaminone was successfully removed from 1 and 1' with hydroxylamine hydrochloride to give immobilised 4-aminobenzoic acid with a free amino group 2, which was confirmed using IR spectroscopy. This reaction takes place, via cyclisation of hydroxylamine with enaminone, which cleaves from the silica gel. The structure of heterocyclic by-product of this reaction was confirmed using NMR spectroscopy. The binding of new enaminones onto the 'free' amine group was then considered to gain new products 4a–c, but the reactions proved unsuccessful even under harsher conditions. Because of that, copper was coordinated onto starting material 1 to gain the catalyst 5. The prepared catalyst was then tested on a model reaction for the synthesis of bicyclic pyrazolidinone, methyl 6,7-dihydro-7,7-dimethyl-1-(3,4,5-trimethoxyphenyl)-5-oxo-1H,5H-pyrazolo[1,2-a]pyrazole-2-carboxylate (9). The full conversion with this catalyst was confirmed by NMR spectroscopy.

• Keywords: 4-aminobenzoic acid, enaminone, copper catalyst, bicyclic pyrazolidinone