Physical Sciences and Mathematics Commons^™

Heterocyclic Syntheses Utilizing Aryl Cyanates, Joseph Eugene Drumm

Masters Theses

No abstract provided.

The Kinetics Of The Metal Exchange Reaction Between N-(2-Hydroxyethyl) Iminodiacetatonickelate (Il) And Copper(Ii), Craig R. Weed

Masters Theses

The reaction between copper(II) and N -(2-hydroxyethyl)iminodiacetatonickelate( II) (NiHEIDA) was studied between pH 4.0 and 5.6 over a 70 fold variation in copper concentration at an ionic strength of 1.25 and a temperature of 25° C. The reaction order in both NiHEIDA and Cu(U) is first. The reaction rate is pH sensitive and a hydrogen dependent pathway as w ell as copper dependent and copper and hydrogen independent pathways were found.

Evidence is given for a stepwise mechanism for the unwrapping of HEIDA from its nickel complex, follow ed by copper attack to give a dinuclear intermediate, which then breaks …

The Application Of Multiderivative Infrared Spectroscopy To Iodine Number Determination, Jeffrey C. Lowry

Masters Theses

The Food and Drug Administration requires the disclosure of total unsaturation of commercial products as an indication of nutritional value. This unsaturation is a guide to the expected stability of food additives, such as edible oils and foods in which they are used. Unsaturation is typically evaluated as an iodine number, calculated for these additives based on their consumption of iodine through addition across the carbon-carbon double bonds. This titration method can typically take 45 minutes.

The investigation presented develops an alternative method for determining iodine numbers of some common oils using a computerized infrared spectophotometer. The analysis time, as …

Kinetics Of The Formation Of The Nickel(Ii) Complex With N, N' -Dimethylethylenediaminediacetic Acid And The Metal Exchange Reaction Between N,N'-Dimethylethylenediaminediacetatonickel(Ii) And Copper(Ii), Roger A. Karel

Masters Theses

The kinetics of the reaction of aquonickel (II) ion with N'N'-dimethlethylenediaminediacetic acid has been studied at 25°C and 0.1M iconic strength over a pH range of 6.0 to 9.3 using stopped-flow techniques. Formation reactions in all cases were first-order in Ni (II) and in ligand. The formation rate constant for the protonated and unprotonated species were evaluated and compared to their theoretical value. The rate-determining step is shown to be ring closure. A comparison of this system with other studies involving complexation of nickel (II) confirm the magnitude of the internal conjugate base effect and also shows a correlation between …

Aromatic Amine--Haloboranes : Evidence For Trigonal Boronium Cations, Debra H. Reid

Master's Theses

In the last twenty years Lewis adducts of boron trihalides and mixed boron trihalides have been examined using nuclear magnetic resonance spectroscopy. The donor to which the boron trihalide attaches has generally been some type of amine (strong donor), though oxygen, sulfur, phosphorous, and other donors ahve also been studied. The boron trihalide portion serves as the Lewis acid. Various nuclei (1H, 13C, 15N, 11B, 19F) have been examined in such boron trihalide adducts and the general trend in signal position in all 5 nuclei observed is (in order of increasing downfield shift) BF3

The acid strength of the boron …

Naphthalene-2,3-Dialdehyde: A Synthon To 7,9-Polymethylene-8h-Cyclohepta[B]Naphthalene-8-One And A Study Of Their Aromaticity, Edward O. Crapps

Dissertations

This report describes the synthesis of naphthalene-2,3-dialdehyde, and an analytical method for determining its purity by thin layer chromatography. Subsequently, the dialdehyde was condensed with various cyclic ketones to generate a series of polymethylene bridged naphthotropones. It was found that planarity and aromaticity increase with the size of the methylene bridge, although, the bridge must contain six or more methylene groups for the latter to be true. The claim for aromaticity is supported by NMR and IR data, which indicates the positive charge for a perchlorate cation salt is delocalized over the naphthalene and tropone ring system. Furthermore, from the …

I. A Temperature Dependent Nmr Study Of 6,6-Dicarbethoxy-5,5-Dideuteodi-Benzo--[A,C]-[L, 3]-Cycloheptadiene Ii. The Synthesis Of Four Deuterated Analogs Of 6, 6-Dicarbethoxydibenzo-[A,C]-[1,3]-Cycloheptadiene, Patrick F. Jonas

Masters Theses

The kinetics of conformational interchange of 6,6-dicarbethoxydi-benzo- a,c - 1,3 -cyloheptadiene and its 5,5-dideuterated analog were studied using variable temperature NMR techniques. The free energy of activation for conformational interchange of the parent compound was found to be 9.02 kcal mol^-1 and that of the 5,5-dideuterated analog to be 9.42 kcal mol^-1. Values of the entropy of activation were found to be -19.91 e. u. and -18.12 e. u. respectively. The spectra were recorded on a Nicolet NMC-360 wide bore spectrometer and the data collected treated as an AB spin system.

The 4,8-dideutero, 4,5,5,8-tetradeutero and 5,5,7,7-tetradeutero analogs …

Determination Of The Internal Rotational Energy Of Gaseous 1,2-Dichloroethane In An Argon Matrix Using Fourier Transform Spectroscopy, Susan Lynn Clarke

Chemistry & Biochemistry Theses & Dissertations

A sample cell and delivery system for rapid matrix isolation of gas mixtures at constant gas temperature was designed and evaluated. The rotational energy differences of 1,2-dichlorosthane and of its deuterium compound wars then determined to test this technique.

The rotational energy barriers calculated from Boltzman plots of ths gases at different temperatures were; 1.21 + 0.38 keel/mole, 1.33 + 0.70 Real/mole, and 1.12 + 0.45 kcal/mole for the CH2 wagging„ C-Cl stretching and CD₂ wagging modes respectively. These values were in good agreement with previously published values.

These results allowed evaluation of this apparatus and experimental design and …

Characterization Of Trihalomethane Formation From Proteins In Chlorinated Water, Robert Aaron Kravitz

Chemistry & Biochemistry Theses & Dissertations

Traditionally humates have been considered the most significant precursor in the formation of trihalomethanes in finished drinking water. This study investigates another potential precursor, namely proteins. The chlorination of aqueous protein solutions yields significant levels of trihalomethanes in terms of the maximum contaminant level (MCL) of 0.100 mg/L imposed by the USEPA. Molar yields for several proteins were determined. The average yield per unit of organic carbon was 0.5% as compared to 0.8% for a humic acid studied. A model protein, bovine serum albumin, was studied extensively to ascertain the effects of total organic carbon, chlorine dose, and time on …

The Magnitude Of Charge Effects On The Fluorescence Quenching Of Peptidyl Tryptophan By Iodide, James L. Danziger

Honors Theses

The magnitude of charge effects on the quenching of tryptophan containing peptides by Iodine is compared for those peptides containing a positvely charged tryptophan to those peptides containing a negatively or uncharged tryptophan.

The Development Of An Optical Ph Sensor Based On Fluorescence, Kimberley Ann Forbes

Honors Theses

We are interested in developing optical pH sensors based on the fluorescence of an immobilized fluorophor confined on the end of a bifurcated fiber optic. Such optical pH sensors have several potential advantages: they should be inherently less sensitive to electrical noise than conventional pH electro1es, they require no reference electrode, and they make possible remote measurements. The fluorophors evaluated are bound electrostatically to an ion exchange membrane which is then attached to the common end of a bifurcated fiber optic, The fluorophor is excited through one arm and the fluorescence emission is passed through the other arm of the …

The Preparation Of Cyclic Organic Carbonyl Compounds From Ƞ5-Cyclopentadienyltetracarbonylvanadium And Substituted Acetylenes, Ronald C. Newbold

Honors Theses

Studies on the reactivity of many transition metal carbonyl complexes with various acetylenes have generated significant interest in the field of organometallic chemistry, but little effort has been put forth to make use of these compounds as genuine organic reagents. Most metal carbonyl compounds generate both organic and organometallic products, where oxidative cleavage becomes necessary to obtain the organic moiety. (35-c5H5)v(CO)4 is an oxygen-sensitive carbonyl complex which has been shown to thermally react with bis-(pentafluoro­phenyl)acetylene to produce cyclic carbonyl compounds in high yield, particularly the quinone derivative, with few organometallic products. The thermal reactivity of (35-c5H5)v(CO)4 is characterized with various …

Determination Of Aldehydes In Ambient Air By High Performance Liquid Chromatography With Fluorescence Detection, Carol B. Berman

Honors Theses

Two methods for the determination of aldehydes in ambient air were investigated. The methods involved derivatization of the aldehydes by 2-diphenylacetyl-1,3-indandione-1-hydrazone (DAIH) and 1-dimethylaminoaphthalene-5-sulfonylhydrazine (dansylhydrazine) in acetonitrile solution. The deriviatives were then separated by high performance liquid chromatography and detected and quantified by flourescence detection. The DAIH method was found to be unsuitable and was therefore abandoned. The dansyl hydrazine method was found to be a potentially uncomplicated, rapid, and senstitive procedure for the detection of aldehydes.

Conformational Energy Calculations On Valinomycin, Rachel J. Cohen

Honors Theses

The antibiotic action of the ionophore valinomycin is a result of its ability to preferentially bind potassium ions and transport them across cellular membranes. Complexation is solely due to the molecular structure of this cyclic depsipeptide. In solution, the molecule exists in different conformers depending upon solvent polarity. Exact knowledge as to the structure of valinomycin in the aqueous and lipid cellular layers is thus difficult to determine. Many spectral studies of valinomycin have been undertaken utilizing a variety of instrumental methods and conformations existing in different solvents have been proposed. We have performed energy minimization procedures on these structures. …

The Microstructure Determination Of Poly(B-Pinene), Kevin G. Perrigno

Honors Theses

The microstructure of poly(B-pinene) was determined through analysis of pyrolysis products.

Synthesis And Spectral Studies Of Amides Of 9-Anthroic Acid, Juliana Rodgers

Honors Theses

The fluorescence energy, shape of the fluorescence spectrum, and the fluorescence efficiency of 9-anthramide (9-CONH2) and N,N-diethyl-9-anthramide (9-CONEt2) have been investigated as a function of solvent. For the 9-CONH2, the Sl energy decreases and the fluorescence spectra become structureless at the polar and nonpolar extremes of the solvent scale. This unusual solvent-dependent fluorescence behavior for 9-CONH2 is explained by a significant geometry change subsequent to excitation, whereby the exocyclic group rotates about the anthracene rings. In contrast, 9-CONEt2 shows solvent-independent behavior. The Sl energy generally remains constant and the fluorescence spectra show well-defined vibrational structure in a wide variety of …

Detection And Quantification Of Atmospheric Carbonyl Compounds, Peter Gerard Schulam

Honors Theses

Ambient air aldehyde analysis was performed in Schenectady, NY. The Technique, as prescribed by Kuntz et. Al. (7), entailed the trapping of the volatile aldehydes as their 2,4-dinitrophenylhydrazone derivatives in an acetonitrile solution. The derivatives were then separated on a reversed phase HPLC column and detexted by UV absorption at 254 and 360 nm., simultaneously. The air in Schenectady was found to contain formaedehyde and acetaldehyde at concentrations which ranged from .70 to 30.5 ppb and below that of detection to 1.6 ppb, respectively. Formaldehyde's daily average in Schenectady was 7.6 ppb. The formaldehyde and acetaldehyde levels at Whiteface Mtn. …

Quantitative Evaluation Of Substituent Effects On Stabilization Energies Of Strained And Unsaturated Molecules, Tyler Arthur Stevenson

Theses

Thermodynamic stabilization energies are presented for a series of monosubstituted vinyl, cyclopropyl, ethynyl, and phenyl compounds. The energies are calculated using ab initio molecular orbital calculations at the 4-31G level, and also with published experimental heat of formation data. Correlation analyses are then attempted with the dual substituent parameter approach with the stabilization energies. The analyses are also attempted with a triple-parameter approach using Topsom's theoretically calculated X, F, and Ro constants. Among the findings are the facts that π-donating substituents correlate well, while π-accepting substituents do not. Indications of the relative sensitivities of hydrocarbon frameworks to substituent electrostatic and …

Synthesis Of Cyclobutenyl Ketals, Atef Z. Boulos

Theses

A series of dialkoxy derivatives of N,N'-di-tert-butyl-2-butylamino-3,3-dichloro-4-dichloromethylene cyclobutenyl carboxamidinum chloride, were prepared by dissolving either Na+ or K+ alkoxide in the appropriate alcohol, or by treatment with potassium hydroxide in the appropriate alcohols. Thus, the dimethoxy, diethoxy, di-isopropoxy, di-n-butoxy, di-tertbutoxy derivatives were obtained.

Derivatives Of Trifluorovinylsulfur Pentafluoride And F-(Tert-Butyl) Hypochlorite, Jo Ann Marie Canich

Dissertations and Theses

Trifluorovinylsulfur pentafluoride dimerizes to (SF₅CFCF₂)₂ in the presence of cesium fluoride. Two derivatives of trifluorovinylsulfur pentafluoride, SF₅CF(CF₃)C(O)F and SF₅CF(CF₃)C(O)NH₂, were used to prepare the new compounds, SF₅CF(CF₃)CO₂H and SF₅CF(CF₃)CN, respectively. The first was prepared by reacting the SF₅-acid fluoride with water, while the second involved the abstraction of water from the SF₅-amide using P₄O₁₀. The attempted preparation of a bis-pentafluorosulfur ketone and a pentafluorosulfur containing acid anhydride …

Photoaffinity Labeling Of The Antimycin Binding Site In Rhodopseudomonas Sphaeroides, Emily Wilson

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The purpose of this study was to identify the site of interaction of antimycin with the ubiquinone-cytochrome b-c1 oxidoreductase in the photosynthetic bacteria, Rhodopseudomonas sphaeroides. To accomplish this goal, three areas of research were undertaken: the synthesis of a radiolabeled, photoaffinity analog of antimycin, identification of the inhibitory characteristics of this analog, and the photoaffinity labeling of the antimycin binding site. All three areas were accomplished.

The major finding of this study was the identification of an 11,000 dalton polypeptide as the predominantly labeled protein. Although this polypeptide was not exclusively labeled, it was consistently labeled and showed competition …

The Synthesis And Characterization Of Some Transition Metal Complexes Prom Mixtures Of Poly Pyrazolyl Borates, Robert Matthew Alway

Masters Theses

This is a report of the synthesis and separation of transition metal complexes of hydrotris(1-pyrazolyl)- borate and hydrotris(3,5-dimethyl-l-pyrazolyl)borate. These complexes contain a central metal ion and two tridentate ligands, one hydrotris(1-pyrazolyl)borate and one hydrotris(3,5-dimethyl-l-pyrazolyl)borate. Mass spectrometry proved to be an extremely useful technique for identifying products. Many mass spectra are included and discussed extensively.

Complexes containing hydrobis(pyrazole)(3,5-dimethyl -1-pyrazolyl)borate and hydrobis(3,5-dimethyl-l-pyrazole) (pyrazolyl)borate also were synthesised and mass spectra obtained.

Investigation Of Matrix Effects On The Furnace Atomic Absorption Signals Of Chromium, Nickel And Selenium, Susan Marie Viet

Chemistry & Biochemistry Theses & Dissertations

The flameless atomic absorption signals of chromium, nickel and selenium are subject to matrix interferences arising from inorganic salts and anions commonly found in urine. The effects of such salts on the atomic absorption signals were investigated using Polarized Zeeman Effect background correction in conjunction with a detector/readout system capable of resolving absorbance signals in 18 msec readings. Both optical temperature control and current temperature control were employed for each analysis. Peak area, peak height, peak shape and appearance time were compared for matrix-free standards and matrix-containing standards.

The influence of the inorganic salts on the metal analyses was found …

Effects Of N-Substituents On The Polymerization Properties Of Maleimide, Dilip R. Abayasekara

Theses and Dissertations

The effect of the amide function and the carbethoxy function on the polymerization properties of maleimide are reported. The effects of these functions on homopolymerization and copolymerization (with styrene) were examined. These electron-withdrawing groups appeared to decrease the rate of homopolymerization and increase the rate of copolymerization.

N-carbamylmaleimide and N-carbethoxymaleimide were copolymerized with styrene in 1,4 -dioxane at 60.0° C at different feed ratios to high conversion. Copolymer composition, determined by elemental analysis and 1H NMR, indicated that while 1:1 copolymers were obtained with an equimolar feed ratio, the two systems were not alternating. It is of note that the …

A Three Part Research Report: The Synthesis Of Potential Insecticides, N-(4-Heteroaryloxybenzoyl)-N'-(2,4-Dichlorobenzoyl) Hydrazines: A Reinvestigation Of Hexamethylphosphoramide With Ketoximes; Regioselective Fluoralkoxylation And Polyfluoroalkoxylation Of Activated Dihalobenzenes And Dihaloheterocycles, Gary A. Decrescenzo

Retrospective Theses and Dissertations

This report discusses research in three areas of organic synthesis: The synthesis of potential insecticides; the reinvestigation of the reaction of hexamethylphosphoramide with ketoximes; and the regioselective fluoroalkoxylation and polyfluoroalkoxylation of activated dihalobenzenes and dihaloheterocycles. In Part I, a series of N-(4-heteroaryloxybenzoyl)-N'-(2, 3-dichlorobenzoyl) hydrazines are synthesized, and attempts at cyclic dehydration to the corresponding 2, 5-disubstituted-1, 3, 4-oxadiazoles are discussed. In Part II, the synthesis of N, N-dimethyl-N'-aryl amidines by the reaction of aryl alkyl and diaryl ketoximes with HMPA is discussed. In Part III, a series of activated dihalobenzenes and dihaloheterocycles are reacted with sodium trifluoroethoxide to study the …

Measurement Of Low Vapor Pressures : A Kinetic Approach, Samuel Bernard Bliden

Dissertations and Theses

A kinetic model was applied to vapor pressure data obtained by a variable flow method. The vapor pressures of benzoic acid, naphthalene, benzophenone, and phenylhydrazine were measured at temperatures of 293K to 307K. The data are summarized in the data table on the following page. These data were obtained by passing air over a sample of the substance in a tube. The air stream was combusted, and a flame ionization detector was used to measure the mass of CO₂ so obtained. Several different flow rates were used at each temperature with each substance.

An Approach To The Synthesis Of Pyrans, Thomas F. Ball

Dissertations, Theses, and Masters Projects

No abstract provided.

The Synthesis Of Various Substituted 3-Amino-7-Hydroxy-2,2-Dimethyltetralins And Their Opioid-Related Activities, David Alan Lippman

University of the Pacific Theses and Dissertations

A series of aminotetralones and aminotetralins were synthesized from the common intermediate F, 3-amino-2,2-dimethyl-7-methoxy- 1-tetralone. The final compounds derived from F were simple substituted and/or reduced analogues. The products would allow a progressive structure activity relationship to be drawn based on pharmacological testing.

The common intermediate F was synthesized utilizing a six step procedure starting with p-methoxyphenylacetic acid. The overall yield from the precursor to the F:HC1 was 25%. Compound F was either O-demethylated to form 3-amino-2,2-dimethyl-7-hydroxy-l-tetralone (I) or was dimethylated on the amine and subsequently O-demethylated to yield the 3-dimethylamino-7-hydroxy-2,2-dimethyl-l-tetralone (J). The last major modification was the reduction of …

Synthesis And Characterization Of Some Oxoperoxopolycarboxylato Vanadates (V) And Their Biochemical Significance, Myunghi Lee

Dissertations, Theses, and Masters Projects

No abstract provided.

Electrochemical Studies On Peroxo Heteroligand Vanadates (V) In Aqueous Solution, David J. Mayonado

Dissertations, Theses, and Masters Projects

No abstract provided.