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The Formation And Study Of Certain Bicyclic Enolate Monoanions And Dianions, Ernest William Crowe

Masters Theses

No abstract provided.

14th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 14th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, July 31 - August 1, 1972.

Relation Of Aromatic Substitution Patterns To Nmr Shifts Produced Tris - (1,1,1,2,2,3,3 - Heptafluoro - 7,7, Dimethyl - 4,6 - Octanedione) Europium (Iii), Roy R. Reeves

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Sciences and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Roy R. Reeves on July 27, 1972.

Relation Of Shift Magnitude Of Alkyl Substituents To Aromatic Substitution Patterns, Michael E. Evans

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Science and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science by Michael E. Evans on July 27, 1972.

A Correlation Of The Idealized Heat Of Vaporization To Molecular Weight, Harold Earl Bennett

Master's Theses

Using the Clausius-Clapeyron equation as a base, many investigators have tried to develop variations to better describe both ideal and non-ideal systems. The literature is abundant with correlations of vapor pressure to temperature and associated correlations of latent heats of vaporization to molecular characteristics; often molecular weight or carbon number.

The Synthesis And Characterization Of The 2,2'-Bisacylazide Of 3,3'-Bipyridine, Magdy Adly Guirguis El-Fayoumy

Chemistry & Biochemistry Theses & Dissertations

The primary objective of this research has been the synthesis and characterization of a new heterocyclic diacylazide, the 2,2'-bisacylazide of 3,3'-bipyridine 19. This heterocyclic diacylazide has been successfully synthesized from the phenanthrolin-5,6-dione 14, and examined with regard to its.thermal and photolytic decomposition.

Thermal decomposition of this disacylazide seems to go by a double-barreled Curtius rearrangement leading to a series of pyridonaphthyridinone (20) compounds such as 22 and 29.

An initial study of the photolysis of this bisacylazide has been initiated to examine the possible formation of nitrene-type intermediates.

Synthesis Of Derivatives Of Pyrido [3,4-D]Pyridazines, Diane (D'Ottavio) Martin

Chemistry and Chemical Biology ETDs

The current interest in the biological activity of certain 1 ,4-disubstituted pyrido[2 ,3-d]pyridazines prompted the investigation of various derivatives of the isomeric pyrido[3,4-d]pyridazine ring system. Thus, 1,4 ­ dichloro[3,4-d]pyridazine was treated with thiourea and the intermediate thiouronium salt hydrolyzed to give pyrido[3, 4-d]pyridazine-1,4(2H,3H)-dithione which was subsequently alkylated to give 1,4-bis(alkylthio)pyrido­[3,4-d]pyridazines. On the other hand, 1,4-bis(arylthio)­pyrido[3,4-d]pyridazines were prepared by the reaction of 1,4-dichloropyrido[3,4-d]pyridazine with various substituted thiophenols. Furthermore, treatment of 1,4-dichloropyrido[3,4-d]­pyridazine with a variety of substituted anilines gave the corresponding 1,4-disubstituted aniline derivatives, whereas reaction with alkylamines afforded only the 1(4)-chloro-4(1)-alkylaminopyrido[3,4-d]pyridazines. When 1-chloropyrido[3,4-d]pyridazine-4(3H)-one or 4-chloropyrido[3,4-d]pyridazine-1(2H)-one was treated with hydrazine, the corresponding …

An Acid Alkylation Of 8-Hydroxyquinoline, James D. Searcy

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Science and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science by James D. Searcy on May 11, 1972.

Electrolytic Synthesis Of [Gamma]-Diketones, Leon F. Pahler

Theses and Dissertations

Four γ-diketones were synthesized by using a modification of the Kolbe electrolytic condensation of β-ketocarboxylic acids. [--see equation in thesis--] The following γ-diketones were synthesized in moderate yields: 2,5-hexanedione, 4,7-decanedione, 2,2,7,7-tetramethyl- 3,6-octanedione, and 1,4-diphenyl-1,4-butanedione (34, 39, 23, and 27, respectively). However, attempted preparation of the following γ-diketones failed: 3,4-dimethyl- 2,5-hexanedione, 3,3,4,4-tetramethyl-2,5-hexanedione, and 1,4-di(2-thienyl)-1,4-butanedione. Attempts to electrolytically condense α-alkyl and α, α-dialkyl substituted monocarboxylic acids have been reported and all attempts have ended in failure; similarly, the attempts to synthesize 3,4-dimethyl and 3,3,4,4-tetramethyl- 2,5-hexanedione from 2-methyl and 2,2-dimethyl-3- oxobutanoic acid, respectively, failed. The preparation of 1,4-di(2-thienyl)-l,4-butanedione failed because the product or …

Chelation Of Two Polyhydroxyamines With Copper (Ii) Ion, David H. Powell

Master's Theses

Two polyamines, 2,8-bishydroxymethyl-2,8-dimethyl- 3, 7-diaza-1,5,9-nonanetriol and 2,8-bishydroxymethyl-2,8- dimethyl-3,7-diaza-l,9-nonanediol, were prepared and the coordination of these compounds with Cu (II) ions in solution was investigated. Spectrophotometric study of the solutions of these compounds gives evidence of the formation of two complexes, containing one mole of ligand per metal ion and two moles of ligand per metal ion, respectively. The two stability constants for these complexes and the basicity constants for these ligands were calculated from potentiometric titrations at 30°C. A compadson of the stabj lity constants and basici ty cons tan ts for the two compounds was made to determine the …

A New Method For The Preparation Of Alkylnaphthyl Ethers And Sulfides, Edward Ying-Shih Chen

Theses and Dissertations

The reaction of monohalonaphthalenes with metal alkoxides and mercaptides in a solvent mixture of the corresponding alcohol and dimethyl sulfoxide (DMSO) has been studied. These reactions are convenient methods for the preparation of alkylnaphthyl ethers and sulfides. Only direct nucleophilic substitution was observed in the reactions of bromonaphthalenes with sodium methoxide and sodium nbutyl mercaptide. The reaction of fluoronaphthalene with potassium t-butoxide also proceeded by way of direct nucleophilic substitution rather than the 1,2-dehydronaphthalene intermediate as in the reactions of bromonaphthalene with potassium t-butoxide. The use of a base which is weaker than t-butoxide can change the apparent reaction mechanism …

Rhenium Catalyzed Hydrogenation Of Maleic Anhydride And Crotonaldehyde, William Russel Dixon

Theses and Dissertations

The preparation of a number of supported rhenium catalysts is reported. The determination of their activity and selectivity and of optimal reaction parameters for the reduction of maleic anhydride and crotonaldehyde is reported. Optimal time of hydrogenation was chosen as one hour and pressures were chosen as 2000 psig for crotonaldehyde and 3000 psig for maleic anhydride. Quantitative reduction of maleic anhydride to tetrahydrofuran occurred at 275° with charcoal supported rhenium catalysts. Lower temperatures (ca. 200°) produce quantitative amounts of butyrolactone. Unsupported catalysts at low temperatures (100°) selectively reduce crotonaldehyde to crotyl alcohol, but at very low conversion rates. Temperatures …

Toward Hydrogen Bonds Of Predictable Geometry, Robert Shao-Chih Hsu

Theses and Dissertations

A literature review on the geometry of hydrogen bonding showed that the geometry is often de-emphasized or even ignored, probably because of the inherent flexibility of many systems studied. Examination of molecular models suggested the geometrically constrained bicyclo [2, 2, 1] heptane system wherein hydrogen bond distances and angles might be more easily predicted. Dihydroboration-oxidation of norbornadiene was shown to yield exo, exo-2,5-norbornadiol, thus clarifying uncertainties in the literature. 2, 5-Norbornadiol was oxidized to the corresponding dione, heretofore inadequately characterized. Several derivatives of the dione were prepared, and spectral data were accumulated for the dione, its precursor, and its derivatives. …

The Synthetic Chemistry Of Carboxyalkyl-P, P-Diphenyl Phosphines, Larry S. Andrews

Chemistry Honors Papers

This 55 page thesis examines the preparation of carboxyalkyl-P and P-diphenyl phosphines to determine their acidity characteristics as a function of structure and to characterize their ability to function as chelating agents.

Synthesis And Metal Coordination Properties Of Some Cyclic Polyethers And Polythioethers, Barry Lant Haymore

Theses and Dissertations

Thermodynamic values for cation-cyclic polyether interactions for several systems are reported and discussed in light of ligand geometry, cation selectivity, solvent effects, structure, stoichiometry and the nature of the coordinate bond. Cyclic polyethers are shown to be remarkably good ligands even in water and to have marked selectivity for d0, d10 and d10 s2 cations. Syntheses of one new cyclic polyether and several new mixed cyclic polyether-thioethers are reported. Cyclic chelates with smaller rings are shown to prefer smaller cations, but this selectivity is masked by the hydration energy of the cation. Except for thiophillic cations such as Hg2+ and …

Enzymatic Synthesis Of Oligoribonucleotides Of Defined Base Sequence, Mark J. Rowe

Theses and Dissertations

The synthetic reaction of ribonuclease T_1 has been studied as to its potential for the synthesis of oligoribonucleotides of defined base sequence. Conditions have been determined for maximum synthesis with respect to percentage incorporation of both guanosine 2',3'-cyclic phosphate (donor), and cytidine (acceptor). With regard to maximum acceptor incorporation, a donor blocked at the 5'-hydroxyl has been used to drive the reaction. It has also been shown that acceptor incorporation decreases as the chain-length increases up to the hexanucleotide. Synthesis of a 3'-blocked substrate for polynucleotide phosphorylase for use in chain termination studies was attempted using adenylate kinase. In this …

Acid-Base Titrations In Sulfolane, Francine O. Lawrence

Chemistry and Chemical Biology ETDs

A study of the solvent effects of sulfolane (tetrahydrothiophene 1, 1-dioxide, tetramethylene sulfone) upon a series of acids and several bases has been conducted. A procedure is presented for purifying sulfolane which results in a solvent of very low water content (5 x 10^-4 M) and very few impurities, as shown by its cooling curve. Potentiometric and conductometric measurements of additions of acids and bases to purified sulfolane and of various acid-base titrations were made. The series of carboxylic acids included benzoic, orthomethoxybenzoic, and three different monochlorobenzoic acids. The bases investigated included sodium methoxide, pyridine, and diphenylguanidine. Interpretation of …

19f Nmr And Bx3 Complexes, Nancy Toole Tucker

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Sciences and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Nancy Toole Tucker on April 21, 1972.

Preparation And Reactions Of 2-Benzo [B] Thienylsodium, Larry Kennard

Morehead State Theses and Dissertations

A thesis presented to the faculty of the School of Science and Mathematics at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science in Chemistry by Larry Kennard on April 21, 1972.

Influence Of An External Electric Field On The Charge Transfer State Of The Tcne-Trans-Stilbene Molecular Complex, Craig J. Eckhardt

Craig J. Eckhardt Publications

An experimental investigation of the effect of an external electric field on the absorption spectrum of the tetracyanoethylene-trans-stilbene molecular complex in cyclohexane solution yielded values of 1.1±0.1 D for the ground state electric dipole moment and 10.5±0.9 D for the change of the electric dipole moment upon transition to the charge transfer excited state. The ground state electric dipole moment determined by the electro-optic effect is in agreement with the value of 1.4±0.5 D obtained from the dielectric constant measurements made on solutions of the complex. The directions of the transition moment, the ground state electric dipole moment, and the …

A Spectrophotometric Study Of The Reaction Between Benzoyl Peroxide And N, N-Dimethyl-P-Phenylenediamine, Bertha Cosby King

Master's Theses

A special need for methods to determine low concentrations of organic peroxides originated because of their hazardous and harmful effects, Even the small amounts of organic peroxide formed by autoxidation in ethers exposed to air make the ethers highly explosive and unsuitable for use as anesthesia or laboratory solvents. The formation of organic peroxides in fats and oils causes rancidity. They have been named as pollutants, and some of them are known to have detrimental physiological effects.

The purpose of this research was to improve this method of analysis and to determine better conditions for the measurement of color by …

Kinetics Of Free Radical-Initiated Polymerization Of Α-Methylstyrene In The Region Of The Ceiling Temperature, Fred E. Huang

Masters Theses

No abstract provided.

Heats Of Combustion Of Alpha-Methylstyrene Oligomers, Dale Keith Humbert

Masters Theses

Introduction

The heat of polymerization (∆H_p) of α-methylstyrene (AMS) has been a source of study for many years. The structure of AMS is shown in Figure 1.

The first quantitative work was done by Roberts and Jessup.¹ Their values were more positive than those theoretically calculated by Flory² and compared with ∆H_p data of other systems. This was not totally unexpected and could be satisfactorily explained on the basis of steric hindrance and loss of resonance energy of conjugation. This steric hindrance arose from "head-to-tail" polymerization of the 1, 1-disubstituted ethylene structure.³ Their data …

The Relationship Between Degree Of Clay Dispersion And The Optical And Pore Properties Of Starch - Clay Coatings, Chinu S. Dalal

Masters Theses

No abstract provided.

Development Of An Ultra High Shear Recording Viscometer, David C. Thornton

Masters Theses

No abstract provided.

Continuous Wave Co2 Laser Degradation And Mass Spectrometric Analysis Of Organic Polymers, Stanley G. Coloff

Chemistry and Chemical Biology ETDs

Previous laser-mass spectrometer and laser-gas-chromatographic instruments for study of organic polymer degradation have used high power pulsed lasers (ruby, Nd-glass) which limit sample characterization due to extensive fragmentation. A new experimental technique has been developed for high temperature pyrolysis and rapid analysis of organic polymers. The experimental technique combines a low power continuous wave CO₂ laser for sample pyrolysis and a time-of-flight mass spectrometer to analyze degradation products. The laser built for use in this study was a continuous flow CO₂ gas-molecular laser excited by high voltage direct current with maximum power of 10 watts at a wavelength …

Catechol Effected Dissolution Of Silicate Minerals, James Maurice Kelley

Dissertations and Theses

The chemical properties of guanidinium tris(catecholato)siliconate, [(H₂N)₂C=NH₂]₂[Si(C₆H₄O₂)₃]·XH₂O (0 < X < 1), precipitated from an ammoniacal solution of silica and catechol by adding guanidinium hydrochloride, (H₂N)₂C=NH·HC1, were studied, and infrared, nmr, x-ray powder diffraction, and analytical data were gathered.

This same compound was, upon addition of' (H₂N)₂C=NH·HC1, isolated from 0.25, M aqueous catechol solutions buffered at pH 10 and containing the silicate minerals albite, andradite, muscovite, pyrophyllite, talc, and wollastonite, and also from unbuffered catechol solutions containing wollastonite and andradite.

It is concluded from this work that the formation of an anionic catechol-silicon complex, Si(C₆H₄O₂)₃²⁻, is largely responsible for the dissolution of the minerals mentioned above. From this conclusion, it is proposed that naturally occurring members of the class of organic compounds to which catechol belongs, the aromatic v̲i̲̲c̲-diols, may play …

On The Mechanism Of Low-Temperature Termolecular Atomic Recombination, Russell T. Pack, Richard L. Snow, Wesley D. Smith

Faculty Publications

A simple theory of gas-phase termolecular atomic recombination kinetics is presented which treats the bound-complex (BC) mechanism in a fashion which parallels the Roberts, Bernstein, and Curtiss resonance theory of the energy-transfer (ET) mechanism. The ET rate constant has a low temperature maximum, but the BC rate constant does not. The contributions of the two mechanisms to the low-temperature recombination of hydrogen atoms, with He, Ar, and H2 as third bodies, are estimated and compared. The presence (absence) of a low-temperature maximum in the observable total rate constant is determined by absence (presence) of bound vibrational levels of the hydrogen-third …

Isopiestic Studies Of Some Aqueous Electrolyte Solutions At 80°C, John T. Moore

Faculty Publications

No abstract provided.

Equilibrium And Kinetic Study Of The Substitution Reactions Of Pentacarbonylaminetungsten (O) With Triphenylphosphine, William O. Bailey

Masters Theses

A kinetic and equilibrium study of the reaction of triphenylphosphine (PPh₃) with pentacarbonylaminetungsten (O) [(CO)₅WNH₂C₆H₅] has been reported previously. Equilibrium constants for the reaction (CO)₅WNH₂C₆H₅ + PPh₃ = (CO)₅W[P(C₆H₅)₃] + C₆H₅NH₂ in toluene were reported to be 17.1, 49.2 and 65.7 respectively. In addition, the entropy change (ΔS) for the reaction was found to be 86±5 cal mol^-1 deg^-1.

In this study the above reaction was …