Use this URL to cite or link to this record in EThOS: https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.776679
Title: Some studies in the field of non-benzenoid aromatic compounds
Author: Rodger, William James
Awarding Body: University of Glasgow
Current Institution: University of Glasgow
Date of Award: 1965
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Abstract:
Some chemical Investigations of 1-thia-4-pyrone have been carried out. In experiments with hydroxylamine and hydrazines, 1-thia-4-pyrone was shown to react somewhat similarly to 4-pyrone. Thus 4-hydroxylaminopyridino-N-oxide was obtained from the reaction of 1-thia-4-pyrone and hydroxy1-amine, and with hydrazine a pyrazole derivative was obtained. In contrast, little or no reaction was observed with phenyl and p-nitrophonylhydrazines; with 2,4-dinitrophonylhydrazino l-thia-4- pyrone-2,4-dinitrophenylhydrazono was obtained. Methyl magnesium iodide and eyelopentadleny1 sodium did not condense with 1-thia-4-pyrone. No evidence of nuclear bromination was found. l-Thia-h-4-pyrone with bromine in various solvents gave a complex to which is assigned the formula C3 H4OS.HBr.3Br2. Numerous attempts to synthesis metal carbonyl derivatives of 1-thia-4-pyrone were unsuccessful. The n.m.r. spectrum of I-thia-4-pyrone has been studied. Several routes to a tricyelo[9,3,0,04.8]tetradocane system were attempted using cis.cls-1.3-cyelo-ootadieno as starting material. The tetrabromo-derivation, 1,2:5,6-tetrabromo-cyclo-octane was unreactive to sodio- and magnosio-malonic esters. Frtedel-Crafts reactions of 1,5-cyclo-octadiene with ethyl malonyl chloride and beta-chloropropionyl chloride were unsuccessful. Possible reasons wore suggested. Synthesis and subsequent transformations of several tropylphenols have been studied. From p-tropylpheno1 via triphenylmethyl perchlorate dehydrogenation and basification, tropilidene-p-quinone was obtained which was unstable to air and could not toe purified. Ditropyl ether and thiophenol afforded tropyl phenyl thioether which reacted with triphonyl- methyl perohlorato to give tropylium perchlorate and triphenyl-methyl phenyl thioether. Dehydrovenation of tropylphenols which were obtained toy the action of ditropyl ether on the corresponding phenol afforded benzo[b]eyeloheptatrieno[d]furens which could be further dehydrogenatod to benzofuranotropylium salts. Basification of the latter afforded three products. The first was the original benzo[b]eyeloheptatrieno[d]furan. The other two were bonzofuranotropone isomers whose structure are assigned on the basis of n.m.r. spectra.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.776679  DOI: Not available
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