Chemistry Commons^™

Synthesis Of Some N2-Alkyl- And Dialkylsubstituted 2'-Deozyguanosines, Carl D. Carter

Chemistry and Chemical Biology ETDs

Various N²-alkyl- and dialkylsubstituted 2’-deoxyguanosines have been synthesized. After future conversion into nucleotides, these compounds are to be used for incorporation into DNA. The modified DNA is expected to be useful in complexing studies with actinomycin. The presence of the 2-amino group in a purine has earlier been shown to be required for binding of actinomycin. Possible reasons for this requirement are an electronic effect or a precise steric fit involving hydrogen bonding. By comparing the relative stability of the complex formed between actinomycin and modified DNA versus actinomycin and normal DNA a better understanding of the mechanism …

The Synthesis And Reactivity Of Pyrrolopyridazines, Phillip Dan Cook

Chemistry and Chemical Biology ETDs

A new general synthetic sequence and cyclization method was developed which utilizes parts of both the Reissert and Madelung indole cyclization methods and leads to substituted pyrrolo[2,3-d]pyridazines,pyrrolo[3,2-c]-pyridazines, and pyrrolo[2,3-c]pyridazines. Thus, ethyl pyridazinylpyruvatel-oxides substituted with an ethyl formimidate or acetimidate group adjacent to the pyruvate group provides immediate precursors to pyrrolopyridazines. Mild acid hydrolysis of the acylimidate and subsequent cyclodehydration. Parallel to the latter stage of the Reissert indole cyclization method, affords ethyl pyrrolopyridazine carboxylates in high yields. On the other hand, treatment of the acylimidates with base provided ethyl pyrrolopyridazine glyxalates in high yields in a manner similar to the …

Solution Diffusion Coefficients -- New And Improved Methods For Their Determination, Newton C. Fawcett

Chemistry and Chemical Biology ETDs

The previously existing method of determining diffusion coefficients (D values) by diffusion from capillaries is critically reviewed. A differential error analysis of the method is given, and a formula is derived for the upper error bound on D as a function of capillary length, time span of the experiment, and ratio of final to initial diffusant concentrations. It is concluded that when the initial concentration and capillary length are not corrected for convective loss of diffusant solution from the capillary, the errors in concentration and length are additive and can significantly affect the accuracy of D. A new method (the …

The Synthesis Of Imidazo [4, 5-C] Pyridazines And Pyridazino-As-Triazines, Dennis King Chesney

Chemistry and Chemical Biology ETDs

The preparation of the first examples of imidazo[4, 5-c]­pyridazine-2, 7-dithiones is described herein. Several of the S-methyl and S-benzyl derivatives have been prepared and the conditions required for the selective monoalkylation of the 2, 7-dithione have been determined. Several new derivatives of imidazo[4, 5-c]pyridazine and imidazo[4, 5-c]pyridazine-2 or 7-thione are also described. The preparation of several examples of the previously unknown heterocyclic ring systems, 1, 2-dihydropyridazino[4, 5-c]­-as-triazine and 3, 4-dihydropyridazino[4, 3-e]-as-triazine, is described. The preparation, isolation, and structure determination of the products from the reaction of methylamine with 3, 4, 5-tri­chloropyridazine are described. It was found that the reaction of …

The Synthesis Of Pyrimidines And Condensed Pyridazines As Potential Antimetabolites, Judith A. Wagner

Chemistry and Chemical Biology ETDs

Interest in the compounds described by this thesis was first aroused in the early 1930's when a research team began to investigate the mass poisonings of the population in Indonesia. The cause of the poisonings seemed to be the foodstuffs which the people made for themselves from the abundant coconut. Two products in particular, Bongkrek and Semaji, made from coconut presscakes and grated coconut, were apparently the source of the toxic substance. When made under improper conditions, the toxic principle developed in an otherwise harmless food product. A compound was finally isolated and established as the toxic principle by …

New Techniques In Precision Gamma Scanning: Application To Fast Breeder Reactor Fuel Pins, John R. Phillips

Chemistry and Chemical Biology ETDs

A new precision gamma scanning system is described. The system is designed for the thorough, detailed, nondestructive characterization of irradiated fast reactor fuel pins. Gamma scanning data are given for failed fuel pin , transfer mechanisms of fission products, quantitative isotopic scan­ning, and differential burnup profiles.

The system consists of a scanning mechanism for the precise positioning (±0.001 in.) of the irradiated fuel pin, high density tungsten alloy collimators for defining the volume segment from which the gamma-ray spectra are collected, a large high resolution an anticoincidence detector assembly for resolving complex gamma-ray spectra, and a computer con­trolled data acquisition …

Computer Investigation Of The Variation Of Conductivity With Concentration, Larry Macpeers Shadwick

Masters Theses

Computer programs were developed tor the conductance equations of R. M. Fuoss and L. Onsager as well as for the conductance equations of T. J. Murphy and E. G. D. Cohen. These programs were used to calculate values from selected conductance measurements. The resulting values were compared with values produced by other computer programs using the equations of Fuoss and Onsager as well as the equations of E. Pitts. The comparisons demonstrated the equations of Murphy and Cohen to be the equal of or superior to the other equations for the majority of cases. The equations of Pitta were superior …

The Conductance Of Some Polyvalent Electrolytes, Jack Lee Worthington

Masters Theses

A new compound, 1,3,5-triphenylbenzene-4' ,4",4"'-trisulfonic acid, was synthesized by treating triphenylbenzene in 1,2-dichloroethane with chlorosulfonic acid. The reaction appears to be quantitative. Conductance measurements were then made on the sodium, potassium, and lanthanum salts of this new acid and of 1,3,5-benzenetrisulfonic acid.

The choice of these acids was based on two factors: 1) the desire to prepare a 3-3 symmetrical unassociated electrolyte which would allow the determination of a more reliable equivalent ionic conductance value for La³⁺ and 2) an interest in using the Murphy-Cohen equation to determine solute parameters such as association constants if association is present.

Conductance …

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 …

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 …

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 …

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 …

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 …

The Mechanism Of The Reaction Of Lead(Iv) Acetate, Thallium(Iii) Acetate And Mercury(Ii) Acetate With Ketones, Su Hsiung Tsung

Masters Theses

No abstract provided.

The Conductance Of Some Non-Rigid Bolaform Electrolytes, William Terry Schmidt

Masters Theses

Bolaform electrolytes are those which contain two or more charges separated by an inert framework. These are intermediate in structure between simple electrolytes and polyelectrolytes. Since these are similar to both synthetic and biological electrolytes, this investigation has been undertaken to determine some of their properties in solution.

The sodium and magnesium salts of ethane, propane, butane, pentane, hexane and decane α,ω-disulfonates were prepared. Each acid was prepared by refluxing the α,ω-dibromide of the desired salt with sodium sulfite. The sodium and magnesium salts were prepared by ion-exchange techniques.

The conductance of each salt was determined in methanol utilizing the …

On The Mechanism Of The Diels-Alder Reaction--Dimerization Of Trans-Phenylbutadiene, Michael Ward Mcnicholas

Dissertations and Theses

The Diels-Alder dimerization of trans-1-substituted butadienes is expected to yield a cyclohexene adduct with the substituents in the 3 and 4 positions cis to one another. This prediction is based on past observations of other Diels-Alder additions. The cis-isomer is the only one consistent with a two-stage mechanism proposed by Woodward and Katz.

In the case of trans-phenylbutadiene, the expected adduct is cis-3-phenyl 1-4-(trans-styry1) cyclohexene. Alder, Haydn and Vogt, however, reported that the corresponding trans-isomer is the dimerization product. There is reason to believe that the observation of the trans-isomer may have been the result of product isomerization during purification. …

A Kinetic Analysis Of The Iodination Of Pyruvic Acid And Pyruvate Esters, Mohamed M. Fahmi Hegazi

All Master's Theses

In the present work the relative rates of iodination of pyruvic acid and ethyl and methyl pyruvate have been compared at 25.0° C. These studies allow the determination of the respective free energies of activation for these processes. Measurements have also been carried out at various temperatures to determine the enthalpies and entropies of activation for the spontaneous and base catalysed iodinations of these pyruvate systems. The present thesis also includes a comparison of the solvent deuterium isotope effects associated with the spontaneous rate of iodination of pyruvic acid and the alkyl pyruvates. Also, the catalytic rate coefficients associated with …

Analytical Aspects Of Laser-Induced Degradation Of Organic And Inorganic Compounds, William T. Ristau

Chemistry and Chemical Biology ETDs

The rapid deposition of energy by means of a pulsed ruby laser to degrade organic and inorganic materials is investigated as an analytical tool. Advantages and disadvantages of using a laser are discussed and compared to current conventional pyrolysis methods. The interaction of laser radiation with matter is briefly discussed. A number of different organic compounds including saturated and aromatic hydrocarbons, heterocyclic compounds, and polymers have been studied. The degradation products were separated and identified by use of a gas chromatograph. Degradation studies have also been done on a series of inorganic salts including nitrates, sulfates, thiosulfates, and oxalates. The …

The Synthesis Of Some New Condensed Pyridazines, Pyridazine N-Oxides And Pyrimidines As Potential Chemotherapeutic Agents, Donald E. Pichler

Chemistry and Chemical Biology ETDs

The need for new antimicrobial and antifungal agents as well as medicinals possessing antiprotozoal activity against special strains of malaria resistant to most synthetic antimalarials prompted the synthesis of new compounds that may have the desired antimetabolite properties. The structural similarities of the 1,2,5-thiadiazolo[3,4-d] pyridazines and the v-triazolo[4,5-d]pyridazines with the biologically important purines prompted the synthesis of members of these ring systems. The 1,2,5-thiadiazoles synthesized as intermediates ware also screened as potential chemotherapeutic agents. Similarly, the pyridazine N-oxides and the 5-nitro substituted pyrimidines are structurally similar to the pyrazine N-oxides and the pyridine N-oxides, which are known to possess a …

Analytical And Other Applications Of Some Quaternary Ammonium Compounds, Robert Grant Dosch

Chemistry and Chemical Biology ETDs

Analytical and other applications of some quaternary ammonium compounds were studied. Conditions are described for the quantitative determination of perchlorate by precipitation as tetra-n-pentylammonium perchlorate. Results of qualitative studies of interferences from other anions and quantitative studies on the separation and determination of perchlorate in the presence of chlorate are presented. With careful work, relative errors of ± 0.2% can be expected in the range of 50-100 mg of perchlorate, ± 1.0% in the 10-50 mg range, and ± 5.0% in the range from 2-10 mg of perchlorate. A method is described for the separation and determination of Ta in …

A Theoretical Analysis Of The Electronic States Of 2nd And 3rd Row Transition-Metal Complexes;-A Spectroscopic Investigation Of D5 And D6 Systems, Howard James Clifford

Chemistry and Chemical Biology ETDs

A theoretical and experimental investigation of a number of transition-metal complexes was conducted. The compounds of primary interest were six-coordinated complexes containing group VIII metal ions belonging to the second and third transition series. The investigation involved the synthesis and purification of the compounds, the measurement of absorption and emission spectra and luminescent lifetimes, and the analysis of the observed spectral properties using a crystal-field model based on solutions of large secular determinants. The effects of variations of the Racah parameters on the energy­level diagrams of dⁿ ions (n = 2, 3, ... , 8) in an octahedral crystal …

Optical Studies Of Metal- Semiconductor Transmutations Produced By Intercalation, Juana Vivó Acrivos, Y. Liang, J. Wilson, A. Yoffe

Faculty Publications, Chemistry

Spectra of the alkali metal intercalation products of MoS2 and NbSc2 arc interpreted in terms of a previously published band model.

Liquid Scintillators. The Photooxidation Of 2,5-Diphenyloxazole, Margaret E. Ackerman

Chemistry and Chemical Biology ETDs

Mackay had found that prolonged ultraviolet irradiation of solutions of 2,5-diphenyloxazole (PPO) (1) in toluene resulted in the formation of an insoluble crystalline product 2 which accumulated above the meniscus; the formation of 2 was dependent upon the presence of dissolved oxygen and water in the solutions. The Compound 2 was not a simple degradation product of PPO (1); elemental analysis was compatible with the empirical formula C₂₂H₁₇O₅N and the thermal decomposition of 2 gave equal molar amounts of carbon monoxide, benzoic acid, and dibenzamide. The study described in this dissertation was initiated to …

A Quantum Mechanical Investigation Of The Heh3+ Energy Surface, Merle J. Benson

Chemistry and Chemical Biology ETDs

An all-electron ab-initio calculation of the energy surface for the reaction He+ H⁺₃ → HeH⁺ + H₂ was performed using a 9slp gaussian basis set for helium and a 4slp gaussian basis for hydrogen. Reaction paths calculated were of C_2V, C_S, and C_3V symmetry. The lowest energy configuration was found with the molecule in C_2V symmetry with the three hydrogen atoms in an equilateral triangle of side length 1.64 a.u. with the helium atom 3.85283 a.u. from an apex of the triangle. The molecule was found to remain in C …

Effects Of Hydrocarbon Chain Length On The Thermodynamics Of Formation Of Bis(N-Alkylamino)-Silver (I) Complex Ions, Don J. Temer

Chemistry and Chemical Biology ETDs

As part of a comprehensive study of the thermodynamics of conformational changes of n-alkyl groups in aqueous solution, the equilibrium constants, enthalpy changes, and entropy changes have been measured for the stepwise formation of bis(n-alkylamino)silver(I) complex ions at 25° in dilute aqueous solution. The attachment of the charged Ag⁺ to the end of the amine molecule is thought to cause changes in the conformation of the n-alkyl chain. The effects of these conformational changes on the formation constants, enthalpy changes, and entropy changes of the Ag⁺ complexes are discussed and compared with the effects on the formation constants, …

Molecular Luminescence From Turhenium, Osmium, And Terbium Chelates: 2°K To 300°K, Raymond William Harrigan

Chemistry and Chemical Biology ETDs

Two experimental spectroscopic investigations spanning the temperature range 300°K to 2°K were carried out on molecular complexes. The nature of charge-transfer phenomena in transition-metal chelates was studied extensively, and the thermal quenching of the luminescence of terbium (III) chelates was briefly investigated. The experimental methods employed were absorption and luminescence spectroscopy including photoflash excitation for studying transient luminescence decays. Measurements were performed on three osmium and three ruthenium complexes, all containing bidentate or tridentate heterocyclic aromatics as ligands. The compounds were studied in rigid solvent glasses, in poly(methyl methacrylate) (PMM), in an isomorphic host of tris(2, 2'-bipyridine)zinc(II) sulfate, and in …

The Synthesis Of Some New Azabenzo[A]Pyrene And Monomethyl Azabenzo[A]Pyrene Derivatives, Richard E. Phillips

Chemistry and Chemical Biology ETDs

The synthesis of six new azabenzo[a]pyrenes was undertaken in order that the carcinogenic and carcinostatic properties of these com­pounds might be tested. The compounds thus synthesized were 4-aza­ benzo[a]pyrene (1), 5-methyl-4-azabenzo[a]pyrene (2), 12-azabenzo[a]­pyrene (3), 11-methyl-12-azabenzo [a]pyrene (4),5 -azabenzo [a]pyrene (5), and 4-methy1-5-azabenzo[a]pyrene (6).

Compounds 1 and 2 were prepared from the intermediate 4-keto-1,2,3,4-tctrahydrochrysene. The azine from this ketone was dehydro­genated and the resulting aromatic amine was both formylated and acetylated. The amides were cyclized with polyphosphoric acid in a Bischler-Napieralski cyclodchydration giving fair yields of 1 and 2. The synthesis of compounds 3 and 4 was carried out in a …

Paths Of Energy Degradation In Transition Metal Complexes, James N. Demas

Chemistry and Chemical Biology ETDs

To elucidate the paths and rates of energy degradation in transition-metal complexes following photoexcitation, a comprehensive experimental study was carried out on a total of fourteen complexes of Ru(II), Os(II), Ir(III), and Rh(III). Photoluminescence lifetimes, spectra, wavelength dependences of the quantum yields, and absolute quantum yields were determined. The complexes all contained organic ligands—pyridine, 2, 2’bypyridine, 2, 2’ 2”-terpyridine, and 1, 10-phenanthroline. The ruthenium, osmium, and iridium complexes all exhibited charge transfer (CT) phosphorescences with quantum yields of 1-60% and lifetimes of 0.6-11 µsec in an alcoholic glass at 77°K. The rhodium complexes gave d-d* phosphorescences with yields in the …

The Control Of Algae, G R W Meadly

Journal of the Department of Agriculture, Western Australia, Series 4

CONDITIONS in areas of still, stored water in Western Australia can easily become ideal for the development of algae and control measures may become necessary in farm dams and swimming pools.

Thermodynamics Of Proton Ionization In Dilute Aqueous Solution At 25°, Ernest J. Baca Jr.

Chemistry and Chemical Biology ETDs

This dissertation consists of four studies and is divided into five parts. Part I contains a description of the calculations and equipment used for these four studies.

Part II is a study of tris(hydroxymethyl)nminomethane (THAM) for use as a standard in solution calorimetry. The heat of solution of THAM in 0.100 M HCL was determined at 25°.

Part III is a study of the thermodynamics of proton ionization

from some unsaturated, five membered, nitrogen ring compounds in dilute aqueous solution at 25°. Values of deltaK, pK and deltaS are reported for 1,2,3-triazole, benzotriazole, 4,5-dibromo-1,2,3-triazole, 1-phenyl- 5-methyl-1, 2, 3-triazole-4-carboxylic acid, …