Physical Sciences and Mathematics Commons^™

Some Quadrivalent Compounds Of Rhenium And Technetium Containing Fluorine, David E. Lavalle

Masters Theses

The work in this laboratory was begun with the aim of producing pure K₂ReF₆, as a possible intermediate in the preparation of the lower fluorides of rhenium and as a "stand-in" for the preparation of K₂TcF₆. It meant, therefore, the preparation of the white form of K₂ReF₆ which both Weise and Peacock had described as the pure form of the compound.

I. Preparation And Properties Of Alkyl And Aryl Substituted Thioquinazolines And Sulfoxides ; Ii. An Investigation Of The Quinazoline 3-Oxide--1,4-Benzodiazepine 4-Oxide Rearrangement, Marvin C. J. Kuchar

Theses and Dissertations

I. The quinazolines, a branch of the benzodiazine class of aromatic nitrogen hetercycles, do not occur to any great extent in naturally occurring compounds. The discovery of the antimalarial febrifugine and its structure elucidation led to the preparation and investigation of a host of new quinazolines in the search for new and more effective antimalarials. Most of the present body of information governing the quinazolines arose out of these synthetic studies. The present study has been accomplished with a four-fold purpose in mind: (1) to investigate the susceptibility of chloroquinazolines to nucleophilic displacement reactions by thiols or their salts, (2) …

Energy Migration In Rare Earth Complexes, John Jerome Freeman

Chemistry and Chemical Biology ETDs

Complexes of trivalent samarium, europium, terbium, and dysprosium were prepared for investigations of the luminescence properties of complexed rare earth ions. Rare earth chilates derived from benzoylacetone, dibenzoylmethane, and acetylacetone; rare earth chlorides solvated with water and deuterium oxide; and rare earth oxides dissolved in sodium metaphosphate glasses were synthesized for these studies.

Radiochemical Studies: Isotopic Exchange Reactions, Solvent Effects, Preparation And Properties Of Carrier-Free Amalgams, Hans L. Hamster

Chemistry and Chemical Biology ETDs

The work described in this section is concerned with the kinetics of an S_N2 reaction, the isotopic exchange reaction between iodide ions and p-nitrobenzyl iodide, carried out in an aprotic solvent, acetone, in the presence of various substituted phenols and anisole. This reaction was carried out at concentration of potassium iodide low enough to insure the absence of ion pairs.

A Modified Procedure For The Quantitative Determination Of Fluoride And The Application Of This Procedure To A Fluoride Balance Study In Children, Beatrice Shuang Wu

Masters Theses

Introduction

This research problem was done in connection with the fluoride balance studies on twelve children at Plymouth State Home. The retention balance studies of fluoride by children can be studied indirectly by measuring the amounts of fluoride excreted in the urine and feces after administration of the fluoride in water or in vitamins as sodium fluoride. The fluoride balance study was repeated, because in the previous study (19), there were no samples collected for a base day in which the fluoride was not given. The previous data also indicated that fluoride retention was merely a function of the interval …

Thermodynamics Of I) Metal Cyanide Coordination, Ii) Water Formation, And Iii) Metal Halide Coordination, John Dewey Hale

Theses and Dissertations

ΔH values for the formation of Ni(CN)4(aq)= have been determined calorimetrically at 25° using a simple calorimeter and a thermometric titration procedure at high and low ionic strengths, respectively. Extrapolation of these ΔH values to infinite dilution resulted in a ΔH° value of -42.7 kcal./mole. Combination of ΔH° and ΔF° values gives a ΔS° value of -5.5 e.u. for Ni(CN)4(aq)= formation. A value of +70 e.u. is calculated for the ionic entropy of Ni(CN)4(aq)=. A preliminary investigation of the Zn(CN)4(aq)= system indicated the existence of zinc cyanide complexes other than Zn(CN)4= and allowed calculation of an approximate ΔH° value of …

An Investigation Of Steric Inhibition Of Resonance In Liquid Scintillators, Richard L. Taber

Chemistry and Chemical Biology ETDs

It is well known that the replacement of two or more of the ortho hydrogen atoms in the benzene rings of biphenyl by lager atoms or groups hinders the rotation about the l.l'-carbon single bond in the biphenyl system. If the groups are so large that they are unable to pass each other upon rotation of the l,l'-bond, then the two benzene rings are forced to assume a non-planar configuration.

Investigations Into The Diazoketone Synthesis Of 3-Methyl-2-Cyclopentenone, Robert Alan English

Honors Theses

This research was carried out in order to determine the effects of both the etherate and anhydrous forms of RF3 catalyst upon l-diazo-4-methyl-4-penten-2-one (I). It was hoped that cyclization could be induced to occur due to the presence of the neighboring olefinic bond. 3-Methyl-2-cyclopentenone, itself had been synthesized by a much more direct method than proposed here. (1)

The Preparation Of 1, 1'Tetramethylene Ferrocene, Arthur F. Grand

Honors Theses

The discovery of ferrocene, bis-cyclopentadienyl iron, in 1951 stimulated further research into a relatively new field of Organic Chemistry, organometallies. Ferrocene is the first of a series of transition metal-organic ring compounds in which the metallic atom is bound covalently to two cyclopentadiene rings (Fig III). The rings are superimposed over one another with the single atom inbetween; thus, they are often referred to as “sandwich compounds.” The following procedure is that which Rinehart (11) used to prepare the acid derivative β-ferrocenoylpropionic acid (VII). The preparation consists of adding 7.4 g. of ferrocene and 2.0 g. of succinic anhydride in …

Addition Reactions Of Quinones, Herman Helber

Honors Theses

The general purpose of this project has been to obtain a knowledge about the reaction of para-benzoquinone when irradiated with ultraviolet light in water or ethanol. The 1, 4, benzoquinone, often called simply quinone, is a yellow crystalline solid melting at 116°C and having a sharp penetrating odor. Quinone shows a marked increase in reactivity when it is irradiated with U.V. A possible explanation for this could be that the electrons in central carbon atoms of the quinone absorb quanta of energy. The resulting excited state could then leas to a free radical formation. This could account for the increased …

Polarographic Studies Of The Dicyanoaurate And Tetracyanoaurate Complexes, Peter Neddermeyer

Honors Theses

A polarographic study of the dicyanoaurate and the tetracyanoaurate complexes has been made. Distinct current-voltage curves were obtained for both complexes with and without supporting electrolyte.Polarography has been shown to be a good quantitative method of analysis for the two gold-cyanide complexes.

The Effects Of Ph And Salts On The Viscosity Of Protein Solutions, John H. Smith

Honors Theses

The purpose of this work was to determine, as a function of pH, the viscosity of gelatin solutions containing various monovalent anions. The sequence of these anions in their ability to depress viscosity, that is, the Hofmeister or Lyotropic series of anions, will be validated for the following salts: Sodium bromide, sodium iodate, sodium formate, sodium chloride and sodium nitrate.

A Preliminary Investigation Of The Photo-Induced Rearrangement Of Phenylnitromethane And Problems In Its Synthesis, Peter Barry Fleming

Honors Theses

As originally envisioned, this project was to involve the synthesis of phenylnitromethane and the subsequent photolysis of that compound. It was hoped that identification and separation of the photochemical products would lead to some basic conclusions regarding inter- and intra- molecular photo-induced rearrangements. Some light might also be thrown on energy transfer in a system of non-conjugated double bonds. Comparison of the products obtained from phenylnitromethane and higher homologs of the series, where n = 2,3,4 with the known reaction nitrobenzene could lead to conclusion on structure versus products and structure versus efficiency of energy transfer along an alkyl chain. …

Investigation Into The Reactions Of Aliphatic Methoxydiazo-Ketones Upon Treatment With Boron Trifluoride Etherate, Donald Paul Hoster

Honors Theses

This research was a study of the possible cyclization reactions of the aliphatic methoxydiazoketones (I) and (II) upon treatment with BF3 etherate. Previous work in this area had dealt with aromatic systems. J. Moore and H. Shaffer (10) showed that 1-diazo-3-(o-anisyl)-2-propanone (III) is converted in about 35% yield to chromanone (IV) upon treatment with BF3. They obtained lesser amounts of chromanone and larger amounts of open chain products when mineral acids were employed. Diazoketones such as (V) and (VI) have shown a pronounced tendency to form four-membered rings upon treatment with mineral acids. (8) No open chain products were isolated …

The Thermal, Catalytic Decomposition Of Sugar, Herman Carl Kluge

Honors Theses

During the past year, an attempt was made to determine the products of a thermal decomposition of both glucose and fructose and also, the effects of certain catalysts upon this decomposition. From these data, an attempt was also made to devise a mechanism for this decomposition.

Synthesis And Reactions Of Diazoketones, William H. Thielking

Honors Theses

The object of the present research, to extend the previous work to an aliphatic system by replacing the aromatic ring by one or more alkyl groups. Specifically, it is the object of this work to effect the closure of the ring compound from its respective diazoketone.

Inter- And Intra-Molecular Alkylbenzene Rearrangements With Aluminum Chloride Catalyst Using C14 Proportional Counting Of Vapor Phase Chromatographic Effluents, Robert Donald Farina

Honors Theses

End products were examined from six reactions between o-xylene and carbon-14 ring labeled toluene using an excess of aluminum chloride catalyst. The reactions were carried out at different temperatures and for periods of varying duration in order to observe the effects of temperature and heating time on the product mixtures.

Self-Diffusion In Single-Crystal Tungsten And Diffusion Of Rhenium Tracer In Single-Crystal Tungsten, Robert L. Andelin

Chemistry and Chemical Biology ETDs

Self-diffusion in single-crystal tungsten and diffusion of rhenium tracer in single-crystal tungsten have been measured over the temperature range 2660 C to 3230 C by the direct sectioning technique. The initial radioactive layer of tungsten and rhenium tracers was produced on the diffusion samples by bombardment with 9. 0-MeV deutrons. It was shown that the initial radioactive layer satisfactorily approximated the boundary-condition requirements of the one-dimensional diffusion equation. The tracers observed in determining the diffusion coefficients were W^185, Re^183, and Re^184.

Molecular Addition Compounds :|Bi. Systems Of P-Dioxane With Alkyl Halides, Anisole, And Silicon Tetrachloride ; Ii. Titanium Tetrachloride Chargetransfer Complexes Of Benzene, P-Xylene, And Pseudocumene, Nolan F. Mangelson

Theses and Dissertations

Freezing-point diagrams were detennined tor a number or p-dioxane systems. The system, p-dioxane:carbon tetrachloride, was found to contain a 1:2 complex with a congruent melting point of 255.71 °K. This confirmed work reported in the literature. Solid solutions in the region between 0.0000 and 0.4796 mole fraction of p-dioxane were found in the present study. The system, p-dioxane:chloroform, was found to contain a 1:2 complex with a congruent melting point of 215.65 °K. It was determined that no other complexes formed in the solid state. This information resolved contradicting reports in the literature. The system, p-dioxane:dichloromethane, was found to contain …

Nitrite Reactions In Soil, John Otto Reuss

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Losses of soil nitrogen that cannot be attributed to leaching or crop removal have been observed in many field experiments. Several mechanisms have been proposed to account for these losses.

Differentiation Between The Ph Effect And The Bicarbonate Ion Effect In Causing Lime-Induced Chlorosis, Hyrum Del Var Petersen

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Lime-induced chlorosis has been recognized for many years as a problem where plants are grown on calcareous soils. There are many factors associated with and influencing this form of iron chlorosis and because of this it has been very difficult to determine the relationship between the factors and chlorosis.

The Synthesis Of 2, 4, 6, 8 - Tetraoxo - 1, 2, 3, 4, 6, 7, 8, 9 - Octahydro-Benzo (1, 2-D:-5, 4-D') Bis (1, 3) Oxazine, Calvin L. Moyer

Chemistry Honors Papers

This 29 page thesis examines the synthesis of the three ring heterocyclic system containing two dioxo-1, 3-oxazine rings.

The Synthesis And Reactions Of 7-Carboxy Isatoic Anhydride, Elsa M. Janle

Chemistry Honors Papers

This 16 page thesis examines the preparation and characterization of 7-carboxy isatoic anhydride and the study of the reactions of this compound of new composition.

The Kinetics Of The Hydrolysis Of Some 2-Imidazolines, Bobby G. Harnsberger

Chemistry and Chemical Biology ETDs

In recent years, 2-imidazolines have become important industrially. Possible applications include uses as drugs, fungicides, emulsifying agents, demulsifying agents, corrosion inhibitors, fuel oil additives and gasoline additives.

Directive Effects In The Sulfonation Of Toluene ; Synthesis And Attempted Rearrangement Of Some Anilinoketones ; The Kinetics And Mechanism Of The Addition Of Bromine To Cyclohexene In Dichloromethane. Solution, John Joseph Duvall

Theses and Dissertations

The pure sodium salts of the toluenesulfonic acids were prepared by one of two ways. Both methods started with diazotization of the toluidine. In the first method, the diazonium solution was treated with sulfur dioxide and copper powder, and the resulting sulfinic acid was oxidized to the sulfonic acid with potassium permanganate. In the second method, the diazonium solution was treated with cuprous chloride and sulfur dioxide to give the sulfonyl chloride which was hydrolyzed to the sulfonate. Toluene was sulfonated by SO3 (enriched with S-35) in refluxing SO2 solution. The isotope dilution technique was used to determine the isomer …

The Preparation And Chemical Properties Of Tetracyclo [3.3.0.0^2,8.0^4,6] Octan-3-One, Arnold G. Phillips

Wayne State University Theses

No abstract provided.

High Temperature Adsorption Studies On Solid Adsorbents, Julian Joseph Hamerski

University of the Pacific Theses and Dissertations

It has been found that there exist certain crystalline aluminosilicates which provide regular net-works of channels with diameters no bigger than those of molecules. Such crystals can act as sieves (thus the name "molecular sieves" now marketed by the Linde Air Products Company) and bring about a separation of molecular species by occluding small molecules while not adsorbing larger molecules or molecules with shapes that do not "fit."

The aluminosilicates were termed zeolites first by Baron Cronstedt (1) some 200 years ago. He observed that certain mineral crystals, when heated, appeared to melt and to boil at the same time. …

Estimation Of Periodate By Oxindolamine, Lester Dale Burgess

University of the Pacific Theses and Dissertations

The carbohydrates play a vital role in the chemistry of the life processes. As man’s study of these processes, both fundamentally and in applied areas such as medicine, becomes ever more intensive, the limitations of our analytical procedures become ever more serious. While there are innumerable quantitative analytic procedures for the monosaccharides, there is a severe dearth of good micro colorimetric procedures. A particularly useful and widely used micro and semimicro procedure, based upon periodic acid oxidation, was originally introduced by Malaprade in France in 1928. In general, the consumption of the periodic acid in estimated by a back titration …

Preparation Of The Cis And Trans Isomers Of Methylcyclohexanecarboxylic Acids And Their 2-Diethylaminoethyl Esters, Paul Allen Meulman

Masters Theses

Introduction

The purpose of this research is to prepare the CIS and TRANS isomers of the 2, 3 and 4-methylcyclohecanecarboxylic acids and their 2-diethylaminoethyl esters.

This series of compounds is of interest because of the anti-tumor activity shown by some ethanolamine derivatives. The compounds to be prepared in this study represent modifications of these structures to determine if further investigation in this area is worthwhile. A pharmacological evaluation of these compounds will be made since many esters of amino alcohols have demonstrated pharmacological activity. The cancer chemotherapeutic and pharmacological test results are not included in this paper, but will be …

Preparation And Properties Of 3, 3’ -Disbubstituted-2, 2’ – Three-Carbon-Atom Bridged Biphenyls, Allan E. Nader

Masters Theses

Introduction

The configuration of biphenyl has been treated in numerous articles and reviews (1, 5, 6, 7, 8, 16, 22, 23). In particular the configuration of 2,2'-bridged biphenyl derivatives has obtained attention. The synthesis of an optically active 2,2'-three-carbon-atom-bridged biphenyl possessing an ultraviolet absorption maximum at 250 mμ has been reported by Iffland and Siegel (15). These properties require first, a non-planar configuration for the molecule and second, significant inter-ring conjugation as demonstrated by ultraviolet spectra.

Several 2,2'-three-atom-bridged biphenyls have been prepared by Ahmed and Hall (2, 3) in order to obtain some measure of their specific rotation. The use …