Physical Sciences and Mathematics Commons^™

Acidities In Ethanol/Water Solvents;The Pka Of Hf., Raymond M. Merrill

Chemistry and Chemical Biology ETDs

The acidity of hydrofluoric acid in mixed ethanol/ water solvent systems was studied by determining the pKa of HF in a number of different ethanol concentrations. The effect of changing temperature on the acidity of HF in these media was also examined.

The pKa's were determined using a lanthanum fluoride membrane Fluoride Specific Ion Electrode and a glass pH electrode versus the same reference electrode. The method eliminates the need to determine liquid junction potentials. By determining the pKa for HF in each ethanol/water mixture, at a number of different temperatures, thermodynamic parameters, such as free energy, enthalpy, entropy, and …

The Effect Of Stereoelectronic Control And Long Range Interaction On The Stability Of Bicyclic Enolate Anions, Edwin M. Van Dam

Dissertations

No abstract provided.

Magnetic Nonequivalence In Higher Alkyl Groups, Philip Anthony Reitano

Masters Theses

The phenomenon of magnetic nonequivalence has been growing in recent years. Unequal populations of the various conformers in such molecules are normally accepted as the cause of nonequivalence, but nuclei which are stereochemically nonequivalent are not necessarily magnetically nonequivalent. This nonequivalence has been demonstrated for molecules of the type ABDC⁸CHR₁R₂, where R + H, F, and Me. Although in principle the effect is quite general this has not been previously observed in "freely rotating" systems for groups larger than methyl. The role of steric factors, the size of the substituents and the distances between …

Principles Of Control Theory As Applied To A Thermostat, Joseph Peter Stidham

Master's Theses

The recent development of solid state electronics has opened new possibilities in instrumentation design. One development has been the availability of compact, low cost, high gain, D. C. amplifiers which can be used in the design and construction of sensitive laboratory instruments (11). Using these amplifiers a thermostat capable of precise control can be constructed and its performance compared with the performance expected by an analysis of the closed loop control equations.

The Wittig Reaction With Carbohydrates And The Addition Of Benzenesulfonyl Azides To Indoles, George R. Wellman

Dissertations

No abstract provided.

The Dimetalation And Subsequent Functionalization Of 1,3-Dimethylnaphthalene By Means Of Amylsodium In The Presence Of Certain Tertiary Amines, Atilla Tuncay

Masters Theses

I. Introduction

It is well known that the hydrogen atoms of a methyl group directly attached to an aromatic system are sufficiently acidic to be abstracted by suitable bases to generate the corresponding α-anion.^1,2 These monoanions have frequently served as suitable intermediates for the formation of a large variety of a-condensation products in good to excellent yields² On the other hand, attempts to obtain α,α-dianions from various dimethylaromatic systems have met with limited success.² Due to the lack of sufficiently strong bases, dimetalation products were obtained only in poor yields even at high temperatures and prolonged reaction …

Kinetics Of The Formation Of Nickel(Ii) Complexes With N,N’-Dibenzylethylenediamine And N,N’-Bis(2-Picolyl)Ethylenediamine, Zahid Amjad

Masters Theses

No abstract provided.

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

Masters Theses

No abstract provided.

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 …

The Preparation And Kinetics Of Sterically Hindered Gold (Iii) Complexes, David Luther Fant

Honors Theses

The purpose of this research was to prepare and study complexes with steric hindrance greater than that of the dien complex but less than that of the Et4dien complex.

Some Aspects Of Quantum Mechanics In Chemical Theory, Thomas Freeman Babson

Honors Theses

The physics of microscopic phenomena is called quantum mechanics. When quantum mechanics is extended to the macroscopic scale, the classical macroscopic physics results. Atomic interactions such as the formation of bonds between atoms falls into the range of physics described by quantum mechanics. Because of the interest of a chemist in such interatomic effects, it seems reasonable that a chemist would be interested in quantum mechanics because it is the physics governing these effects. The point of this thesis is to present some of those aspects of quantum mechanics that are directly applicable to molecular systems and that can aid …

The Developement [Sic] Of Phosphorometric, Fluorometric And Absorption Analyses For The Measurement Of Carbamates And Carbamic Acids As An Explanation Of Carbon Dioxide Transport In Blood, Edward Theodore Gray

Honors Theses

Phosphorometric, flourometric, and absorption analyses have been developed for the measurement of amino acids, carbamic acids, and carbamates. The absorption analysis may be done in any solvent while the other two methods are limited to non-re-emitting solvents. Water is not excluded in any of the analyses. A carbamate or carbamic acid can be detected even in the presence of amino acids as low as 0.5%, with an overall accuracy of ± 0.3)%. Tentative assignments have been made for the n, π* direct triplet excitation bands for the carbonyls of glycine and its carbamic acid, acetyl chloride, ethyl acetate, and acetamide. …

Synthetic Approaches To Certain Acenapthalene Drivatives, Douglas Jeffrey Binder

Honors Theses

The purpose of this investigation is the synthesis of bis- acenaphth- (1, 2a)- acenaphthene. The experimental procedures used generally follow those of previous workers. The use of 1, 8- dibromonaphthalene is necessary throughout the synthesis. The preparation used follows that of letsinger, after a preferred synthesis of 8- bromo- 1- naphthotic acid. The latter compound reacted via a modified Hunsdiecker reaction to yield 1, 8- dibromo- naphthalene. Other approaches tried never seemed to result in improved yields, or were successful. Besides this approach to 1, 8- dibromonaphthalene, an attempt to circumvent its need has been made by running a dilute …

1-3 Dipolar Cycloadditions Of Nitrile Ylides, Steven Paul Braff

Honors Theses

1-3 dipolar cycloaddition is the union of a 1-3 dipole, a-b-c, with a system containing a multiple bond, d-e, to form a five membered ring. In this scheme, center c contains an electron sextet, and concommitant positive charge, while center c contains an unshared pair of electrons and is the anionic center of the dipole. In the cycloaddition reaction, the 1-3 dipole and the multiple bond system (called the dipolarophile), collapse to form a five membered ring with loss of all formal charges. All together, eighteen 1-3 dipolar systems have been mentioned. The synthetic potential with respect to heterocyclic adducts …

Cationic Copolymerization Of B-Pinene And Styrene, Charles Peter Snyder

Honors Theses

Cationic polymerizations are the least understood of all polymerization reactions. Perhaps even less understood are copolymerizations using cationic catalysts. Very little can be found in the literature concerning B-pinene and styrene copolymers. This work was done to shed some light on this interesting subject.

Attempted Synthesis Of Diethyl 7-Dimethylsilabicyclo 2.2.1 Hepta-2,5-Dione-1,4-Dioate, David Kenneth Tart

Honors Theses

An attempt was made to synthesize diethyl 7-dimethylsilabicyclo [2.2.1) hepta-2,5-dione-l,4-dioate by reacting dimethyldichlorosilane with the dianion of 1,4-dicarbethoxy- 2,5-cyclohexadione. The products formed in the reaction were silicones and 0-silylated polymeric materials. If any of the desired product was formed, it was not detected.

Synthesis Of C14-Labeled Bis (P-Chlorophenyl) Acetic Acid (Dda), William Michael Silver

Honors Theses

The past three decade has seen the widespread use of DDT as an insecticide. As a persistent insecticide, its use has prompted a great amount of research into the fate of DDT in living organisms. A large number of metabolites of DDT has been found and many identified, although not all of the metabolites were found in all of the experimental bacterium, insects, or mammals.

Photochemical Solvolysis Of Optically Active 3,5-Dimethoxy-Α-D-Benzyl Acetate, Peter Jerry Frank

Honors Theses

The purpose of this work was the stereochemical study of the photochemical solvolytic reaction of 3,5-dimethoxybenzoic acid, optically active 3,5-dimethoxy-α-d-benzyl alcohol was prepared. The specific rotation of the alcohol was compared to the alcohol produced from the photochemical solvolytic reaction of 3,5-dimethoxy-α-d-benzyl acetate.

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.

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 …

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. …

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 …

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 …

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 …

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 …

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 …