There are two sections to this research dissertation. Part one includes syntheses of fused-ring heterocycles derived from thiazole, oxazole, benzoxazole and benzothiazole derivatives and trifluoroacetylations of in situ generated N-methyl cyclic ketene-N,O/Sacetals. Attempted functionalized polymer syntheses from plant-derived 5-(hydroxymethyl) furfural are discussed in part two. Three 2-methylthiazoles, 2,4,5-trimethyloxazole, 2-methylbenzoxazole and 2- methyl-benzothiazole were each reacted with benzoyl chloride in acetonitrile/triethylamine to generate benzyl-vinyl esters. Base hydrolysis of these benzyl-vinyl esters formed 2-(heterocyclic)-1-phenylethenols which exist in both ketoenol tautomeric forms. These tautomers were used as starting materials for fused-ring heterocycle syntheses. Each tautomeric pair react with dimethyl acetylenedicarboxylate in methanol giving the 5,6-ringused 8-benzoyl-5-oxo-5H-thiazolo-, 8-benzoyl-5-oxo-5H-oxazolo-, 4-benzoyl-1-oxo-1H-benzo[4,5]oxazolo- and 4-benzoyl-1-oxo-1H-benzo[4,5]thiazolo [3,2-a]pyridinecarboxylate derivatives. Two novel 5,7-ringused 9-benzoyl-2,3- dimethyl-5,6-dihydrothiazolo- and 9-benzoyl-2,3-dimethyl-5,6-dihydrooxazolo[3,2-a] azepine-5,6,7,8-tetracarboxylates formed when the tautomers formed from 2,4,5- trimethyl thiazole and 2,4,5-trimethyl oxazole were reacted with DMADC. These tautomers react with 1,3-diacid chlorides in acetonitrile/triethylamine affording the 5,6-ringused 8-benzoyl-6,6-dialkyl-6H-thiazolo- and 8-benzoyl-6,6- dimethy-6H-oxazolo-, 4-benzoyl-2,2-dimethyl-1H-benzo[4,5]thiazolo- and 4-benzoyl- 2,2-dimethyl-1H-benzo[4,5]oxazolo[3,2,-a]pyridinedione derivatives. Functionalized 5,6- ringused 8-benzoyl-6H-thiazolo- and 8-benzoyl-6H-oxazolo[3,2]pyrimidine-5,7- diones, and 4-benzoyl-1H-benzo[4,5]thiazolo- and 4-benzoyl-1H-benzo[4,5]oxazolo[3,2- c]pyrimidine-1,3(2H)-diones formed reacting the tautomers with N-chlorocarbonyl isocyanate in THF/triethylamine. Significant ring size and substituent effects were observed in trifluoroacetylations of in situ-generated cyclic ketene-N,O/S acetals. In situ-generated 3,4,4-trimethyl-2- methylene-oxazolidine, 3-methyl-2-methylene-oxazolidine and 3-methyl-2-methylene- 1,3-oxazinane each formed β,β-bistrifluoroacetylated products. However, 3-methyl-2- methylene-oxazolidine also afforded a γ-lactam by an iodide-catalyzed rearrangement of its β,β-bistrifluoroacetylated derivative. In situ-generated 3-methyl-2-methylenethiazolidine gave both β-mono- and β,β-bistrifluoroacetylation products. 5-(Hydroxymethyl)furfural synthesized from sucrose was converted to 2,5- bis(hydroxymethyl)furan (2,5-BHMF). 7-Oxanorbornene-type Diels-Alder adducts synthesized from 2,5-BHMF were used as monomers for both ring opening metathesis polymerizations (ROMPs) and polycondensations. ROMP, followed by polycondensation or vise versa were expected to give highly functionalized cross-linked polymers. ROMP of the monomers using three Grubbs’ 1st, 2nd and 3rd generation catalysts were unsuccessful due to the presence of hydroxymethyl groups at one or both bridgeheads that could coordinate Ruthenium. With one bridgehead methyl present ROMP proceeded. Low molecular weight polyesters were synthesized via polycondensation. One was crosslinked using ROMP, but not to its gel point.

This work deals with the design and synthesis of building blocks, usable for creating dynamic polymers based on the reversible formation of hemiacetals bond. Next part is focused on the study of the formation of hemiacetal between polyfunctional alcohols and trifluoromethylketones via NMR spectroscopy. Key words: constitutional dynamic chemistry, hemiacetals, trifluoromethylketones, diols and polyols

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Syftet med projektet var att samla in återvunnen polyeten och omvandla den till återvinningsbara högstyrke-härdplaster genom att designa ett kovalent anpassningsbart nätverk för det. Återvunnen polyeten samlades in och ympades med maleinsyraanhydrid genom reaktiv extrudering och en friradikalmekanism, vilket sedan tvärbands med laboratoriesyntetiserad polyimid. Den resulterande tvärbundna blandningen bearbetades genom formsprutning, och tester visade att den förväntade reaktionen hade utförts framgångsrikt och de mekaniska egenskaperna förbättrades avsevärt. Materialet bearbetades också om för att testa dess återvinningsbarhet och denna process samt analysen av materialet efteråt visade också lovande resultat. / The aim of the project was to collect recycled polyethylene and transform it into recyclable high-strength thermosets by designing a covalent adaptable network. Recycled polyethylene was collected and grafted with maleic anhydride through reactive extrusion and free radical mechanism, which was then cross-linked with laboratory synthesized polyimide. The resulting cross-linked blend was processed using injection molding, and testing showed that the expected reaction had been carried out successfully and mechanical properties were significantly enhanced. The material was also reprocessed to test its recyclability and this process and analysis of material after it showed promising results as well.