Physical Sciences and Mathematics Commons^™

Synthesis And Reactions Of P-Nitrobenzyl 4,6-0-Benzylidene-2,3-Di-0-Methoxymethyl-Β-D-Glucopyranoside, Ray Douglas Carpenter

University of the Pacific Theses and Dissertations

The purpose of this work was the preparation of specifically blocked D-glucose derivatives with a free hydroxyl group on the anomeric carbon (C-1).

Comparative Phytochemistry Of Saururaceae Essential Oils., Lohit Venkateswara Tutupalli

University of the Pacific Theses and Dissertations

In view of their native medicinal uses, a systematic investigation of the phytochemistry and Hippocratic screening of three members of the Saururaceac namely, Anemopsis californica, Saururus cernuus and Houttuynia cordata was undertaken.

The Chemical And Electrochemical Oxidative Decarboxylation Of Methyliminodiacetic Acid In Acid Media, Rita Kathleen Hessley

Doctoral Dissertations

"Methyliminodiacetic acid (MIDA) is oxidized with cerium. (IV) in both perchloric and sulfuric acids to give sarcosine, formaldehyde, and carbon dioxide"--Abstract, page 2.

A Study Of The Kinetic And Thermodynamic Properties Of Carbon Acids In Methanol, Dennis L. Filger

Doctoral Dissertations

The thermodynamic acidity (pK_a) of iodoform in methanol was determined at 25°C and 35°C; the values are 18.74 and 18.05, respectively . These acidity constants were determined by a modification of the equilibrium quenching technique which involves the conversion of the conjugate base of iodoform, present at equilibrium, to the radioactively labelled acid.

The rate constants for the methoxide-catalyzed hydrogentritium exchange of chloroform, iodoform, 9-phenylfluorene and indene were determined in methanol at various temperatures. The second-order rate constants obtained from these studies were shown to be the rate constants for removal of a triton. The activation parameters (ΔH …

Metal Salt Catalyzed Carbenoids Ii, Robert Stephen Mcdaniel Jr.

Doctoral Dissertations

"The interaction of diazomalonic esters with olefins in the presence of homogeneous Cu(II) catalyst species has been examined relating to olefin structure effects and catalyst structure effects using partial rate data as a method of determining the mechanistic aspects of the various reactions.

It has been possible to examine the mechanistic details of cyclopropanation, C-H insertion, and both "dimer" forming reactions.

Cyclopropanation proceeds via a transition state including olefin, copper (II), ligands, and carbene C-H insertion results from hydrogen abstraction prior to collapse of the transition state. "Dimer" is formed by the attack of diazo compound on the carbenoid carbon, …

Base-Induced Reactions Of P-Nitrobenzyl Compounds, Paul Henry Ruehle

Doctoral Dissertations

"The base-induced reactions of several p-nitrobenzyl compounds were studied. The products varied with changes in the leaving groups. With relatively poor leaving groups (Cl, S⁺(Me)₂), p,p'- dinitrostilbene was produced in good yield. The products of the reaction of p-nitrobenzyl chloride and hydroxide ion in 50% aqueous dioxane were 52.0% p,p'-dinitrostilbene, 43.9% cis- and trans-p,p'-dinitrostilbene oxides, 3.2% p-nitrobenzyl alcohol, and traces of other compounds. With dissolved oxygen, no stilbene was produced; the main product was 88% cis- and trans-p,p'-dinitrostilbene oxides. The addition of small amounts of di-t-butyl nitroxide caused a decrease in both the rate of the reaction and the amount …

Kinetic And Thermodynamic Acidities Of Selected Weakly Acidic Hydrocarbons, Darrell R. Strait

Doctoral Dissertations

"The kinetic and thermodynamic acidities in methanol for bromoform and phenylacetylene have been determined at various temperatures. The thermodynamic acidities of phenylacetylene were obtained through a quench method which involved tritium tagging of the phenylacetylene anions present at equilibrium. With the use of this method, a pK_a of 18.34 for phenylacetylene at 0ºC was obtained. Through the use of these acidities, it was shown that the kinetics for these proton exchange processes are not diffusion controlled.

Isotope effects ( k_H/ k_D) were obtained for chloroform, bromoform and phenylacetylene at three temperatures (0ºC, -10ºC and -20ºC). …

Mechanism Of Solvolysis Of 3-Methyl-2-Butyl Brosylates., Luu Le Nghi

Masters Theses

"The brosylates of 3-methyl-2-butanol and it's a-d₁-, ß-d₁-, B-d₃-, and S-d₄- analogs have been synthesized. The solvolytic rate data for these compounds were determined. The solvolytic products in 70% (vol.) ethanol-water have been identified by flame ionization gas chromatography using a Carbowax 20M column. The amount of each product was measured by integrating the peak areas from the chromatograms. By analyzing the isotope effect data, the rate determining step is shown to be the formation of the hydrogen bridged ion pair intermediate. By evaluating the GC-mass spectral analysis of the isopentenes, a …

A Study On Two Iodine Containing Peptides Isolated From Porcine Thyroglobulin, Frederick E. Bishop Jr.

Masters Theses

"Two iodopeptides were isolated from thyroglobulin that had been digested with trypsin by paper electrophoresis and paper chromatography. The amino acid analysis demonstrated that the amino acid compositions were similar. The N-terminal amino acid of both iodopeptides was shown to be leucine. The amino acid sequence of one of the iodopeptides was determined by the Edman degradation method and digestion with the enzyme Carboxypeptidase A. The sequence was shown to be: NH₂-Leu-Asn-Ala-Ser-Glu-MIT-Gly-Thr-Ser-Gly-COOH. Other workers have shown that synthetic tyrosyl peptides with the sequence Glu-Tyr are iodinated by the thyroid peroxidase enzyme with a greater specificity than other tyrosyl peptides. This …

Metal Salt Catalyzed Carbenoids The Catalysts In Trialkyl Phosphite Copper (I) Complex Catalyzed Decomposition Of Diazo Compounds, Nguyen Van Thinh

Masters Theses

"Partial rate data, asymmetric induction studies, interrupted experiments and additives studies indicate that copper(I) salt-phosphite complexes are destroyed during the course of reactions with dimethyl diazomalonate (1) and ethyl diazoacetate (2). All evidence is consistent with the copper(I) being oxidized to copper(II) and copper(0) being oxidized by impurities in the olefin which most probably are hydroperoxides.

Several new copper(I) salt-phosphite complexes were prepared and examined but none proved as effective for decomposing (1) as copper(II) bis acetylacetonate.

The utility of the copper (I) chloride-trimethyl phosphite complex for decomposing (1) is a function of the means of preparation. The three general …

A Kinetic Study Of The Cerium (Iv)-Oxalic Acid System In Acidic Sulfate Media., Robert Richard Kessler

Masters Theses

"The kinetics of the cerium (IV) oxidation of oxalic acid was studied by a stopped-flow spectrophotometric technique in acidic sulfate media. The media consisted of perchloric acid, sodium sulfate and sodium perchlorate which allowed for the determination and control of the various sulfate and hydroxo species of cerium (IV) at prescribed hydrogen ion concentrations. The rate of reaction decreases rapidly with increasing sulfate concentration which yields evidence against previous reports indicating Ce (SO₄)₂ and Ce (SO₄)^2-₃ as the reactive cerium (IV) species. The results indicate that Ce (SO₄)²⁺ is the …

A Phytochemical Investigation Of Liverwort Frullania Franciscana Howe, Timothy Ta-E Huang

Dissertations and Theses

Liverwort Frullania franciscana Howe was found high on the allergic test scale by J. Mitchell of the Medical School of the University of British Columbia and co-workers. Frullanolide was isolated from Frullania tamarisci by J.D. Connoly and by G. Oisson and his co-workers.

The plant sample, collected in Oregon, was hand separated, confirmed, air dried and milled before the extractions were done. A Soxhlet extraction with ether and cold extractions with n-hexane and with ether were carried out. Ether is a better extraction solvent than n-hexane for cold extraction.

Column chromatography was used for the separation of the extract based …

Ua66/7/2 Newsletter, Wku Chemistry

WKU Archives Records

Newsletter created by and about the WKU Chemistry department.

A Study Of The Adsorption Of Some Atmospheric Gases On Soils Of The Willamette Valley River Basin, Thomas R. Quale

Dissertations and Theses

Recent work indicates that microorganisms present in soils can remove carbon monoxide from the atmosphere and as such constitutes a major sink. B.E.T. adsorption studies were carried out on representative soils from the Willamette Valley River Basin in order to determine their adsorptive characteristics for carbon monoxide and other gases. Attempts were made to isolate, through a non-soildestructive sterilization, the adsorptive characteristics of the soil microorganisms as well as of the test soil.

The carbon monoxide studies show physical adsorption equivalent to the coverage of a few per cent of the surface area at 25.0° and 76 cm-Hg. Adsorption studies …

The Effect Of The Degree Of Cationic Charge On The Binding Strength Of A Cationic Starch-Kaolin Clay Coating, Hugh K. Myers

Masters Theses

No abstract provided.

Kinetics Of The Metal Exchange Reaction Between N, N'-Bis (2-Picolyl) Ethylenediaminenickel (Ii) And Copper (Ii), Craig Lee Barsuhn

Masters Theses

No abstract provided.

The Kinetics Of The Metal Exchange Reaction Between Biseminodiacetatonickelate (Ii) And Copper (Ii), Stephen H. Erickson

Masters Theses

No abstract provided.

Rate Of Initiation Of Pyrolysis Of Pentachloroethane Using The Toluene Carrier Gas Technique, Teodomiro Cuzcano

Masters Theses

No abstract provided.

The Synthesis And Reactions Of Some Α, Β-Unsaturated Diazoketones, Virendra K. Sood

Masters Theses

No abstract provided.

Rotationally Inelastic Molecular Scattering. Computational Tests Of Some Simple Solutions Of The Strong Coupling Problem, Thomas P. Tsien, Gregory A. Parker, Russell T. Pack

Faculty Publications

Partial cross sections (opacity functions) for rotational transitions in atom-diatom collisions are computed in the infinite-order sudden (IOS) approximation and compared with accurate close-coupling (CC) calculations. Agreement is good in the dominant coupling (small total angular momentum J) region. Simple methods for calculating integral inelastic cross sections are discussed, and it is found that accurate cross sections can often be computed very simply, even when large numbers of channels are coupled together, by using IOS or first-order sudden (FOS) approximations for small J and CC or exponential Born (EBDW) methods for large J.

An Indo Investigation Of The Structure And Bonding Of Acetylacetone And Trifluoroacetylacetone, Mark S. Gordon, Robert D. Koob

Mark S. Gordon

The energies of the enol forms of acetylacetone (ACAC) and trifluoroacetylacetone (TFA) have been minimized with respect to all structural parameters using the INDO molecular orbital theory. The internal hydrogen for enol ACAC is found to be symmetrically arranged between the two oxygens with an OHO angle of 152 o and an OH bond length of 1.174 A. Fluorine substitution to produce the electronically asymmetric molecule TFA causes only a slight asymmetry in the position of the internally bonded hydrogen. In both molecules this hydrogen is located in a well-defined single potential energy minimum. Electron density is increased on the …

Case Studies In Systems Chemistry, George Fleck

Open Educational Resources: Textbooks

This publication was produced as a teaching tool for college chemistry.The book is a text for a computer-based unit on the chemistry of acid-base titrations, and is designed for use with FORTRAN or BASIC.computer systems, and with a programmable electronic calculator, in a variety of educational settings. The text attempts to present computer programs that are relatively free of reliance on specialized large computer systems programs. The case-study approach presented is highly research and laboratory oriented. Similar subject matter is conventionally taught in most introductory college chemistry courses, but this text material attempts greater depth of instruction through utilization of …

The Role Of Mannosyl-Phosphoryl-Dihydropolyisoprenol In The Synthesis Of Mammalian Glycoproteins, John W. Baynes, An-Fei Hsu, Edward C. Heath

Faculty Publications

A mouse myeloma tumor was used as a model system to study the biochemical steps involved in the incorporation of mannose into glycoproteins. This tumor, MOPC-46B, synthesizes a K-type immunoglobulin light chain (K-46) which is a glycoprotein with a single oligosaccharide side chain containing mannose as one of its constituent sugars. MOPC-46B microsomal preparations contain enzymes which transfer mannose from the sugar nucleotide, GDPmannose, to endogenous lipid and protein acceptors. Formation of the mannolipid proceeds by the reversible transfer of mannose from GDP-mannose to an endogenous phospholipid. The mannolipid was purified and characterized by chemical methods and mass spectrometry as …

15th Annual Rocky Mountain Spectroscopy Conference

Rocky Mountain Conference on Magnetic Resonance

Program and abstracts from the 15th annual meeting of the Rocky Mountain Spectroscopy Conference, sponsored by the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 20-21, 1973.

Thermodynamic And Electrochemical Studies Of Niobium In Molten Fluorides And Chloroaluminates, Gann Ting

Doctoral Dissertations

The oxide chemistry of niobium(V) has been studied in molten LiF-BeF₂ mixtures. The stoichiometry of an oxygen-containing niobium(V) species (NbO₂F) has been established in molten Li₂BeF₄ from the heterogeneous equilibrations of NiNb₂o₆ and NiO with the melt containing NiF₂, the equilibrium quotient for the reaction was determined. The equilibrium quotient for the heterogeneous reaction of Nb₂O₅ and BeO with molten LiF-BeF₂ mixtures (67-33 and 52-48 mole %) was also determined, and the effect of the melt composition on the solubility of Nb₂O_{5 …}

The Internal Chemical Shift. A Key To Bonding In Aromatic Molecules. I. Internal Shift Correlations, Donald W. Beistel, Holger E. Chen, P. J. Fryatt

Chemistry Faculty Research & Creative Works

The study of proton shift behavior in nine families of disubstituted benzenes has provided quantitative correlations of internal and meta shifts among all families. The equations of correlation are useful in the prediction of shifts to an error of 0.015 ppm. The studies demonstrate shift additivity for the 4-substituted halobenzenes and suggest a chain rule relationship for substituent effects in those compounds. For that reason, previous theories of substituent interactions involving inductive and resonance contributors appear incorrect when applied to proton shift data. In decreasing order of up field shift at the ortho protons the substituents studied include N(CH3)2, NH2, …

The Intensity Of Ligand Absorption, Shing-Bong Chen

Masters Theses & Specialist Projects

The ultraviolet absorption spectra of a number of aryl phosphines and amines and transition metal complexes of triphenylphosphine have been determined. These data indicate that the intensity of the Õ* ¬ Õ phenyl ring transition is not only sensitive to the central atom attached to the ring but is also affected by the metal ion in the complex. Since the degree of covalency depends on the degree of back donation, the oxidation state of the metal ion was found to be the most important factor in determining the intensity of the absorption. The more covalent the metal-phosphine bond, the lower …

Triplet-Triplet Energy Transfer In Indolylketones, Larry E. Hewitt

Dissertations

No abstract provided.

Separation Of Copper (Ii) And Silver (I) By Differential Rates Of Extraction & Extraction Rate Studies Of Copper(Ii), Jon Hines

Masters Theses & Specialist Projects

It was the purpose of this work to study the extraction of Cu(II) and Ag(I) with dithizone in chloroform. This particular pair of elements was chosen for study for several reasons. The most prominent of these reasons is that these two elements are found together in nature and are often found combined in manufactured products. Being in the same periodic group, they exhibit similar chemical characteristics making them difficult to separate without special procedures. These similar chemical characteristics make the analysis of these elements difficult when in the presence of each other. Finally, it is of importance that both elements …

Electron Transfer Rate Between Cobalt(Ii)-Cobalt(Iii) Polypyridyl Complexes In Nonaqueous Solvents, William Prow

Masters Theses & Specialist Projects

Numerous studies have been made in recent years on electron transfer reactions of transition metal complexes which proceed by either an inner- or an outer-sphere mechanism. However, except for the Fe(II)/ Fe(III) isotopic electron exchange system, few of the studies have been conducted in other than aqueous media. This study was undertaken to examine solvent effects on redox reactions of transition metal complexes which proceed by an outer-sphere mechanism.

During this study, the electron exchange rate between the bis(2,2',2"-tripyridyl)cobalt(II) complex and the tris(2,2'-dipyridyl) cobalt(III) complex was measured in a number of nonaqueous solvents. Rate measurements were made at three or …