Some studies in the field of non-benzenoid aromatic compounds

Rodger, William James (1965) Some studies in the field of non-benzenoid aromatic compounds. PhD thesis, University of Glasgow.

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.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Additional Information: Adviser: P L Pauson
• Keywords: Organic chemistry
• Date of Award: 1965
• Depositing User: Enlighten Team
• Unique ID: glathesis:1965-72600
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 11 Jun 2019 11:06
• Last Modified: 11 Jun 2019 11:06
• URI: https://theses.gla.ac.uk/id/eprint/72600