Physical Sciences and Mathematics Commons^™

Cobalt (Iii) Complexes With (R) - 1, 2-Diaminopropane And Its Derivatives, Christopher John Rudy

Masters Theses

(R)-1, 2-Diethylaminopropane (N,N' -Etlpn) was prepared by LialH₄ reduction of (R)-1-2-diacetamidopropane (m.p. 153.5°C). The [∝]_D of N, N'-Melpn and N,N'-Etlpn was related to that of 1pn and was concentration dependent. (R)-1, 2-Dibenzylaminopropane was prepared. Complexes of trans, trans- and trans, cis-dinitrobis ((R)- 1, 2-diethylaminopropane) cobalt (III) were perpared. The hexadecadal rule was used to help assign the nitro oxygens of the complexes to sectors adjacent to the axial amine hydrogens and within the boundaries of the λ- chelate rings. The CD spectra was solvent dependent. The instability of trans-[Co (III)N₄X₂]⁺ complexes was related …

Synthesis Of Pyridine Nucleosides By Cycloaddition Reactions And Synthesis And Condensation Reactions Of 4-Aryl-2-Oxytetronimides, Glenn L. Heise

Masters Theses

Experiment 1: The reaction of various glutaconaldehyde salts (Na⁺ or K⁺) with glycosyl isothiocyanates has resulted in the formation of a novel class of compounds. Relatively mild conditions were utilized for the synthesis which occurs in four steps, and in good yield, starting from glucpseptentaacetate. These reactions were found to be regiospecific. The unique physical and spectral properties of the model compound 1-(2,3,4,6-tetra-0-acetyl-β-D-glycopranosyl)-2-thiono-3-pyridine carboxaldehyde are also discussed.

Experiement 2: Early synthetic methodologies have recently been utilized in the synthesis of 4-aryl-2-oxytetronimides. These compounds have been found to participate in condensation reactions with various substituted o-phenylene diamines. A …

The Design And Construction Of Microprocessor-Computer Controlled Rapid Scanning Fiberoptic Spectrophotometer, Kathleen Marie Tobin

Masters Theses

Conventional spectrophometers require the transfer of a sample to a cuvette for obtaining spectra. The measurement of absorbance in situ can be accomplished using a fiber optic probe which can be placed directly in the sample. The fiber optic probe also minimizes environmental factors such as thermal or vibrational which may affect the absorbing species. A rapid scanning speed allows for essentially simultaneous wavelength monitoring.

The effect of coupling a rapid scanning spectrophotometer with a fiber optic probe provides for an extremely versatile system. When used in comjunction with a microprocessor or computer, this approach offers advantages such as data …

Reactions Of Supercritical Water With Quinolone And Related Compounds, Zhuangjie Li

Masters Theses

One function which coal processing can perform is the removal of heteroatoms to yield a less polluting product. The removal of nitrogen atoms from the model compounds quinoline and aniline, which are believed to be representative of the nitrogen functional groups found in coal, was studied using supercritical water (SW) as the fluid. Water at these conditions serves as a reactant, helping to promote the rupture of the heterocyclic ring and in the removal of nitrogen attached to an aromatic ring. Heterocyclic ring rupture leads to the formation of several methylated products, methyl and dimethyl anilines, phenols and quinolines. The …

The Survival Of Mesophilic And Thermophilic Bacteria Subjected To Uv Irradiation, Sajida A. Shaikh

Masters Theses

Survival curves were determined for the mesophile, Bacillus licheniformis and the thermophile, Bacillus stearothermophilus after subjecting the cells to ultraviolet irradiation. Cells were grown at 37°C for the mesophile and at 55°C for the thermophile.

At low UV exposure times, the thermophile was more resistant to UV irradiation (had a better survival rate) than was the case for the mesophile. At higher exposure times, the situation was reversed, the mesophile having a greater survival rate than the thermophile.

The effect of changes in the temperature during irradiation was also determined. Thermophiles were greatly affected by changes in temperature while the …

Development Of An On-Line Computer System For Cyclic Voltammetry Studies, Tai-Lee Leo Huo

Chemistry & Biochemistry Theses & Dissertations

An Apple II Plus microcomputer was interfaced to a PAR 174A Polarographic Analyser, an HP 7O4OA X-Y recorder and a three-electrode system. This on-line computer system was applied to Cyclic Voltammetry (CV) studies. The interfacing involved both hardware and software development. Various hardware components were used to amplify and transmit the analog signal both going into the computer and coming from the computer. Software programs were written for staircase waveform generation, data acquisition, and plotting the voltammograms obtained.

A package was designed for CV experiments to be used by the students in the instrumental analysis laboratory. This package contains several …

Detection And Analysis Of Carbonyl Compounds In Rural Cloudwater, Steven Bart Bertman

Honors Theses

A new technique for aqueous determination of aldehydes and ketones was field tested along with a new technique for ambient air analysis. The work was done during the summer of 1984 on Whiteface Mountain in Wilmington, NY. Both techniques utilized carbonyl derivitization as their 2,4-dinitrophenyl hydrazones and subsequent analysis by reversed phase HPLC. Analysis of the blank levels for the ambient air method shows the levels found to be non-detectable. The aqueous method worked well. Formaldehyde, acetaldehyde, and acetone were the only species found in cloud water. They were generally present in concentrations between .5 uM and 4 uM. Little …

The Syntheses Of Benzo-(2.2)-Paracyclophane, 2, 15-Dithia-(3.3)-Napthalenophane, And Hexamethylbenzene Dichloride, David Gene Barrett

Honors Theses

The purpose of this study was the preparation by a novel approach of benzo-(2.2)-paracyclophane. Also synthesized were the syn-and anti-isomers of 2,15-dithia (3.3)- napthalenophane. The results of these syntheses are supported by spectral studies. In preparation for future study of the ruthenium complexes of these cyclophanes, hexamethylbenzeruthenium dichloride was also synthesized.

Determination Of The Equilibrium Constant For The Acetaldehyde-Bisulfite Addition Compound, Mark B. Richard

Honors Theses

Synthesis of the addition compounds of formaldehyde, acetaldehyde, acetone, and propionaldehyde with sodium bisulfite was achieved using the method of Stewart and Donnally. Recognition of a water comtamination led to a method for determining purity using the integrations from NMR spectrometry. An equilibrium constant for the acetaldehyde-bisulfite addition compound was determined using the method of Dasgupta. A value of 6.3 x 10-5 was determined at a ph of 4.7. This value correlates well in magnitude when compared to the value of 1.56 x 10-5 for the formaldehyde-bisulfite addition compound at pH 5.0 determined by Dasgupta and also with Stewart and …

A Study Of Chemiluminescence Via Flash Photolysis, Craig Lawrence Shalmi

Honors Theses

We are interested in understanding the mechanistic details of photo-initiated chemiluminescent reactions. Currently, we are examining reactions which lead to luminescent from electronically excited nitric oxide. Stedman has reported observing NO gamma-band emission in the thermal reaction of hydrazoic acid, HN3 with O(3P). The rate constant for the production of NO* is low and, consequently, the emission intensity is weak. We are endeavoring to generate excited NO from HN3 and O(1D), the later produced in the flash photolysis of ozone. It is hoped that a greater population of NO* will be produced yielding a greater chemiluminescent intensity. By observing the …

Reaction Of Atomic Hydrogen With Chloroform In A Discharge Flow Reactor, Wan-Kuen Jo

Theses

The reactions of atomic hydrogen with chloroform were studied in a tubular flow reactor both in a 4 cm i.d. and 2.6 i.d. discharge flow reactor at pressure of 2.22 to 2.82 mmHg and room temperature using GC and GC/MS for analysis of the reaction. The hydrogen atom concentration at the reaction flame was measured by Chemiluminescence titration with nitrogen dioxide. The hydrogen concentrations are in the 2.48 x 10⁺¹⁴ to 4.83 x 10⁺¹⁴ atoms/cc range at six different hydrogen flow rates. Evidence was found for the formation of atomic carbon intermediate in the reaction, but methane was …

Reactivity Of Some Nitrogen-Containing Compounds At Supercritical Water Conditions, David M. Tiffany

Masters Theses

The use of water at cuperctirical conditions to remove nitrogen from several nitrogen-containing compounds was studied with the purpose of exploring the use of supercritical water as a method of removing nitrogen from the extraction products of coal. Quinoline and isoquinolone were the primary model compounds used with benzonitrile and carbazole also being examined briefly. Reaction conditions varied in temperature (350-500°C), pressure (3500-5200 psi), and water density (0.170-.0.426g/cc). The major products formed by isoquinoline were benzene, toluene, ethylbenzene, and o-xylene as well as nonvolatile tar and char. Quinoline produced aniline and toluidine in addition to those obtained from isoquinoline. Most …

The Synthesis And Evaluation Of A New Analog Of Phencyclidine (Pcp), William H. Johnson Jr.

Chemistry & Biochemistry Theses & Dissertations

Based on an interpretation of the literature of phencyclidine (PCP) together with an examination of the relevant models or prototype structures, this research has attempted to design and synthesize a rigid analog of the phencyclidine structure. The parent ring systems suggested for this study were the 1-arnino and 2-arninornethyltetralins, 10 and, 12.

Several organic compounds, based on this design, have been prepared by classical examples of reductive alkylation reactions of the corresponding 2-hydroxyciethylene-1-tetralones, 11, and by the condensation and subsequent reductive alkylation of the 1-arninotetralin, 9. These arninomethyltetralones, 28, 29 and 30, together with an example of a substituted 1-arninotetralin, …

Chemical Studies On Oxomolybdenum(Vi,Iv) Complexes As Bioinorganic Models For The Molybdenum Oxidases, James Thomas Lyon Iii

Theses and Dissertations

The synthesis, characterization, and chemical properties of Mo(VI)o₂(5-X-SSP) and Mo(VI)o₂(5-X-SSE), (5-X- SSP²- = 2-((5-X-salicylidene)amino)benzenethiolate; 5-X- SSE^2- = 2-((5-X-salicylidene)amino)ethanethiolate; X = Br, Cl, H, CH₃O), which contain tridentate (ONS) Schiff base ligands is described. The chemical properties of these molybdenum complexes are compared with those which possess tridentate (ONO) Schiff base ligands. Cyclic voltammetry was used to obtain cathodic reduction potentials (E_PC) for the quasi-reversible reduction of the cis-dioxomolybdenum (VI) complexes. Although the reductions are quasi-reversible, trends are observed in E_PC both within series and when different series are …

The Determination Of Biological Activity And Biochemical Mode Of Action For The Oxadiazole And Diacylhdrazine Insecticides, Bonnie M. Gunn

Retrospective Theses and Dissertations

This report includes the determination of activity and possible mode of action for a group of potential new insecticides. The biological screening procedure was developed using Drosophila melanogaster as the test organism while Musca domestica was used for mode of action assays. The percent kill for each compound is based on the number of eggs placed on media containing the insecticide minus the number of adults enclosed as compared to the control media reared flies. Observations were made on all stages from eggs through adults to determine time of death and if any malformations were present. These observations aided in …

Dilithiation Reactions Of N-Substituted Benzylamines, Richard Patrick Franks

Theses & Honors Papers

N-Cyclohexyl -2-methylbenzylamine was metalated with two equivalents of n-butyllithium activated with one equivalent of tetramethylethylenediamine (T.M.E.D.A.) , and the solvent system, time, and temperature were varied to establish a maximum yield . It was experimentally found that a thirty minute ice-water bath metalation in diethyl ether, followed by a fifteen minute condensation with benzophenone in refluxing diethyl ether gave the best yield with the benzophenone electrophile. The product was characterized by N.M.R. and found · to be 2- ( cyclohexylamino)-2-(2-toluyl ) -1 ,1-diphenylethanol (the benzylic adduct) in a 29% yield.

When N-cyclohexyl -2-methylbenzylamine was metalated for three hours in an …

Thermodynamics Of Ion Association In Aqueous Fluoride Solutions. Determination Of Stability Constants For (Naf), (Mgf)+ And (Caf)+ Ion Pairs, Waldo Zamorano-Santander

Masters Theses

Stoichiometric ion-association constants were determined at several ionic strengths for (NaF) over the temperature range 15-40°C and for (MgF)⁺ and (CaF)⁺ over the temperature range 25-45°C using fluoride ion selective electrode measurements.

Thermodynamic association constants, K°, were obtained through extrapolation of the stoichiometric values to infinite dilution. Values of K° for (NaF) are 1.70, 2.16 and 2.54 at 15, 25 and 40°C, respectively. The K° values for (MgF)⁺ are 73.4, 88.0 and 98.2, and for (CaF)⁺ are 13.7, 17.5 and 21.9 at 25, 35 and 45°C., respectively.

The stoichiometric association constants for (NaF) can be reproduced …

Preparation Of Methyl-Substituted Dienols By The Hydromethylation Of Ene-Yn-Ol Substrates With Titanium Tetrachloride And Trimethylaluminum, Terry James Zitzelberger

Dissertations, Theses, and Masters Projects

No abstract provided.

The Irreversible Inhibition Of D-Amino Acid Oxidase With Trans-3-Bromoacrylic Acid And Four Others Halo-Vinylic Acids, Christopher D. Kontos

Dissertations, Theses, and Masters Projects

No abstract provided.

Bimetallic Tungsten Carbonyl Complexes, Jin-Guu Wang

Masters Theses

Two heterobimetallic complexes, [(CO)₄W(PPh₂CH₂CH₂-PPh₂)₂MCl₂]_n ( M = Pd or Pt ), were prepared from the reaction of trans-W(CO)₄(ŋ¹-PPh₂CH₂CH₂PPh₂) ₂ with M(COD)Cl₂ (COD = cyclooctadiene). A trans arrangement about tungsten was found for both the palladium and platinum complexes. The square planar palladium center was shown to have a trans geometry in solution while a cis arrangement for the platinum moiety was observed. Far infrared studies indicated a mixture of cis and trans …

Synergistic Effects In Bimetallic Hydrogenation Catalysts, Kathleen L. Mcintyre

Retrospective Theses and Dissertations

Mono and bimetallic catalysts of varying composition were prepared in order to examine any synergistic effect that may occur by mixing metals on a support. The test reactions were hydrogenation of 1, 3-butadiene and piperylene, a mixture of similar boiling 5-carbon olefins. Catalysts containing ruthenium and rhodium displayed some synergistic effects when supported on silica gel and 13X molecular sieves. The use of 5A molecular sieves as a support was used to examine the feasibility of selective hydrogenation as a separation tool for the piperylene mixture.

I. The Use Of Polyethers As Phase Transfer Catalysts For The Fluoroalkoxylation Of Halogenated Aromatic And Heteroaromatic Systems Ii. The Grignard Addition And Sodium Cyanoborohydride Reduction Of Arylchloropropeniminium Salts, Martin A.M. Moebus

Retrospective Theses and Dissertations

This research addresses two distinct areas of synthetic organic chemistry: the use of phase transfer catalysts for the fluoroalkoxylation of activated haloaromatic and haloheteroaromatic systems, as well as the Grignard addition and sodium cyanoborohydride reduction of aryl chloropropeniminium salts. In Part I of this research, a number of macrocyclic- and linear polytethers were studied as phase transfer catalysts in the nucleophilic aromatic substitution of haloaromitc systems. The most effective catalyst was determined to be poly(ethylene glycol)-8000 and the reaction conditions were optimized for this catalyst. Subsequently isomer reactivity, effects of activating groups, effects of leaving groups, and nucleophiles were studied …

Attenuation Of Infrared Radiation By Diesel Fuel Generated Particle And Droplet Aerosols, Soodabeh Karimi

Retrospective Theses and Dissertations

The object of this project was to explore the absorbance and scattering properties of carbon particle smoke in the infrared and visible regions of the spectrum. Laboratory scale apparatus were developed to produce smoke in the form of carbon particles, droplet aerosols and combinations of the two. These smokes were made from diesel fuel and fog oil.

Thermodynamics And Kinetics Of Aqueous Solution Of Liquid Hydrocarbon Mixtures (Solutes, Petroleum), David Robert. Burris

Dissertations, Theses, and Masters Projects

Two-phase systems of a liquid hydrocarbon mixture, containing medium molecular weight (C(,7)-C(,12)) aromatic and aliphatic hydrocarbons, and water were examined in both equilibrium and kinetic experiments. Knowledge of the aqueous solution behavior of liquid hydrocarbon mixtures is of importance in determining the fate of hydrocarbon components in such systems of an environmental or geologic nature. Solute concentrations were determined by solvent extraction followed by gas chromatography. The equilibrium solute concentration for a given component i (C(,i)) is related to the pure compound solubility (C(,i)('o)), mole fraction of component i in the hydrocarbon phase (x(,i(h))) and the activity coefficient of component …

Acidic And Chemical Properties Of Molten Salt Hydrates, Stephen Keith Franzyshen

Dissertations, Theses, and Masters Projects

No abstract provided.

The Examination Of The Adsorption Capabilities Of The "Magic" Black Rocks Of The Little Missouri River, Denise Leverett

Honors Theses

It has been seen that manganese oxides precipitate from aqueous solution as they pass downstream from cold water release reservoirs. This precipitation is visible in the form of black coatings on gravels in the river or stream bed. These oxide coatings not only cause the further oxidation and precipitation of manganese ions but also have the capacity for adsorbing trace metals from the system. The amount of metal adsorbed varies with the element. This study not only addresses the various elements which may be adsorbed but also the rates at which adsorption occurs and the factors which affect those rates.

Bimetallic Complexes Of Tungsten And Mercury, Zakariah Abdullah

Masters Theses

A tungsten-mercury bimetallic complex [(CO)₄W(PPh₂CH₂CH₂PPh₂)₂HgCl₂]_n has been synthesized from the reaction of trans-(CO)₄W(η¹-PPh₂CH₂CH₂PPh₂)₂ and HgCl₂. The value of n has not been determined due to the insolubility of the complex. The anologous reaction with HgI₂ gave an insoluble, uncharacterizable complex, which best corresponds to (CO)₄W(PPh₂CH₂CH₂PPh₂)₂Hg₂I₄.

The geometry about tungsten in [(CO)_{4 …}

Search For New Membrane Active Substances: Synthesis Of 3-Tropanols With Alkyl, Alkenyl And Alkenynyl Group At The Bridgehead, Ramalinga Murty Dharanipragada

Graduate Theses, Dissertations, and Problem Reports

In recent years, Witkop and coworkers have isolated several structurally unique alkaloids from the colombian frog belonging to the genera Dendrobates. These alkaloids, which occur in the defensive skin secretions of the frog have been found to be highly active venoms as well as mucosal tissue irritants towards both mammals and reptiles. Among them are three important alkaloids histrionicotoxin, isodihydrohistronicotoxin and octahydrohistronicotoxin.

Trans Diequatorially Fused 3',3'-Diphenyl-2'-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Glucose, Julian Guardado Puentes

University of the Pacific Theses and Dissertations

The chemistry of amino sugar compounds has been studied in the last years in connection with the study of natural products, and many of them have been isolated. ^57,17,18 Amino sugars play an important role in biochemistry, forming blocks of homo- and heteropolymers and complex molecules such as microbial polysaccharides, enzymes, gangliosides, glycoproteins, and antibiotics.

This research project had the purpose of preparing a derivative of 2-amino-2-deoxy-D-glucose, with a free hydroxyl group at the anomeric carbon, with the 4,6-positions blocked with the benzylidene cyclic acetal, and the 2,3-positions being blocked by a 3,3-diphenyl-2-morpholinone ring trans diequatorially fused to the amino …