Thesis (Ph. D.)--Lehigh University, 2004. / Includes vita. Includes bibliographical references (leaves 179-187).

Nitrogen oxide trifluoride was prepared in trace quantities by the reaction of nitric oxide and fluorine. Low, but improved yields were obtained when nitrosyl fluoride and fluorine were heated together at 220°. It was found that (NO)₂2NiF₆ was formed by the reaction of the walls of the Monel reaction vessels, with nitrosyl fluoride, and fluorine, and that pyrolysis of this salt (in 70 p.s.i. fluorine at 350°) gave the new compound in good yield. The reactions of platinum and iridium hexafluoride with nitrosyl fluoride were investigated as routes to ONF₃. Nitrogen oxide trifluoride was colourless in the solid, liquid, and gaseous phases, melting at -161° and boiling at -87.5°. The vapour pressure was determined over the range -128° to -78°. The empirical formula was established by elemental analysis, and by determination of its molecular weight. The structural formula ONF₃ was established from the ¹⁹F n.m.r., and the infrared spectrum of the compound. Nitrogen oxide trifluoride was found to be only moderately reactive. There was no evidence that ONF₃ could be protonated by strong acids. A 1:1 adduct was formed with AsF₅. The chemical behaviour and infrared spectrum of ONF3,AsF₅ was consistent with the formulation ONF₂⁺AsF₆⁻. The empirical formula of (NO)₂^NiF₆ was established by elemental analysis. Its infrared spectrum, and magnetic susceptibility showed that it contained the (NO)⁺ and (NiF₆)²⁻ ions, and a low spin d⁶ arrangement for Ni(IV). The X-ray powder diffraction patterns of (NO)₂NiF₆ could be indexed on the basis of a hexagonal unit cell a = 5.524 Å, c = 5.097 Å, except for five diffuse lines that varied in intensity from sample to sample. Weissenberg (h k 0, h k 1,h k 2, h k 3) photographs showed two sets of reflections. One sharp strong set that could be indexed on the basis of the same hexagonal cell as the lines of the powder photograph, and a weak diffuse set of reflections that together with the strong reflections could be indexed on the hexagonal unit cell, a = 4x5.524, c = 5.097 Å. A structure determination was carried out using the strong sharp set of reflections. The diffraction data were consistent with various models, but the most likely model consisted of (NiF₆)²⁻ groups with the fluorine atoms in a regular octahedron around the nickel atom and the Ni-F bond distance equal to 1.76 Å. The N-O bond distance was very short, 0.88Å, and had associated with it regions of electron density normal to the axis defined by the nitrogen and oxygen atoms. A similar situation for the O2⁺ ion in O₂PtF₆ was reported by Ibers and Hamilton.(108) At 200° chlorine pentafluoride and iridium hexafluoride reacted to give small quantities of a yellow compound which was characterised as ClF₂⁺IrF₆⁻ from elemental analysis, magnetic susceptibility measurements, and its infrared spectrum. A structural determination was attempted from single crystal X-ray data. Preliminary results suggest that the iridium atoms form an ab face centred array, and the chlorine atoms are situated almost in the centre of the square pyramidal holes defined by the iridium atoms. / Arts, Faculty of / Philosophy, Department of / Graduate

Thesis (Ph. D.)--University of Wisconsin--Madison, 1969. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

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We present the synthetic studies of coerulescine, horsfiline, and streptorubin B in this report. And we also present the new synthesis of 3-arylpyrrolines and cis-3,4-diarylpyrrolidines via an easy and straightforward pathway in this report. All of these researches are using 4-hydroxypiperidine and 4-hydroxyproline as the starting material.

This thesis describes investigations into the utility of boron fluorides and tetrafluoroborates as sources of nucleophilic fluorine. Chapter 1 discusses the history and importance of the field of organofluorine chemistry and outlines some of the principle motivations for the site-selective fluorination of organic molecules. Some of the most commonly useed methods of nucleophilic fluorination are briefly surveyed, with an emphasis on the formation of fluorinated stereogenic centres. Literature precedent for the use of tetrafluoroborates and boron trifluoride as nucleophilic fluorinating agents is also presented. Chapter 2 describes the development of a highly regio- and stereoselective S_Ni-type ring-opening fluorination of trans-β-substituted aryl epoxides using BF₃●OEt₂ as a nucleophilic fluorinating agent. This robust and scalable protocol grants efficient access to a variety of functionalised benzylic fluoride building blocks, and provides a solution to the problem of stereocontrol in the synthesis of this class of compounds. To highlight the utility of the resultant syn-fluorohydrins in the synthesis of stereodefined β-fluoro β-aryl amines, their elaboration to a range of aryl-substituted β-fluoroamphetamines is demonstrated. Chapter 3 introduces the concept of tuning the reactivity of BF₃ by replacing one or two of the fluoro ligands on boron for electron-donating alkoxy group(s). On this basis, pinacolatoboron fluoride (pinBF) [which may be prepared in situ by pre-mixing BF₃●OEt₂ and bis(O-trimethylsilyl)pinacol] is identified as a superior reagent to BF₃●OEt₂ for the ring-opening fluorination of trans-β-substituted aryl epoxides bearing electron-rich aryl groups. Chapter 4 details a highly regioselective and stereospecific S_N2-type ring-opening fluorination of 2,3- and 3,4-epoxy amines using HBF₄●OEt₂ as a nucleophilic flurine source. The reactions are both operationally simple to perform and readily scalable, and proceed to completion within 5 min at ambient temperature, providing a highly practical and economical route to stereodefined amino fluorohydrins. To highlight the synthetic utility of this reaction in the preparation of pharmaceutically-important β-fluoro amines, a concise de novo asymmetric synthesis of (S,S)-3-deoxy-3-fluorosafingol is performed. Chapter 5 chronicles the successful development of a protocol for the direct hydroxyfluorination of allylic amines to the corresponding amino fluorohydrins, using m--CPBA as the oxidant and HBF₄●OEt₂ in a dual role as both the Brønstead acid N-protecting agent and nucleophilic fluorine source. With chiral allylic amines which are conformationally biased or constrained, the diastereofacial selectivity of the reaction can be controlled by altering the concentration of HBF₄●OEt₂ employed in the reaction, allowing for a diastereodivergent hydroxyfluorination process. The synthetic utility of this methodology is demonstrated via its application to the diastereodivergent synthesis of 4-deoxy-4-fluoro-L-xylo-phytosphingosine and 4-deoxy-4-fluoro-L-lyxo-phytosphingosine, each in 5 steps from Garner's aldehyde. Chapter 6 contains full experimental procedures and characterisation data for all compounds synthesised in chapters 2, 3, 4 and 5.

Density functional theory is an efficient and useful method of solving single-reference computational chemistry problems, however it struggles with multi-reference systems. Modifications have been developed in order to improve the capabilities of density functional theory. In this work, density functional theory has been successfully applied to solve multi-reference systems with large amounts of non-dynamical correlation by use of modifications. It has also been successfully applied for geometry optimizations for lanthanide trifluorides.

Dans le premier chapitre de cette thèse, nous nous sommes intéressés aux virus de l'immunodéficience humaine et des hépatites B et C ainsi qu'aux thérapies utilisées dans le traitement de ces affections. Nous avons introduit l'importance des nucléosides fluorés, et nous avons donné quelques exemples de nucléosides fluorés utilisés en chimiothérapie antivirale et antitumorale. Dans le second chapitre, nous avons présenté une synthèse rapide de 2',3'-didésoxy-3'-fluoro-beta-D-thréo-nucléosides portant les bases pyrimidiques naturelles et substituées en position N3 par un groupement nitro ou amino. Les composés obtenus ont été évaluées contre divers virus à ADN et ARN (y compris le VIH) dans des expériences de culture cellulaire. Dans le troisième chapitre, nous nous somme intéressés à la synthèse de différents 2',3'-didésoxy-2'-fluoro-3'-(N-hydroxyimino), (N-methoxyimino) and (hydroxyl-amino) nucléosides en série pyrimidine. Les composés obtenus ont été évaluées contre divers virus à ADN et ARN dans des expériences de culture cellulaire. / In the first chapter, we presented the human immunodeficiency virus (HIV), hepatitis B virus (HBV), and hepatitis C virus (HCV), as well as the therapies used to treat these diseases. In a second part, we discussed about the importance of the incorporation of fluorine atom into nucleoside analogues, and in a third part of this chapter, we presented the recent literature sources of the synthesis and biological activity of fluorinated nucleosides. In the second chapter, we designed and synthesized a series of 2',3'-dideoxy-3'-fluoro-threo-pyrimidine nucleosides by direct and rapid methodology and evaluated them for their inhibitory effects on a number of RNA and DNA viruses in cell culture experiments. None of these nucleoside derivatives showed any antiretroviral activity nor cytotoxicity. In the third chapter of this manuscript, we synthesized a new series of 2',3'-dideoxy-2'-fluoro-3'-(N-hydroxyimino),(N-methoxyimino) and (hydroxylamino)pyrim idine nucleosides and also evaluated for their inhibitory effects on a number of RNA and DNA viruses, without finding any activity or cytotoxicity.

Acid/Base characterizations of metal oxide surfaces are often used to explain their catalytic behavior. However, the vast majority of these studies have been performed on powders or supported oxides, and there is very little information available in the literature on the interaction of acid/base probe molecules with well-defined oxide surfaces of known coordination geometry and oxidation state. The well-defined, single crystal surfaces of Cu₂O (111), SnO₂ (110), and Cr₂O₃ (101̲2) were investigated for their acid/base properties by the interactions between the probe molecules and the well-defined surface features. The adsorption of NH₃ at cation sites was used to characterize the Lewis acidity of SnO₂ (110) and Cu₂O (111) surfaces. The adsorption of CO₂, a standard acidic probe molecule, was used to characterize the Lewis basicity of the oxygen anions on SnO₂ (110), Cu₂O (111) , and Cr₂O₃ (101̲2) surfaces. BF₃, while not a standard probe molecule, has been tested as a probe of the Lewis basicity of the oxygen anions on SnO₂ (110) and Cr₂O₃ (101̲2). By studying probe molecules on well-defined metal oxide surfaces with known coordination geometry and oxidation state, an overall evaluation of NH₃, CO₂, and BF₃ as probe molecules can be made using the surfaces studied. NH₃ probed differences in Lewis acidity of Sn cations on SnO₂ (110), which had differences in coordination environments and oxidation states. But, NH₃ adsorption failed to provide any direct information on differences in Lewis acidity of Cu cations in different local coordination geometries on Cu₂O (111). CO₂ is a poor probe of the Lewis basicity of oxygen anions on the metal oxide surfaces studied here. CO₂ does not strongly adsorb to either SnO₂ (110) or Cu₂O (111). On Cr₂O₃ (101̲2), CO₂ does interact with oxygen sites but in two different coordinations, which vary with surface condition, making a comparison of basicity difficult. In the cases studied here, CO₂ either does not adsorb, or it does not provide a clear set of results that can be related simply to Lewis basicity. BF₃ seems to be a much better probe of the Lewis basicity than CO₂ for the well-defined metal oxide surfaces studied here. On SnO₂ (110) and Cr₂O₃ (101̲2), the boron atom of BF₃ directly interacts with oxygen sites by accepting their electrons. BF₃ thermal desorption seems to provide a direct measure of the Lewis basicity of different surface oxygen species as long as they are thermally-stable in vacuum. / Ph. D.