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The exceptional properties of polymers containing the pyrrolidone functional group (aqueous & organic solvent soluble, high complexation ability, non-toxic and FDA approved) allow for wide-ranging product application. The development of pyrrolidone containing polymers is therefore, a highly interesting area for academic and commercial research. The focus of this project is the synthesis and characterisation of a range of novel pyrrolidone containing homo- and co-polymers. The work uses two approaches: 1) a bottom up, with the synthesis of known and novel pyrrolidone containing monomers and, 2) a top down, by functionalisation of commercially available polymer precursors. A range of molecules containing the pyrrolidone moiety and monomer functional groups (styrene, epoxide and acrylate), were prepared. The homo- and co-polymerisation of the known and novel monomers, 1-(2-(oxiran-2-ylmethoxy) ethyl) pyrrolidin-2-one) or glycidyl ethylpyrrolidone (GEP, 1), 4-vinylbenzyloxy ethyl pyrrolidone (2) and 5-ethacryloxyethyl-12-ethylpyrrolidyl-N,N’hexane biscarbamate (3) were explored. The polymerisation methods were chosen to be synthetically simple, industrially viable and, were designed to produce pyrrolidone containing polymers with varying properties. The polymeric products were characterised by solution and solid state NMR, thermal analysis, mass spectrometry and, FTIR. GEP (1) was also successfully utilised in the post polymerisation modification of two commercial (poly(epichlorohydrin), poly(butadiene)) and one novel (poly(vinyl alcohol-graft-hyperbranched polyglycerol) (PVA-g-hPG)) polymer motifs. The development, synthesis and characterisation of a range of novel pyrrolidone containing homo- and co-polymers is detailed herein. The success of the synthesis in an industrially viable manner provides a unique insight into the possibilities of pyrrolidone polymer progress.

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Four isomers of pyridpyrrolizinones were made by FVP of the appropriately substituted pyrrole pyridine esters. The mechanism of the cyclisation is believed to follow the cascade mechanism. The structure of two of the ismoers has been confirmed by X-ray crystallography, the NMR properties of all four ismoers is also discussed in detail. The chemistry of 9-azapyrrolo[2,l-a]isoindol-5-one was also investigated, it was shown to undergo ring opening with LAH the product of which can then be repyrolysed to give a pyridopyrrolizine. Ring opening also occurs in methanol to give a nicotinate and the pyrrole ring can be hydrogenated to give a tetrahydropyridopyrrolizinone. The synthesis of pyrrolizin-l-one has been achieved by the FVP of methyl-3- (pyrrol-1-yl)-acrylate over W03 catalyst, the reaction is believed to proceed via an intramolecular electrophilic substitution reaction. The chemistry of pyrrolizin-l-one was investigated, reaction with nucleophiles proceeds via addition across the enone double bond. When a nitrogen nucleophile is used ring opening occurs. Hydrogenation occurs at the enone bond to give a dihydrpyrrolizin-l-one. Pyrrolinzin-l,3-dione was made by the oxidation of l-hydroxypyrrolizin-3-one using pyridinium dichromate. The dione shows ketone properties (eg. Formation of DNP derivative) and, in common with other pyrrolizinones, the lactam unit is readily ring opened by methanol under basic conditions. The active methylene unit of pyrrolinine-l,3dione couples readily with diazonium salts to provide a hydrazone whose structure was confirmed by X-ray crystallography. It also reacts with methoxymethylene Meldrum's acid to give a Meldrumsated pyrrolizine-l,3-dione whose FVP at 700 c gives a pyronopyrrolizinine. Reaction of pyrrolizine-l,3-dione with DMF acetal gives the 2-dimethylaminomethylene derivative which exists as a mixture of rotomers at room temperature. 8-Azaindolizine was made by FVP of DBN over a W03 catalyst. 8-Azaindolizine shows reactivity towards electrophiles in substitution reactions at the 3-position. It also reacts with methoxymethylene Meldrum's acid to give a Meldrumsated derivated whose FVP at 950 C reacts with 3-t-butyl-4-[l-methoxymethylene]-4H-isoxazol-5-one to give a isoxazolone whose FVP at 950 C gives a cyclazine.

The reactions of malonyl chloride with isocyanates and phenylisothiocyanate were reinvestigated. The products were proved to be N-substituted 7-chloro-2,3- dihydro-21 4,5-trioxo-pyrano(3,4-e)-(1,3)-oxazines. The substituent at position 3 depended on the isocyanate. In the case of phenylisothiocyanate, the product was 7-chloro-2,3-dihydro-40-dioxo-3-phenyl-2-thiopyrano (3,4-e)- (1,3)-oxazine. 'The structures of these products were elucidated by partial synthesis from 6-chloro-4-hydroxy- oxopyran-3-earbonylehloride and by degradation. The chloro-products were degraded with alcohols to derivatives of 2,3-dihydro-2.,4-dioxo-1,3-oxazine and then to amides of acetone-1,1,3-tricarbethoxylate, which gave crystalline copper enolates. The structure of the amides was supported by the infra-red and nuclear magnetic resonance spectra. Similarly, the chloro-products were reacted with secondary and primary amines to form substituted amino-pyrano oxazines and thence diamidoderivatives of dihydro-dioxo-1,3-oxazine. One of the latter compounds was further degraded to give an acetonetricarboxy amide in which the amide groupings were all different. Support Support for the structures assigned to the amine products was obtained from the u.v., infrared and the proton magnetic resonance spectra. Two novel methods of forming N-substituted dihydroxypyridones were discovered and their general nature was established. One route was the oyolisation of mono amides of acetone-1,1,3-tricarbethoxylate: the other was from dialkyl ester deriiratives of 2,3-dihydro-2,4-dioxo-1,3-oxazine. The structures of the pyridones were confirmed by spectroscopy and by degradation. For instance, 5-ethoxycaibony1-4,6-dihydroxyl- pheny1-2-pyridone was transformed to the known compound, N-phenyl-2-piperidone. The synthesis of 5-ethoxycarbony1-416-dihydroxy-lpheny1- 2-pyridone from 7-anilino-2,2-dimethy1-2,4- dioxopyrano(41 3-d)-(113)-dioxin illustrated the use of another acetone-tricarboxylic precursor. A number of amino and methoxy derivatives of acetone-tricarbethoxylate was also cyclised to the corresponding pyridones. The reactions of malonyl chloride with enolic 1,3- diketones yielded 5,6-substituted 4-hydroxy-2-oxopyrans. The constitution of the latter was established by transforming them into known compounds. The behaviour of these pyrones towards amines was also studied. The nuclear magnetic resonance of these compounds showed that they existed in the mono enol-form rather than the, diketone form usually employed to represent them.