Thesis (Ph. D.)--University of Wisconsin--Madison, 1966. / Typescript. Vita. Description based on print version record. Includes bibliographical references.

Thesis (Ph.D.) - University of St Andrews, November 2009.

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references. Available also in a digital version from Dissertation Abstracts.

This thesis comprises three parts, Parts A, B and C. Part A commences with a very brief survey based on the chemical literature of the concept of aromaticity. A number of excellent reviews covering both the historical and theoretical aspects of this subject have appeared recently and, in view of this, a more detailed consideration of aromaticity was deemed unnecessary. This is followed by a discussion of the chemistry of the mulenes with particular emphasis on the theoretical aspects of the subject. The chemistry of perinaphthene and its derivatives is then reviewed in detail and this leads logically to a reasoned description of the aims of the experimental investigation. Part B is a discussion of the results achieved in the course of investigations centred on the perinaghtene nucleus. Part C is devoted entirely to a description of experimental details, and is the complement to part B.

The thesis comprises three parts, A, B and C. Each part is divided into a number of principle sections which are prefixed by Roman numerals. Most sections are divided into subsections prefixed by Roman numerals. Part A commences with a brief survey of aromaticity and aromatic reactivity in non-benzenoid aromatic compounds. This is followed by a detailed review of the chemistry of perinaphthene and its derivatives. Part B is a discussion of the results achieved in the course of investigations on the perinaphthane nucleus. Part C is the complement to part B, being a description of experimental details.

[No abstract submitted] / Science, Faculty of / Chemistry, Department of / Graduate

[No abstract submitted] / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

The radical anions and ion-pairs of 1,8-dinitro-naphthalene and 1,4,5,8-tetranitronaphthalene have been perpared and the electron spin resonance spectra have been investigated in detail. The spectra were interpreted completely in terms of a set of two equivalent nitrogen atoms and three sets of two equivalent hydrogen atoms for the 1,8-dinitronaphthalene radical, four equivalent nitrogen atoms and four equivalent hydrogen atoms for the 1,4,5, 8-tetranitronaphthalene radical, respectively. The hyper-fine splitting constants obtained are compared with the values derived from molecular orbital calculations. In the ion-pairs of 1,8-dinitronaphthalene the distinct alkali metal hyperfine splitting have been observed The magnitude of the metal hyperfine splitting shows remarkable temperature dependency, and the temperature dependence is interpreted in terms of the cation exchange mechanism b between two nitro groups of 1,8-dinitronaphthalene. In the anion radical of 1,8-dinitronaphthalene as well as in the corresponding ion-pairs, anormalous line width variation has been observed. This behaviour is interpreted in terms of the cation exchange mechanism and supports the hypothesis proposed for the temperature dependence of alkali metal splitting in the ion-pairs of the compound. In the anion radical of 1,4,5,8-tetranitronaphtha-lene the twisting angle of the nitro group from the plane of aromatic ring is estimated to be (35 ±10)° from the observed splitting constants by employing the spin densities obtained with McLachlan method. The temperature dependency of the nitrogen and hydrogen splittings has been determined. The phenomenon is explained in terms of a hindered rotation of.the nitro group in 1,4,5,8-tetranitronaphthalene. From the asymmetry of the spectra it is predicted that the spin density on the nitrogen nucleus is positive. / Science, Faculty of / Chemistry, Department of / Graduate

Includes bibliographical references. / The ansamycins are a large group of natural products which have attracted considerable attention, largely as a result of their range of biological activity. The laboratory synthesis of an ansamycin has been simplified into the independent construction of the aromatic nucleus and the ansa chain, followed by their combination to form the macrocyle. The project described in Chapter 1 was designed to devise a novel, convenient, and efficient synthesis of a substituted 1,4-naphthoquinone which would function as a model for the naphthoquinonoid nucleus of the rifamycin subclass of these antibiotics. In this synthesis, 1,4-benzoquinone was converted into 8- acetyl-5,7-dihydroxy-6-methyl-3-propionylamino-1,4-naphthoquinone in six steps in an overall yield of 20%. The key step in this reaction sequence was the introduction of the C-6 methyl group via a regioselective lithiation/methylation reaction. Compounds which can be structurally defined as bioreductive alkylating agents have considerable potential as antineoplastic agents, according to H.W. Moore (Science, 1977). The protoaphins possess certain structural features which suggest their capability to function as such alkylating agents. Reductive cleavage of the aphid pigment, protoaphin-fb has been shown to give quinone A together with glucoside B, while protoaphin-sl on similar treatment affords quinone A', epimeric with quinone A at C-4, together with the same glucoside B. Professor Giles and co-workers have synthesised the 7,9-dideoxyquinone derivatives of both quinone A and A', as well as quinone A and A' themselves. The second chapter in this thesis describes three different approaches to the synthesis of a 4,10-dihydroxy-7,9-dimethoxy- 1,3-dimethyl-1H-naphtho[2,3-c]pyran analogous to glucoside B. The first two routes describe the construction of a naphtho[ 2,3-c]pyran of the correct relative stereochemistry using the novel reactions pioneered in this Department during the synthesis of 7,9-dideoxyquinone A. In the first method, the pyran ring was constructed with a C-5 oxygen substituent which was subsequently removed. The second method however, differs substantially from this route in that the C-5 substituent was not present during ring closure, hence eliminating the need to remove it at a later stage. The key step in the third approach involved the isomerisation of a dioxolane substituted naphthalene by an intramolecular version of the Mukaiyama reaction. Treatment of a C-8 brominated dioxolanyl naphthalene with titanium tetrachloride resulted in the formation of two angular naphtho[l,2-c]pyrans with the same relative stereochemistry of the pyran ring. An interesting bromine migration occurred after isomerisation had taken place. However, it is suggested that decreasing the size of the C-4 protecting group on the naphthalene nucleus prior to isomerisation, may allow the formation of the linear naphthopyran.

The reactions of butyl mercaptides with fluoro-, bromo-, nitro-, and methoxynaphthalenes in DMSO and methanol have been studied. The halonaphthalene reactions gave reasonably good yields of alkyl naphthyl sulfides via direct nucleophilic substitution. 1-Halonaphthalene gave only 1-substituted alkyl naphthyl sulfide and 2-halo- naphthalenes gave only 2-substituted alkyl naphthyl sulfides. No alkyl naphthyl sulfide was produced from either methoxynaphthalene or nitronaphthalene.