Sinteza biciklo[2.2.2]oktenov iz različnih 2H-piran-2-onov ter maleimida oziroma njegovih derivatov kot osnova za raziskovanje halogenskih vezi

Kos, Grega (author), Kranjc, Krištof (mentor)

V prvi fazi magistrskega dela sem sintetiziral serijo biciklo[2.2.2]oktenov iz primerno substituiranih 2H-piran-2-onov ter maleimida. Reakcije so potekale v skladu s pričakovanji dobro poznanih Diels–Alderjevih cikloadicij. Pripravljeni biciklo[2.2.2]okteni so predstavljali izhodne spojine v naslednji stopnji, t.j. reakciji N-halogeniranja, kjer sem želel ustvariti vez med halogenom (klorom) ter obročnim dušikovim atomom. Z modifikacijo postopkov iz literature sem tako razvil okolju prijazno N-kloriranje. Uporabil sem NaCl, ki je bil vir klora, oksidant okson, trdni Al2O3 ter kloroform kot topilo. Reakcije sem izvajal v zaprti ACE cevki pri temperaturi 45 °C, s spreminjanjem reakcijskih pogojev sem na ta način uspešno pripravil tri nove N,N'-dikloro derivate pripojenih biciklo[2.2.2]oktenskih sistemov. V drugi fazi eksperimentalnega dela sem poizkusil iz predhodno sintetiziranih N-halogeniranih biciklo[2.2.2]oktenov in ustreznih piridinskih derivatov pripraviti kokristale, ki bi vsebovali halogensko vez. Za ta namen sem kot akceptorja halogenske vezi uporabil 2,2'-bipiridil ter 4,4'-bipiridil, kar bi omogočilo nadaljnje raziskave narave halogenske vezi. Žal priprava kristalov ni uspela.

• Language: Slovenian
• Keywords: 2H-piran-2-oni, Diels–Alderjeva reakcija, biciklo[2.2.2]okteni, halogenirani biciklo[2.2.2]okteni, halogenska vez.
• Work type: Master's thesis/paper
• Typology: 2.09 - Master's Thesis
• Organization: FKKT - Faculty of Chemistry and Chemical Technology
• Year: 2020
• PID: 20.500.12556/RUL-117332
• COBISS.SI-ID: 22864131
• Publication date in RUL: 07.07.2020

Secondary language

• Language: English
• Title: Synthesis of bicyclo[2.2.2]octenes from various 2H-pyran-2-ones and maleimide or its derivatives as a basis for investigating halogen bonding

Abstract

In the first phase of my master's thesis, I synthesized a variety of bicyclo[2.2.2]octenes from suitably substituted 2H-pyran-2-ones and maleimide. The reactions were took place according to the well known Diels–Alder cycloadditions. The prepared bicyclo[2.2.2]octenes represented the starting reactant in the following step of N-halogenation reaction where I tried to form a bond between a halogen (chlorine) and a ring nitrogen. By appropriate modifications of the literature reaction conditions, I developed environmentally friendly N-chlorination, using NaCl, which was the source of chlorine, oxone as the oxidant, solid Al2O3, and chloroform as the solvent. The reactions were carried out in closed ACE tubes at 45 °C. By changing the reaction parameters I managed to successfully synthesize three new N,N'-dichloro derivatives of fused bicyclo[2.2.2]octene systems. In the second phase of the experimental work, I tried to prepare co-crystals from previously synthesized N-halogenated bicyclo[2.2.2]octenes and suitable pyridine derivatives, which would presumably contain halogen bond, using 2,2'-bipyridyl and 4,4'-bipyridyl, as the halogen bond acceptors. Preparation of such crystals would allow further investigations into the nature of halogen bonding. Unfortunately, the preparation of the crystals was not successful.

• Keywords: 2H-pyran-2-ones, Diels–Alder reaction, bicyclo[2.2.2]octenes, halogenated bicyclo[2.2.2]octenes, halogen bond.