Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.653366
Title: Chemical modification of alkene-carbon monoxide alternating copolymers
Author: Khansawai, Paveena
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2000
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Abstract:
Reactions of isolated carbonyl groups in ethene/propene-carbon monoxide alternating copolymers were accomplished by acid-catalysed condensation with alkene-1,2-diols (ethane-, propane-, butane- and hexane-1,2-diols) affording alkene-dioxolane copolymers. Oximation with hydroxylamine, O- methylhydroxylamine and O-benzylhydroxylamine resulted in complete conversion of the carbonyl groups to their oxime derivatives. In addition, the conversions of polyketoximes, derived from ethene/propene-carbon monoxide copolymers, to 1-acteoxyiminotrimethylene and 1-benzoxyimino-trimethylene polymers were achieved by treatment with acetic anhydride and benzoyl chloride, respectively. Reaction of 1,4-dione units in ethene/propene-carbon monoxide alternating copolymers has been investigated. Paal-Knorr reactions with aniline, benzylamine and glycine ethyl ester yielded poly(alkenepyrrole) derivatives. The conversion of the carbonyl groups in ethene/propene-carbon monoxide alternating copolymers to methoximes allowed directed a-substitution reactions to be carried out on the polymer backbone. Treatment with n-butyllithium followed by addition of electrophiles (e.g. iodomethane, 1-iodopropane, 1-bromobutane, benzyl bromide and allyl bromide) afforded the polymer products in which 20-38% of the a-syn methylene hydrogens were substituted. The syn selectivity of the lithiation process was established b treatment of the polymethoxime with BuLi/[O-2H]methanol and confirmed by the presence of deuterium signal in the 2H-NMR spectrum corresponding to those observed for the model compounds. Beckmann rearrangement reactions of model compounds [2.5-bis(tosyloxyimino)hexane, 2,5-bis(mesyloxyimino)hexane and 2,5-bis(hydroxyimino)hexane] were investigated and resulted in rearrangement products: N,N'-ethanediyl-bis-acetamide, N-acetyl-b-alaninemonomethylamide and N,N'-dimethylsuccinamide.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.653366  DOI: Not available
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