Thesis--Wisconsin. / Vita. Includes bibliographical references.

Thèse--Brussels? / Includes bibliographical references.

Thesis (Ph. D.)--University of Illinois, 1923. / Vita. Caption title: Trihydroxy-methyl-anthraquinones. I, by G.D. Graves with Roger Adams. "Reprinted from the Journal of the American chemical society, vol. XLV, no.10, October, 1923."

Previous work from our laboratory has been concerned with investigating the photochemical reactivity of tetrahydro-1,4-naphthalenedione and tetrahydronaphthoquinol systems, both in the solid state and in solution. The fascinating results obtained prompted us to extend the studies to the analogous tetrahydro-1,4-anthracenediones, tetrahydro-5,12-naphthacenediones and tetrahydroanthraquinol systems. Tetrahydro-1,4-anthracenedione is expected to undergo bis-enolization with extreme ease, and therefore its preparation requires mild and neutral conditions. These compounds were prepared by Diels-Alder reaction between o-quinodimethane and p-benzoquinone and other p-substituted quinones o-Quinodimethane was generated in situ by sulphur dioxide extrusion from 3,6-dihydrobenzo[b]oxathiin-2-oxide. The photochemistry of the tetrahydro-1,4-anthracenediones, tetra-hydro-5,12-naphthalenedione and tetrahydroanthraquinols has been investigated both in the solid state and solution. The effect of the solid state medium on the photoreactivity, compared to the solution, is significant; the nature and/or the number of the photoproducts formed in the solid state is generally different from the results obtained in solution. These differences have been explained on the basis of the crystal and molecular structures of the reactants. Special steric effects, which may impede the photochemical reactions in the solid state have been identified. The values of the geometric parameters (d, r and A) for hydrogen atom abstraction are found to be similar to those observed in earlier studies by Scheffer et al. It has been found that the o-quinodimethane/2,3-dimethyl-l,4-naphthoquinone adduct affords, via β-hydrogen atom abstraction and closure of the resulting 1,3-biradical, a cyclopropanol. The cyclopro-panol itself undergoes photolysis initiated by a novel ring opening process. Irradiation of crystals of the adduct does not result in any cyclopropanol. The reasons for the non-reactivity of the Diels-Alder adduct in the solid state have been suggested to be due to the non-bonded steric interactions between the lattice neighbors as shown by the X-ray crystal structure. The photorearrangement of one substrate, namely 2,3,4a,9a-tetra-methyl-4a,9a,9,10-tetrahydro-1,4-anthracenedione is found to be controlled by the temperature, multiplicity, and phase of the reaction. By carrying out the reaction at or above room temperature or in the presence of a sensitizer or in the crystalline state, the reaction can be forced in one direction. Lowering the photolysis temperature causes the formation of another product. The nature of the photoproduct is independent of the temperature in the crystalline state. The results have been interpreted in terms of a required ring inversion which is needed for the formation of the low temperature photoproduct (see Scheme 44). The ring inversion is not allowed in the solid state. / Science, Faculty of / Chemistry, Department of / Graduate

The oxidation of substituted phenols with phenyliodonium diacetate in methanol was found to afford 2,4-cyclohexadienones, 2,5-cyclohexadienones or mixtures of isomers depending on the substrate being oxidized. A reaction mechanism was proposed for this oxidation which involved an intermediate aryloxenium ion. A strong correlation was observed between the experimentally determined product ratios and the results predicted by calculation of the LUMO coefficients of the proposed intermediates, Annulation of these cyclohexadienones with the anion derived from cyanophthalide afforded substituted anthraquinones in high yields. The chemistry relating to the annulation of Michael acceptors with phthalide anions was comprehensively reviewed. A mild selective method for the oxidation of hydroquinones to quinones using dibenzoyl peroxide and base is presented. A general synthetic approach to C-glycosylanthraquinones was presented, based on the annulation of a C-glycosylcyclohexadienone with the anion derived from cyanophthalide, A suitable precursor to a C-glycosylcyclohexadienone, 2-(2’,3’,4’,6’-tetra-0-acetyl-|3-D-glucopyranosyl)benzyloxybenzene, was prepared via the reaction of benzoylbromoglucose with 2-benzyloxyphenylmagnesium bromide, A group of molecules were prepared by a Marschalk reaction between /ewcoquinizarin and aldehydo-sugsrs. These compounds are potential bioreductive alkylating agents in which molecular simplicity can be achieved without overly sacrificing DNA binding ability.

Thesis (Ph. D.)--Bryn Mawr college, 1929. / Vita.

Thesis (Ph. D.)--Princeton University, 1922. / "Reprinted from the Journal of the American Chemical Society, vol. XLIV, no.10. October, 1922."

No description available.

Thesis (Ph.D.)--Chemical Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Dr. Jeff Empie; Committee Member: Dr. Bill Koros; Committee Member: Dr. Jim Frederick; Committee Member: Dr. Tom McDonough; Committee Member: Dr. Xin-Sheng Chai

Thesis (Ph. D.)--Johns Hopkins University, 1920. / Biography.