<p> The effect of a C-7 substituent on the position of the cycloheptatriene/
norcaradiene equilibrium has been investigated. For this purpose a series of monosubstituted cycloheptatrienes was prepared in which the C-7 substituent was a carbonium ion grouping. From the spectral properties of these systems, it has been concluded that proportion of the norcaradiene valence tautomer present increases as the electron withdrawing ability of the carbonium ion substituent is enhanced.</p> <p> From a comparison of the pmr spectra of 7-norcaradienylmethyl cations with suitable model systems it is suggested that these norcaradienes are aromatic and that they support an induced diamagnetic ring current when in a magnetic field. It would appear that this type of cyclic delocalization is enhanced by the presence of an electron defficient substituent at C-7 of a norcaradiene and possible reasons
for this are discussed.</p> <p> The 7-norcaradienylmethyl cations underwent a thermal isomerization to give benzenoid materials at relatively low temperatures. A mechanism for this rearrangement has been proposed and the implication of these results to the general pathways involved in the rearrangements of the C8H9+ family of cations discussed.</p> <p> Several synthetic routes to 9-substituted-3,4-homotropylidenes were investigated. A number of new compounds were isolated and a new synthetic approach to this class of compounds is suggested.</p> <p> Diamagnetic susceptibility exaltations of a series of substituted
cycloheptatrienes were determined and used as a criterion of aromaticity. It was concluded that cycloheptatrienes are best regarded as homoaromatic molecules. Moreover it would appear that the substantial diamagnetic susceptibility exaltations observed with these compounds are related to the bulk of a C-7 substituent. One neutral norcaradiene was examined by this technique and was found to be nonaromatic.</p> / Thesis / Doctor of Philosophy (PhD)
| Identifer | oai:union.ndltd.org:mcmaster.ca/oai:macsphere.mcmaster.ca:11375/19953 |
| Date | 01 1900 |
| Creators | Pikulik, Ivan Ignac |
| Contributors | Childs, R. F., Chemistry |
| Source Sets | McMaster University |
| Language | en_US |
| Detected Language | English |
| Type | Thesis |
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