Physical Sciences and Mathematics Commons^™

Dimethyl Sulfoxide Oxydation Of Hydroxy-Steroids And Studies On The Oxidation Of The 5’–Hydroxy Group Of Nucleosides, Carmen V. Zenarosa

Dissertations

Introduction

In our earlier work we demonstrated the usefulness of the acidcatalyzed reaction between N-(p -tolyl)diphenylketenimine (21) and dimethyl sulfoxide (DMSO) for the oxidation of secondary alcohols. This was exemplified by the oxidation of 2',3'-O-isopropylideneadenosine and other secondary alcohols.¹ We have now extended this procedure to the oxidation of hydroxy-steroids.

Alkynylamines or ynamines can be written in two resonance forms: R-C≡C-N R'₂ and R-C=C=NR'₂. Because of the close similarity between the latter structure and the structure of a ketenimine (R₂C=C=N-R') and the ability of sulfoxide-ketenimine to effect the oxidation of secondary alcohols, we …

Transpiration Measurements Of The Decomposition Pressures Of Barium Hexafluorosilicate, Kemal Cankaya

Masters Theses

No abstract provided.

Simultaneous Knudsen- And Torsion- Effusion Measurements Of The Vapor Pressures Of Tetraphenyltin And Hexaphenylditin, Dale Keiser

Masters Theses

No abstract provided.

Preparation And Lead Tetraacetate Oxidation Of Aldehydic Hydrazones, Alan J. Quarfoot

Masters Theses

No abstract provided.

The Effect Of The Rate Of Formation On The Structure And Properties Of Paper, William M. Reif

Masters Theses

Paper contains an uneven distribution of fiber fractions through its cross section. The objective of this study was to determine how the rate of formation affected the structure and properties of paper. The structure of paper was analyzed with reference to the cross-sectional distribution of fines and the fines to long fibers ratio in the paper.

The formation rate and distribution of fins were varied by applying a vacuum to the British sheetmold system. As the fines were a different color than the long fibers, their distribution was determined by analyzing the brightness values of layers split from the paper. …

Data Retrieval In Mass Spectrometry By An Optical Coincidence System, Cynthia Helmintoller O'Donohue

Master's Theses

The object of this work was to develop an information storage and retrieval system for use in mass spectroscopy. The information to be stored was the compound's name, the mass spectrum, and distinctive physical and chemical properties. It was desirable that the system be one that could be used in the mass spectral laboratory. At the time this project was initiated, no system for mass spectroscopy had been developed with the characteristics of simplicity, rapid retrieval, and practicality of use in the laboratory without elaborate and space consuming equipment. Thus, a system was needed to aid the laboratory personnel in …

A Kinetic Study Of The Oxidation Of The 2, 3, And 4 Pyridine Aldehydes By Cobalt (Iii) Perchlorate In Aqueous Solution., Ronald Barry Giuntoli

All Master's Theses

Cobalt(III) perchlorate has been shown to be a powerful oxidizing agent and kinetic investigations of the mechanism of oxidation of many organic compounds including organic acids have been performed.

The Effects Of Herbicides On Three Soil Inhabiting Blue Green Algal Species, Lee C. Darlington

All Master's Theses

The object of this study was to examine the effects of varying concentrations of 2, 4-D, Dalapon, and Tordon on the growth of several nitrogen-fixing blue-green algal species obtained from soil samples and grown under culture conditions in the laboratory.

The Wittig Reaction Of Stabalized Phosphonium Ylids With Derivatives Of D-Ribose, George Robert Wellman

Masters Theses

No abstract provided.

Homogenous Catalytic Hydrogenation Of Organic Compounds Using Rhodium-Triarylphosphine Complexes, Jack Lee Parsons

Dissertations

Introduction

The purpose of this research was to study the homogeneous catalytic hydrogenation of α,β-unsaturated organic compounds containing a wide variety of reducible functional groups. The catalysts to be used were rhodium complexes of triarylphosphines. It was also desired to develop these catalytic systems into practical synthetic methods for the reduction of unsaturated compounds.

Solid-Liquid Phase Equilibria Of The Sodium-Rubidium And Sodium-Potassium-Rubidium Alloy Systems, Chen-Chao Hsu

Theses and Dissertations

Thermal methods were used, to determine with high precision, the solid-liquid phase equilibria diagrams for the sodium-rubidium and sodium-potassium-rubidium systems. In the sodium-rubidium system, the results differ greatly from those of earlier works, especially near the eutectic composition where differences in freezing points as large as 25°K occur. A detailed search was made for possible intermetallic compounds (especially Na2Rb). Neither slow temperature cycling in the temperature range where compound formation could occur nor extended periods of annealing just above the eutectic temperature produced any evidence for compound formation in the sodium-rubidium system. A 2:1 (sodium to rubidium) sample was subjected …

The Catalytic Hydrogenation Of Benzodiazines.|Ni.|Pphthlazine.|Nii.|Pquinazoline, Danny Lee Elder

Theses and Dissertations

Quinazoline and phthalazine were hydrogenated at low pressure and temperature (60 psi, room temperature) and high pressure and temperature (2000 psi, 100°C, 150°C} in neutral and acidic solvents over 5% Pd/C, 5% Ru/C, 5% Rh/Al2O3 , 5% Rh/C, and 5% Pt/C. Chromatographic methods for determining the qualitative and quantitative composition of hydrogenation mixtures were developed. The compositions of quinazoline and phthalazine-hydrogenation mixtures were determined. Eight phthalazine-hydrogenation products were detected and isolated: (1) 1,2-dihydrophthalazine, (2) 1,2,3,4-tetrahydrophthalazine, (3) a,a'-diamino-o-xylene, (4) o-methylbenzylamine, (5) 1,3-dihydroisoindole, (6) o-xylene, (7 and 8) cis- and trans- 1,2-dimethylcyclohexane. These products were identified by isolating them from reaction mixtures …

Thermodynamics Of Proton Dissociation And Metal Ion Complexation In Aqueous Solution. I, Cation Binding With Cyclic Polyethers: Significance In Ion Transport Processes. Ii, Proton Dissociation From Adenosine, Several Monosaccharides And Related Compounds. Iii, Proton Dissociation From Several Pyrimidines And Their Nucleosides At 10, 25 And 40°, Joseph Howard Ryttling

Theses and Dissertations

The log K, ΔH° and ΔS° values for the interaction of several metal ions with the two isomers of the cyclic polyether, 2,5,8,15,-18,21 hexaoxatricyclo[20.4.0.0^9,14]hexacosane are reported. The stability order found for alkali metal ion interaction with either isomer is identical to the order of ion permeability through reconstituted biological membranes for structurally related antibiotics. The size of the metal ion is critical in determining the extent of interaction. A calorimetric titration study of proton ionization from several monosaccharides and derivatives, pyrimidine bases and their nucleosides, adenosine and its derivatives, and cycloheptaamylose is described. The heats of reaction obtained in this …

A Thermodynamic Approach To The Study Of Phase Equilibria In The Sodium-Potassium Alloy System I. The Phase Diagram For Nak At Atmospheric Pressure ; Ii. High Pressure Phase Studies, Donald Ray Anderson

Theses and Dissertations

Ultra-pure reagents, platinum resistance thermometry and modern inert atmosphere glove box facilities have made possible a detailed examination of the NaK system at atmospheric pressure. A thermoanalytical study of solid-liquid phase equilibria in the NaK alloy system was conducted in the tetrahedral press to 55 kbars to investigate possible intermediate compound formation and shifting of the invariant points at various pressures. An expected shift in the eutectic composition to lower potassium content with an increase in the halt temperature on increasing pressure was confirmed. A merging of the meritectic and eutectic points at 343 ±2°K and 37 ±3 kbars occurred …

Estimations Of The Effective Electrolytic Surface Area Of Rough And Porous Silver Electrodes ; Ii. Potentiostatic Oxidation Of Silver In Alkaline Electrolyte, James Glenn Bearss

Theses and Dissertations

This dissertation is written in two sections. The first section deals with the development of methods for the estimation of the effective electrolytic surface area of rough and porous silver electrodes in alkaline electrolyte. Data are presented comparing the results of three different methods of surface area estimation. Model pore electrodes were also prepared and oxidized to study the reactions in a pore. Data for constant current oxidations of these electrodes is given. The second section deals with the potentiostatic oxidations of silver in alkaline electrolyte. Data are presented on the total charge acceptance versus applied potential for a potential …

Mechanism Of Water Transport Through Reverse Osmotic Membranes, Cheryl Kay Murphy

Theses and Dissertations

Cellulose acetate membranes show a higher permeability to water than to salt and are being used for desalination of salt water by reverse osmosis. Use of highly acetylated cellulose membranes give a higher salt rejection but also decrease flow rate of the water. The addition of very-short-chain substances or alkyl groups larger than one carbon atom to the cellulose membrane also decreases water flux. A proposed mechanism of transport through the membrane is that the water molecule is passed along the chain by hydrogen bonding with the acetyl groups, The NMR shows a change in the chemical shift of water …

Peracid Oxidation Of 3-Phenylindene, Christopher Peter Johnson

Master's Theses

Indene oxide (indan, 1,2-epoxy; indene 2,3-oxid is first recorded in the literature in 1919. This compound was formed in practically quantitative yield by the treatment of indene bromo­ hydrin in ether with powdered potassium hydroxide. At this time Van Loon also reported the preparation of indene oxide by mechanical shaking of an anhydrous, ethere!al solution of the bromohydrin with finely powdered potassium hydroxide. The desired product was obtained in a 92-97% yield by this method. Indene oxide has been prepared in a similar manner from trans-2-chloro-l-indanol by treatment "with soda," distillation of the acetone in vacuo after 15 hours, and …

A Thermogravimetric Study Of Polyvinylidene Chloride In Polymers, Charles Edward Singleton

Master's Theses

In the manufacturing of thin films such as cellophane, polymers employed as coatings greatly improve film functionality. Polymers such as polyvinylidene chloride, polyvinyl chloride, polyvinyl acetate and many others are used as coatings or components of coatings designed to improve the functionality of a film. Selection of polymers with properties that will meet the requirements of the finished film product is a continuing process of film manufacturers. Physical and chemical characterization of the polymer along with coating functionality are the factors involved in the selection. Chemical composition is the most important factor affecting polymer characteristics and must be known if …

Cyclization Studies Involving The Synthesis Of 5-Substituted-1-Naphthol, Clark Keelock Chow

Dissertations and Theses

The γ-o-substituted-phenylparaconic acids were prepared by a method patterned after that of Fuson. These paraconic acids were prepared in good yield. A re-investigation of the Perkin and Fittig methods of preparing γ-phenylisocrotonic acid was carried out without success.

The synthesis of γ-o-halophenylisocrotonic acids by thermal, and catalyzed decarboxylation of γ-o-halophenylparaconic acid, have been carried out in good yield. An effective catalyst, optimum temperature and reaction period of decarboxylation of the γ-o-halophenylparaconic acids have been determined. Infrared absorptions have characterized the γ-o-halophenylisocrotonic acids formed to be in the stable trans form. …

Synthesis Of Benzyl-Beta-D Alcohol For Use In Studies Of Photolytic Solvolysis Reactions, John Crest Anes

Honors Theses

This project proposes a means for determining whether certain photochemical solvolysis reactions proceed by an SN1 or SN2 type mechanism. The method uses optically active substrates to determine whether the displacement reaction occurs with racemization or retention of configuration. This paper deals with the synthesis of optically active benzyl-α-d alcohol from which various appropriate substrates required for the study can be prepared. Benzaldehyde---d is first prepared by the Stephens reduction of benzonitrile using stannous chloride and deuterium chloride. The optically active alcohol is then prepared by the reduction of thebenzaldehyde-d with optically active isobornyloxymagnesium bromide.

Potentiometric Edta Titrations Using A Bismuth Amalgam Electrode As Indicator, Wayne Michael Butler

Honors Theses

Previous work in the field of potentiometric titrations using bismuth-mercury electrodes with ethylenediaminetetraacetic acid as the titrant have been largely reproduced. The bismuth amalgam electrode has been further developed to provide ease of preparation and maintenance and through improved techniques of cleaning to eliminate electrode poisoning effects. Various titrations have been studied to determine the solution conditions necessary for maximum end point breaks, good electrode poise, and rapid and steady equilibrium of the electrode. These conditions have been adapted to make the electrode suitable for use with automatic titration equipment and for the analysis of multicomponent mixtures.

Toward A Synthesis Of Acenaphth (1,2-A) Acenaphth (1,2-A) Acenaphthene, John Isaac Gerson

Honors Theses

The purpose of this project was to synthesize acenaphth (1, 2-a) acenaphth (1, 2-a) acenaphthene. The project originally followed Letsinger's preparation of a synthetic precursor called acenaphth (1, 2-a) acenaphthylene, which was to be dibrominated, giving the cis-6b, 12b derivative. This derivative was to be reacted with naphthalene to yield the desired product; but this route was abandoned when a necessary forerunner of Letsinger's hydrocarbon called 1, 8-dibromonaphthalene was obtained in very low yield. An alternate procedure leading to Letsinger's hydrocarbon, involving the Friedel-Crafts addition of 1, 8-di (chloromethyl) - naphthalene to naphthalene, was devised, and a synthetic precursor of …

Electrogeneration Of Molybdate Ion, Michael John Milano

Honors Theses

The electrogeneration of molybdate ion (MoO4-2) for possible use in a coulometric determination of thorium or lead has been investigated. Constant current electrolyses were used to study the oxidation of molybdenum to molybdate. It was found that molybdate can be generated in 1N HCl with from 96 to 100% efficiency. The current efficiency for molybdate generation in less acidic media could not be determined accurately. Coulometric titrations of known amounts of thorium with electrogenerated molybdate have been carried out. The endpoints, which were determined amperometrically, were found to be inexact and reproducible to only ± 5%. Coulometric titrations of lead …

Synthesis Of Silicon Compounds For Use In (P -> D) Pi-Bond Studies, Mark Thomas Messe

Honors Theses

A new compound, (CH3CH2)2 NCH2Si (CH3)3 (I), was prepared. Attempts at synthesis of Ø-N (CH3) – CH2Si (CH3)3 (II) failed while synthesis of CH30 – CH2Si (CH3)3 (III) gave approximately 85 percent product. Difficulty was incurred in the purification of III, probably because the reactants were not sufficiently dry. Compound I was only slightly miscible in CD2=S-CD3 in dimethylsulfoxide-D6. The soluble portion showed no exchange of the methylene hydrogens in I by deuterium from the solvent although some decomposition might have occured. The apparent complete absence of an exchange reaction suggests that even in the presence of the electronegative nitrogen, …

Towards Synthesis Of Bis -(N,N'-1,8-Naphthylene)- 1,8 - Diaminonaphthalene, William Chiu-Sheung Ng

Honors Theses

This project is concerned with attempted synthesis of a special highly symetrical compound. In the process of synthesis, It is conceivable than an intermediate product will be formed.

A Fluorometric Study Of Carbamic Acids And Carbamates As An Explanation Of Carbon Dioxide Transport In The Blood, Gerald John Tiberio

Honors Theses

The original project was conceived during the summer of 1967 while Bruce Cassidy was a research fellow of the Maine Heart Association. It is through his efforts I became aware of the problem.

This research project was undertaken in order to determine the applicability of fluorometry as a means of studying the carbamate reaction of simple amino acids to model the physiological substrate hemoglobin.

Nmr Investigation Of Alkylated Diethylene - Triamine Chloro Complexes Of Trivalent Gold, Alan Robert Case

Honors Theses

The rate expression for the su~stitution of a ligand in a square planar complex was first introduced in 1953 by Taube and Rich (1). The present study was undertaken in the hope of gathering some evidence for this postulated steric hinderance by use of Nuclear Magnetic Resonance Spectra (NMR). Study was limited to one family of complexes, the alkylated diethylenetriamine chloro complexes of gold (III).

Radiolysis Of Saturated Aqueous Iodine Solutions, Gregg Alan Foster

Honors Theses

It is a well-known fact that water, when subjected to ionizing radiation such as x-ray or gamma radiation, undergoes a decomposition. The generally accepted decomposition, although complex, may be represented by (1): It is also accepted that "when dilate solutions are irradiated, practically all the energy absorbed is deposited in water molecules and the observed chemical changes are brought about indirectly via the molecular and, particularly, the radical products. Direct action due to energy deposited in the solute is generally unimportant in dilute solutions (i.e at solute concentration below about 0.1M)” (3). Realizing that iodine is an excellent radical scavenger …

Energy Calculations For The 1Εg+, 1Δg, And 3Εg- Electronic States Of The Oxygen Molecule Using A Tangent Spheres Approach, Donald Francis Durocher

Honors Theses

J. W. Linnett has proposed in his book, The Electronic Structure of Molecules (l), an approach to molecular orbital theory which he calls the double-quartet approach. The double-quartet, or d-q approach in a molecule with a completed octet, states that electrons of each spin set assume, or try to assume a tetrahedral array around their 'mother atom'. In the case of molecular oxygen, there are three d-q figures representing the molecule in its ground and 1∑+g , 2∆g, states. This representation is shown in Figure 1. Henry A. Bent, at the University of Minnesota, has proposed that the electrons in …

The Radiolysis Of Aqueous Chloroform Solutions, Francis John Simone

Honors Theses

Saturated aqueous chloroform solutions have been irradiated with a 250 Curie gamma source. G-values for the production of hydrogen gas in neutral and acidic solutions have been determined.