The free radical bromination of several cyclopropylarenes has been studied. The abstraction of a cyclopropyl hydrogen by bromine atom, which to date has been an unrecognized process, is demonstrated in this study. Specifically, when a cyclopropyl group is attached to the 9-position of an anthracene, an unprecedented hydrogen abstraction product, the corresponding cyclopropyl bromide, is obtained. This is believed to be due to stereoelectronic effects. Molecular mechanics calculations and X-ray crystallography have been used to demonstrate that 9-cycIopropylanthracene, unlike other cyclopropylarenes, is effectively locked in a conformation which places the a-cyclopropyl C-H bond in alignment with the p-orbitals of the aromatic system. This proper alignment activates the a-cyclopropyl hydrogen for abstraction by bromine atom. The relative reactivities of several 9-alkylanthracenes towards bromine atom are established, namely: 9-methyI- > 9-cyclopropyI- > 9-ethyl- >> 9-isopropylanthracene. Semi-empirical molecular orbital theory and molecular mechanics calculations have been utilized to demonstrate that the relative reactivities are not a function of bond dissociation energies but rather a function of the size of the dihedral angle between the a C-H bonds and the plane of the central ring of the various 9-alkylanthracenes in their lowest energy conformations. The absolute rate constants for the abstraction of hydrogen by bromine atom from 9-methyl-, 9-cyclopropyl-, and 9·ethylanthracene are estimated to be 1.1 x 10⁸ M⁻¹ sec⁻¹, 3.8 x 10⁷ M⁻¹ sec⁻¹ and 7.2 x 10⁶ M⁻¹ sec⁻¹ respectively. The value for the primary hydrogen/deuterium isotope effect for the abstraction of hydrogen by bromine atom from 9-cyclopropylanthracene is determined to be 2.6. All of the above observations lend support to the importance of stereoelectronic effects in the free radical bromination of the cyclopropylarenes and 9-alkylanthracenes. / Ph. D.

In this thesis the right and left pole structure of a not necessarily regular rational matrix function W is described in terms of pairs of matrices-right and left pole pairs. The concept of orthogonality in Rⁿ is investigated. Using this concept, the right and left zero structure of a rational matrix function W is described in terms of pairs and triples of matrices-right and left null pairs and right and left kernel triples. The definition of a spectral triple of a regular rational matrix function over a subset σ of C is extended to the nonregular case. Given a rational matrix function W and a subset σ of C, the left null-pole subspace of W over σ is described in terms of a left kernel triple and a left σ-spectral triple for W. A sufficient condition for the minimality of McMillan degree of a rational matrix function H which is right equivalent to W on σ, that is a rational matrix function H of the same size and with the same left null-pole subspace over σ as W, is developed. An algorithm for constructing a rational matrix function W with a left kernel triple (A_κ B_κ D_κ) and left null and right pole pairs over σ⊂C (A_ζ, B_ζ) and (C_π, A_π), respectively, from a regular rational matrix function with left null and right pole pairs over σ (A_ζ, B_ζ) and (C_π, A_π) is described. Finally, a necessary and sufficient condition for existence of a rational matrix function W with a given left kernel triple and a given left spectral triple over a subset σ of C is established. / Ph. D.

This work describes a novel family of catalysts denoted Supported Aqueous Phase Catalysts (S.A.P.C.). These catalysts consist of a water-soluble organometallic complex supported in a thin film of water residing on a high surface area hydrophilic solid; the reaction takes place at the water-organic interface where the organic contains the reactants and products. This novel type of catalysis is demonstrated by liquid phase hydroformylation. The support chosen is CPG-240, a porous glass with a narrow pore volume distribution. The catalytic species, HRh(CO)[m-P(PhSO₃Na)₃]₃ was synthesized from Rh(CO)₂(acac) by a new synthetic route and the complex was characterized by ³¹P solution NMR, ¹H solid-state NMR, and FTIR. After dissolving the catalytic species in water, it was impregnated into CPG-240. The hydroformylation of oleyl alcohol (OLOH) was accomplished at l00°C and 725 psig of H₂/CO = 1:1 using 0.002g Rh/g OLOH. As an example, after 5.5 h of contact time, 96.6% conversion was achieved. Evidence of no leaching of Rh was obtained by filtering away the supported catalyst and attempting both the hydroformylation of additional OLOH and the hydrogenation of added 1-hexene. The absence of conversion in both cases indicated that Rh was not leached into the organic phase. Because: (1) OLOH is not water soluble, (2) its double bond is internal and (3) the Rh does not leach into the organic phase, the concept of SAPC, which is to perform catalysis at an interface, is proven. / Ph. D.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Texte remanié de: Diss.--Litt.--Philadelphie--University of Pennsylvania, 1970. / Bibliogr. p. 92-97. Index.

Thesis (M.S.)--Oregon State University, 2007. / Printout. Includes bibliographical references (leaves 111-121). Also available on the World Wide Web.

Orientador: Wilson Suzigan / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Economia / Made available in DSpace on 2018-07-19T11:33:33Z (GMT). No. of bitstreams: 1 Costa_CarlosAnibalNogueira_D.pdf: 6955051 bytes, checksum: 76dc42f903ba4139fe1481b75411909f (MD5) Previous issue date: 1994 / Resumo: Não informado / Abstract: Not informed. / Doutorado / Doutor em Economia

Over the course of his life Beckett's work moves through a process of reduction toward increasing simplicity and concentration of means. 1 trace this reduction in Beckett's later works for the stage and compare it with the dialectics of negative theology, both Buddhist and Orthodox Christian, paying particular attention to structures of visuality and iconicity (both visual and not) in Beckett's work. The visual enjoyed a status of peculiar ontological primacy for Beckett. In it he saw exemplified both the dualisms he worked to overcome throughout his career and the saving grace that will overcome them: a "breathless immediacy" (Beckett's words) that will skip the mediation of language and the linearity of discourse and present exquisitely balanced, essentially still, nondual images. Beckett's metaphorical, that is, vertically structured stage images are subtended by metonymic texts that run through a strategic process of self-emptying in a kind of kenosis of discourse. The aporetic figures thus produced form similarly iconic structures on the textual level as can be found on the visual level. In Beckett's horizontal world a displaced sacramentalism and a phenomenologically motivated process of enquiry into the nature of things combine to create an empty space, a gray area through which the divine can enter if the audience is inclined to make such an act of faith. Beckett creates an art of Erfahrung that leads to a confrontation with an Other beyond the limits of a reductive concept of instrumental reason.

The thesis deals with Czech translations of Swedish literature and their reception between 1948 and 1989. Against the background of contemporary societal changes and culture policy, it tries to answer the questions who, why, when and under which circumstances translated Swedish literature and how the political situation influenced the selection, the translation process and the publishing of the works. The thesis describes individual translations in their contemporary historical, cultural and social context. It also includes reactions to Swedish literature in Czech press, most notably reactions were published in the Světová literatura journal. The thesis also contains a bibliography of the translations that were published during the period and profiles of the most prominent translators.

Dissertation--Universität Frankfurt (Main). / Bibliog. p. 221-247.