Physical Sciences and Mathematics Commons^™

The Deamination Of Deuterated-2-Hydroxy-2-Phenyl-3-Aminonorbornanes, Michael D. Eckart

Doctoral Dissertations

2-endo-Hydroxy-2-phenyl-3-endo-aminonorbornane-5,6-exo-d₂ was synthesized and subjected to nitrous acid deamination in glacial acetic acid. From the cationic rearrangement reaction eight products were isolated by liquid elution chromatography and identified by nuclear magnetic resonance spectroscopy. 2-exo-Hydroxy-2-phenyl-3-endo-aminonorbornane was also synthesized and deaminated under similar conditions. The product yields from this compound as well as the product yields from the 2-endo-hydroxy amine were determined by vapor phase chromatography.

From an examination of the deuterium distribution in the products of the deuterated amine and from the yields of products from both amines it was possible to construct a reasonable reaction sequence for the deamination …

An X-Ray Diffraction Study By The Powder Method Of Solid Solutions In The System Zno-Cro3-H2O At 25° C, William Alan Livingston

Masters Theses

No abstract provided.

Applications Of Modified Wittig Reaction To Butatriene Synthesis, John Pearson

Dissertations and Theses

The preparation of allenes by the condensation of an acyl chloride with a phosphonium ylid and subsequent elimination of an acid salt and a phosphonium oxide has been established by Bestmann and Hartung. It was felt that this process could be expanded to include the synthesis of butatrienes. Butatrienes are stabilized by aromatic substituents while aromatic substituents decrease the nucleophilicity and reactivity of the phosphonium ylids to be used in the synthesis of the butatrienes. The ylids employed were carbomethoxyphenylmethylenetriphenyl phosphorane, and a new compound, carbethoxyphenylmethylenetriphenyl phosphorane, both of which failed to form alkylated condensation products. Both ylids were prepared …

Spectrophotometric Studies Of Complex Formation Of Alpha Aminohydroxamic Acids, Jing Shyong Chen

Masters Theses

No abstract provided.

The Reaction Of Ethylenediamine With Cobalt (Ii) Perchlorate And Oxygen In Dilute Aqueous Solutions, Robert J. Karmy

All Master's Theses

Cobalt (II) perchlorate was reacted with ethylenediamine and molecular oxygen. Various mole ratios of ethylenediamine to cobalt (II) were oxygenated and studied by photometric, potentiometric, conductometric, magnetic susceptibility, freezing point depression, electron spin resonance and cobalt (II) extraction methods. The fact that the complex was brown in color, diamagnetic, contained ethylenediamine to cobalt to oxygen in a mole ratio of 4:2:1 was confirmed. The complex underwent elation to form a polymeric species with excess base. The complex could not be oxidized to a green paramagnetic complex by reacting it with sodium peroxydisulfate, potassium bromate, bromine or chlorine. Ammonia was added …

Preparation Of Phenylsulphur Chloride Tetrafluoride, Dennis T. Sauer

All Master's Theses

The reaction of C6H5SF3, CSF and C12 was studied under a variety of conditions. The reaction run in the presence of a trace of water yielded C6H5SO2F and C1C6H4SO2F. The reaction run in stainless steel at 170°C yielded an amber solid believed to be a polymer with the empirical formula C6H3.67SF2. Chlorination of a C6H5SF3-CSF mixture in monel at 220°C yielded a yellow liquid tentatively identified as a mixture of the new species C6H5SF4C1, FC6H4SF4C1 and C1C6H4SF4C1.

High Pressure, High Temperature Syntheses Of Rare Earth Diantimonides And Th₃P₄ Type Polymorphs Of Rare Earth Sesquisulfides, Normal L. Eatough

Theses and Dissertations

The rare earths form series of compounds which are known for several elements but end abruptly or undergo a change of structure at some member of the series. The diantimonides are one such series. Sb-Sb repulsion becomes stronger as the rare earth size decreases and the previously known series ended at Sm. It was felt that high pressure would overcome the Sb-Sb repulsion and allow bonding to form stable or metastable compounds not possible by ordinary techniques. Synthesis studies were carried out on mixtures of antimony with all the rare earths except Pm and with Sc and Y. The known …

The Thermodynamics (Log K, [Delta]H°, [Delta]S°, [Delta]Cp°) Of Metal Ligand Interaction In Aqueous Solution.|Ni.|P Design And Construction Of An Isothermal Titration Calorimeter.|Nii.|Pthe Interaction Of Cyanide Ion With Bivalent Nickel, Zinc, Cadmium And Mercury.|Niii.|Pthe Interaction Of Glycinate Ion With Bivalent Manganese, Iron, Cobalt, Nickel, Copper, Zinc And Cadmium, Harlin Dee Johnston

Theses and Dissertations

A new isothermal titration calorimeter has been designed to facilitate the study of heats of reaction and heats of solution at constant temperature. With this calorimeter, endothermic or exothermic processes can be studied at temperatures constant to ±0.0002°C. Heat effects are compensated by balancing the heat effect of the process taking place in the calorimeter against a variable heat and a constant cooling Peltier device. The calorimeter was tested by measuring the heat of ionization of water and the heat of dilution of aqueous HClO_4 solutions. For these systems heats were measured to an accuracy of ±0.02 calorie. Log K, …

The Effect Of Thiamine And Its Antagonists On Plasma And Tissue Lactic Dehydrogenase In Rats, Dong Hwa Park

Theses and Dissertations

The lactic dehydrogenase activity in plasma and tissues was measured in the thiamine-deprived, the oxythiamine-treated and the pyrithiamine-treated rats as well as the control rats. The lactic dehydrogenase levels of brain and kidney were significantly increased by oxythiamine treatment. The enzyme activity in heart was markedly decreased only in the thiamine-deprived rats. Unlike the above tissues, the enzyme levels in liver were decreased by 29-44 per cent in all three types of thiamine deficiency, However, the enzyme activity in plasma was significantly increased only by pyrithiamine administration. The distribution patterns of lactic dehydrogenase isozymes were electrophoretically examined in these deficiencies. …

A Study Of Reaction Parameters In The Hydrogenation Of Acetic Acid By Rhenium Heptoxide Catalyst, Victor L. Mylroie

Theses and Dissertations

Rhenium oxides as well as other rhenium compounds are known to display a broad spectrum of catalytic activity,^25 being resistant to attack by acids under nonoxidizing conditions, and showing a remarkable ability to resist poisoning which is a serious limiting factor in many commonly used catalysts. Rhenium catalysts are cheaper than the platinum metals with the exception of palladium. One of the most remarkable properties of the rhenium catalyst is the ability to catalyze the hydrogenation of carboxylic acids and amides to the corresponding alcohols and amines respectively. The carboxyl group (-COOH) is notoriously difficult to reduce catalytically and most …

Determination Of Stability Constants At 25c For The Interaction In Aqueous Solution Of Serine With Co (Ii), Ni (Ii), Cd (Ii), Zn (Ii), And Cu (Ii) Ions, Liak Hwe Ma

Theses and Dissertations

Values of thermodynamic stability constants at 25°C for the complexes of serine with the metal ions. Co^2+, Ni^2+, Cd^2+, Zn^2+, and Cu^2+ were obtained from pH titration data. All measurements were made in aqueous solution, and data were obtained at three different ionic strengths for each metal ion studied. It was assumed that the activity of the zwitterion is unity. The effect of metal ion hydrolysis upon the log K values was taken into account for the calculations. For all the metal ions studied, stability constants for MA^+, MA_2, and MA_3^- were reported with the exception of copper (II) which …

An Ultraviolet Absorption Study Of The Carbamate Reaction As An Explanation Of Carbon Dioxide Transport In The Blood, Bruce Raymond Cassidy

Honors Theses

This research project was undertaken in order to determine the applicability of ultraviolet absorption spectroscopy as a means of studying the carbamate reaction of carbon dioxide with glycine or diglycine. These compounds are thought to model the physiological substrate hemoglobin. Where for glycine R = -CH2- and for diglycine R = -CH2-CO-NH- CH2-. The reaction involves only the non-ionized alpha-amino group of the conjugate base species. It is therefore necessary that the reaction be run in a moderately basic medium, but at pHs not greater than ten. The ultraviolet absorption spectra for the conjugate acid, zwitter-ion, and conjugate base of …

The Chronopotentiometry Of Bismuth, Cynthia Elaine Wilson

Honors Theses

Whenever a constant current electrolysis is performed without stirring, the potentials of the electrodes change with time because the concentrations change at the surfaces of the electrodes. The principle of chronopotentiometry is based upon the idea that since the current is kept constant, the electrolysis proceeds at a constant rate. When the electrolysis circuit is closed, the concentrations of the substances taking part in the electrochemical reaction at the surface of the electrode start to vary. The electrode takes up the equilibrium potential as given by the Nernst equation provided the reaction is reversible. If the transport of the substances …

The Configuration Of Dichlorodiphenylethers, Wayne Lavelle Brantley

Honors Theses

No definite molecular configuration of diphenylethers has ever been substantiated by experimental proof. Due to the free rotation of the benzene rings about the oxygen linkage, the diphenylether can take any number of spatial configurations. Some theoretical work has been done in trying to determine the molecular structure, but it was felt that careful examination of the high resolution nuclear magnetic resonance spectra of the ethers would be useful in determining a structure.

Synthesis And Nitrosation Of 5,8-Dimethylhydrocarbostyril And Hydrocarbostyril, Harold Leigh Frye

Honors Theses

Research was undertaken this year to complete Huisgen's efforts by synthesizing the six-membered ring N-nitrosobenzo­lactam. This gap was left by Huisgen due to his unsuccessful attempt to produce N-nitroeohydrooarbostyril. My efforts were applied to this problem; namely, the synthesis of the six-membered N-nitrosolactam of hydrocarbostyr11 and 5,8-dimethylhydrocarboetyril.

Electrostatic Models Of Bonding In Molecules, John Joseph Moore Jr.

Honors Theses

Calculations of the energy differences between ground and excited states will be presented. A comparison of the results will be made.

Kinetics Of The Deformylation Of 2,6-Dichlorobenzaldehyde In Moderately Concentrated Sodium Hydroxide, Clifford William Coughlin

Honors Theses

Bunnett, Miles, and Nahabedian (3) studied the kinetics of the alkali cleavage of 2, 6-dichlorobenzaldehyde at base concentrations ranging from .211M. to 1.86M. They found that the simplest mechanism which gives an adequate account of the kinetics is represented by equations (I) and (II). For the step presented by equation (II), kc is the concentration independent second-order rate constant. The purpose of this project was to expand the region studied to the highest feasible base concentration.

Radiation Chemistry Of Aqueous Chloroform Solutions, Henry Douglas Kutz

Honors Theses

Saturated aqueous chloroform solutions have been irradiated with gamma rays from a cobalt-60 source. G values for the formation of HCl in oxygenated and deaerated solutions have been determined. Preliminary work involving the determination of hydrogen gas from the irradiated solutions is reported.

A Review Of (P→D) Π-Bonding In Silicon Compounds, Donald Robert Siebert

Honors Theses

In spite of all the work done since Brockway and Coop's articles appeared in 1938, the problem of the use of silicon's 3d-orbitals in bonding still remains inconclusive.

Attempted Oxidation Of Benzaldehyde With Sodium Bismuthate (Part One). Reduction Of Xanthene By Lithium In Methylamine (Part Two), Gordon Lee Schiff

Honors Theses

The purpose of this investigation was to determine whether sodium bismuthate would oxidize an aldehyde containing only one oxygen atom. Benzaldehyde was selected for these studies because it is a relatively good reducing agent and is not likely to undergo condensation reactions. (Part One).

The primary objective of this research is to confirm Nielsen's proposal that (I) and/or (II) is the oxidation product of 1,2,3,4-tetrahydrofluorene. In doing so, this project is also concerned with the attempted reduction of xanthene and the subsequent oxidation of its reduction product. (Part Two).

Determination Of Calcium By The Coulometric Generation Of Oxalate Ion, Brian Jude David Koch

Honors Theses

The purpose of this research was to develop an electrode sensitive to calcium ion concentration that could be used to detect the endpoint in an automatic titration involving the generation of oxalate by the reduction of lead oxalate.

Cerebrosides Of Human Aorta: Isolation And Fatty Acid Distribution, Eric Coles

Masters Theses

No abstract provided.

The Synthesis Of 5- And 8-Dialhylamino-Alkylaminopyrido [2,3-D] Pyridazines As Potential Antimalarial Agents., William M. Rich

Chemistry and Chemical Biology ETDs

The appearance of strains of malaria resistant to most of the synthetic antimalarial agents has prompted the investigation of new compounds for antimalarial activity. The structural similarities of the nucleus of pyrido [2,3-d] pyridazine to pteridine as well as to the known quinoline antimalarials suggested the possibility of development of potential chemotherapeutic agents based on the ring system.

A series of 5,8 substituted pyrido [2,3-d] pyridazines were prepared in which one substituent was a dialkylaminoalkylamino group and the other substituent either a chloro, ethoxy, or hydroxy group. Ultraviolet, infrared, and nuclear magnetic resonance spectra were reported for all compounds. Structures …

Bacterial Degradation Of Methyl Dehydroabietate, Burl C. Carter

Dissertations and Theses

Bacteria (Arthrobacter sp.), isolated from lodgepole pine (Pinus contortus), are capable of utilizing methyl dehydroabietate as the sole source of carbon. Degradation products of methyl dehydroabietate have been obtained by manually extracting the cell-free supernatant solution of a liquid growth medium with methylene chloride. Gas chromatography (G. L. C.) was used for separation of the neutral products. The acid products were converted to their methyl esters diazomethane and then separated by gas chromatography. Structures have been proposed for two G. L. C. fractions (V, II) on the basis of infrared (I.R.) and mass spectral (M. S.) data. …

Isolation And Partial Characterization Of The Toxic Substance From Eremocarpus Setigerus Benth, Shuliang Lee

Loma Linda University Electronic Theses, Dissertations & Projects

The work on the active substance of Eremocarpus setigerus Benth has been previously performed by Naito and Noller. However, the investigation was not complete. Therefore we isolated and tested this substance by steam distillation and thin layer chromatography technique. A yellow sticky toxic substance was isolated with Rf values of 0.15 in benzene system and 0.57 in benzene-absolute ethanol (95:5 v/v) system.

The toxic substance which is free of halogen, nitrogen, and sulfur, is soluble in ethyl ether, ethanol, and concentrated sulfuric acid. It has a maximum absorption in the ultraviolet region that indicates the presence of unsaturation. Its infrared …

The Effect Of Oak Leaves On The Leaching Of Trace Metals From Sand, Thomas Elton Goodwin

Honors Theses

Sand is fairly rich in some common trace metals, notably manganese and iron. However, these metals for the most part are in a state which renders them insoluble in water. It is thought that the presence of organic matter (principally leaves) in the water enhances the dissolution of some of these trace metals into the aqueous solution.

This enhancement of dissolution is generally thought to come about in three main ways: (1) The organic matter present lowers the oxygen content of the water, and the metals are reduced into a soluble form, (2) The organic material, some of which is …

An Investigation Of Column Efficiency And The Relationship To Liquid Phase Distribution On Ultra-Low Loaded Glass Bead Gas Chromatographic Columns, Donald G. Nyberg

Theses and Dissertations

Studies have been made of column efficiencies, extra-column effects, the liquid phase mass transfer term (C_l), and liquid phase distribution at ultra-low liquid loadings on glass bead gas-liquid chromatographic columns. The advantages of using lightly loaded columns are described in detail along with a critical evaluation of the limitations of this liquid phase reduction ad infinitum. Theories have been presented by Giddings^22,23,25,30,32 which predict the mass transfer term (C_l) as a function of two extreme liquid phase distributions. The first equation assumes 100% "capillary" liquid held at the glass bead contact points and represents a very inefficient column. This prediction …

The Approximate Scf Lcao-Mo With Cndo Theory And Electronic Structures Of N-Heterocyclic Benzene Analogues, Jay Jea-Yong Rhee

Chemistry and Chemical Biology ETDs

The approximate MO theory in this study expIicitly refers to the Pople molecular orbitaI treatment. This consists of complete neglect of differential overlap (CNOO) in the self-consistent field treatment of the molecular orbitals, analogous to the Hartree-Fock treatment of atomic systems, which are constructed as Iinear combinations of atomic orbitals (LCAO). Furthermore, the only orbital functions considered in a basis set are those for the valence electrons and the atomic orbitals are Slater-type orbitals. The major investigation of this study is to apply this approximate MO theory to the series of nitrogen heterocyclic benzene analogues. The quantities that have been …

Kinetics Of The Thermal Decomposition Of Acetonitrile, Thomas William Asmus

Masters Theses

No abstract provided.

Acid-Base Titrations In Non-Aqueous Solvents, Gary Rice

Honors Theses

The acid-base titration is one of the simper methods available to the analytical chemist. Many organic compounds exhibit acidic or basic properties. Proper selection of solvent makes possible analytical determination of extremely weak acids and bases. This paper discusses the three solvent properties that are important in determining the acid-base behavior of a solute.