Chemistry Commons^™

Analysis Of Coal Fractions Using Dibromotriphenyl-Phosphorane: A Selective Ether Cleaving Reagent, Michael L. Ballard

Masters Theses

Dibromotriphenylphosphorane (DTP), in acetonitrile at 40°C, was found to cleave benzyl phenyl ether in preference to di-alkyl or other aryl alkyl ethers. Competition between 10 mmoles benzyl phenyl ether and 10 mmoles di-n-octyl ether for 0.92 mmole of DTP gave 48% cleavage of benzyl phenyl ether and 1.3% cleavage of di-n-octyl ether based on DTP. Reaction of benzyl phenyl ether and di-n-octyl ether separately with DTP at 40°C produced 80% and 8% cleavage, respectively. Reactions of DTP with diphenyl ether, butyl phenyl ether, phenyl cyclohexyl ether and benzyl benzoate at 40°C produced less than 3% cleavage in all cases.

Reaction …

Cis Labilization: A Study Of The Reactions Of Group 6 Pentacarbonyl Phosphido Anions, Matthew J. Madigan

Masters Theses

The synthesis of cis-(OC)₄M(PPh₂H)L (M=Cr,Mo,W; L=PPh₃,PPh₂Et,PPhEt₂,PEt₃) can be achieved by treating (OC)₅MPPh₂H with potassium tert-butoxide in the presence of L. […] The products are easily isolated and are not contaminated with trans isomers. Obtained as a minor product is [(OC)₄MPPh₂]₂.

The reaction of (OC)₅WPPh₂H with potassium tert-butoxide generates [(OC)₅WPPh₂]^- which reacts with (OC)₅WPPh₂H to give [(OC)₅WPPh₂W(CO)₅] …

A Column For The High Pressure Liquid Chromatography Of Some Potentially Hazardous Metal Ions, Stephen R. Friebe

Masters Theses

No abstract provided.

Synthesis And Reactivity Of Some Fe(0) And Ru(0) Compounds, Michael E. Hawkins

Masters Theses

The catalytic activity of the compounds used in this study, Ru[P(C₆H₅)₃]₄ (η²-CH₃CN)⋅CH₃CN, Ru(CO)[P(C₆H₅)₃]₃CH₃CN, Ru(CO)₂[P(C₆H₅)₃]₃, Fe(CO)₂[P(C₆H₅)₃]₃ was compared using the isomerization of allylbenzene to β-methylstyrene as the test reaction. The measured decreasing order of reactivity for these complexes is: Ru(CO)[P(C₆H₅)₃]₃CH₃CN > Ru[P(C₆H₅)₃]₄ (η …

A Numerical Method For The Solution Of The Schrödinger Equation By A Trial Wavefunction Improvement Formula, Chun-Sheng Ko

Masters Theses

A numerical method and corresponding computer algorithm for solving the one-dimensional radial Schrödinger equation to any desired accuracy is developed. The method uses a finite difference scheme in which an initial trial wavefunction is digitalized over a lattice covering the region of integration. The values of a rough solution are then altered at each lattice point by a simple improvement formula decreasing the value of the variational energy until the desired minimum is reached. The accuracy of these solutions depends only on the grid size. This method is characterized and tested with a harmonic oscillator potential. Practical evaluations and applications …

Analysis Of Mixtures Of Chlorine, Chlorine Dioxide And Chlorite, Ying-Chien Chu

Masters Theses

No abstract provided.

Kinetic Study Of The Formation Of Mixed Ligand Complexes Formed From Triethylenetetramine Nickel (Ii) And Bidentate Ligands, Burtrand Insung Lee

Masters Theses

No abstract provided.

Photon Counting System For The Determination Of Creatine Phosphokinase, Steven E. Dueball

Masters Theses

No abstract provided.

Preparation Of N,N-Dimethylhydrazones And 1,1-Dimethylpyrazolium-5-Oxides, Tso-Ping Li

Masters Theses

The purpose of this study was to prepare the 1,1-dimethylpyrazolium-5-oxides from a variety of N,N-dimethylhydrazones which can be prepared from the corresponding β-ketoesters.

Substitution of a methyl group at α-position of β-ketoesters makes the formation of N,N-dimethylhydrazones more difficult. The electron-withdrawing group (-NO₂) and the electron-releasing group (-OCH₃) as a parasubstituent of the benzene ring have the electrostatic effect to the nucleophilic attack of dimethylhydrazine to form the N,N-dimethylhydrazones.

It was found that N,N-dimethylhydrazones exist as a mixture of keto and enol tautomers based on the ir and nmr spectra. A semiquantitative analysis of the tautomerism …

Structural Effects On Micellar Catalyzed Reaction Of Hydroxamic Acids, Nop Utrapiromsuk

Masters Theses

Introduction

For many years scientists have tried to find a model which resembles a biological system, so that they can use this model for studying biological systems in human and in living organisms. Micelle systems provide the environment to mimic enzyme systems to some degree.¹

Soaps and detergents generate micelles. Soaps and detergents have been used as cleansing agents for a long time. Their cleansing properties are related to micelle formation. Actually, soap is simply a mixture of sodium salts of long chain fatty acids, R-COO^- Na⁺, and some detergents are general sodium salts of straight …

The Unexpected Preferential Formation Of 1-Alkyl-1-Phenyl-2–Propanones On Monoalkylation Of The 1-Phenyl-2-Propanone Dianion, Jack M. Hinkley

Masters Theses

No abstract provided.

The Effects Of Electron-Donating And Electron-Withdrawing Groups On The Alkylation Sites Of Para-Substituted Phenylacetones, Abraham L. Faburada

Masters Theses

The dianions of phenylacetone and its para-substituted derivatives were generated using potassium hydride and n-butyl lithium in tetrahydrofuran. Methyl, ethyl, and n-butyl iodides were used to alkylate the dianions. The results of alkulation indicated that C₁ is preferentially attacked by the less active ethyl and n-butyl iodides. The results further show that terminal alkylation is enhanced by electron-donating groups at the para-position of the phenyl ring. The results are rationalized in terms of the difference in electron density at C₁ and at C₃ in the dianion, on the basis of resonance theory. The regio-selectivity of alkylation as …

The Analysis Of N-Methylscopolamine Bromide By High Speed Ion Pair Partition Chromatography, John L. Nappier

Masters Theses

No abstract provided.

The Response Of The Micro-Adsorption Detector To Inorganic Anions, Maria E. Munera

Masters Theses

No abstract provided.

Amperometric Determination Of Chemical Oxygen Demand, Catherine Eckert Hutchins

Masters Theses

A method is described for measuring the low level --5 to 50 ppm-- chemical oxygen demand (COD) of water samples by amperometric titration. The method involves digestion of the sample with potassium dichromate in a 50% sulfuric acid solution using one-fifth the reagents and sample required for the standard COD method. This is followed by an amperometric titration using a standard ferrous ammonium sulfate solution and employing a rotating platinum electrode in a three-electrode potentiostatic system. The titration is carried out at a potential of +0.80 volts versus a saturated calomel electrode, thus eliminating the need for O₂ purging …

Ergosterol Effect On The Desaturation Of 14c-Cis-Vaccenate In Tetrahymena, Tiee-Chyau Miin

Masters Theses

Supplement of ergosterol to the growth medium of the ciliated protozoan Tetrahymena pyriformis W leads to incorporation of the foreign sterol within cell membranes and suppression of synthesis of the native sterol-like compound tetrahymanol, as well as to changes in the fatty acid compositions of several major classes of membrane lipid. Alteration of fatty acid composition is thought to represent a regulatory mechanism whereby optimum membrane fluidity is maintained when the slightly dissimilar foreign sterol is added into the phospholipid bilayer of the membranes.

The present study, using several different conditions of growth temperature, substrate concentrations and incubation time, and …

The Synthesis And Characterization Of Several Copper (Ii) Complexes Of Quinuclidinone-Containing Ligands. Possible Models For Type I Copper Blue Proteins., Victor Thomas Wilcox

Masters Theses

Several copper (II) complexes with bidentate quinuclidinone containing ligands have been synthesized and characterized. These complexes appear to be possible models for the type I copper (II) in the copper "blue" proteins. The spectral and magnetic properties indicate that the complexes have a pseudo tetrahedral microsymrnetry about the central metal ion. The complexes contain chromophores of the following forms: CuN₄, CuN₂O₂, and CuN₂x₂, where X is either Cl or Br. While the spectra of these complexes lack the intense 17,000 cm^-1 band typical of copper "blue" proteins, the optical …

Thermodynamics Of Ion Association In Aqueous Solutions Of Sodium Sulfate, Sodium Carbonate And Sodium Bicarbonate, Yan-Chun Chung

Masters Theses

Stoichiometric association constants of NaSO₄^-, NaCO₃^- and NaHCO₃^- ion-pairs were determined over the temperature range 10 - 40°C at several ionic strengths by using a sodium ion selective electrode. At zero ionic strength values for K°_A,NaSO₄^- are 15.8 ± .4, 8.5 ± .2 and 4.6 ± .3 at 10°, 25° and 40°C, respectively; like values for K°_A,NaCO₃^- are 17.1 ± 1.4, 19.1 ± .6 and 21.0 ± .7. Values for K°_A,NaHCO₃° are 3.35 ± .07 and 6.75 ± .02 at 25°C …

Ditertiary Phosphines As Monodentate Ligands In Transition Metal Carbonyl Complexes, Yih-Yau York Sun

Masters Theses

Carbonyl complexes of chromium, molybdenum and tungsten have been synthesized in which two potentially chelating tetraphenyldiphosphinoethane molecules (Ph₂PCH₂CH₂PPh₂) are bound as monodentate ligands. The reaction of trans-(CO)₄M(PPh₂CH=CH₂)₂ (M = Cr, Mo, W) with diphenylphosphine (PPh₂H) in the presence of potassium t-butoxide yields trans-(CO)₄M(PPh₂CH₂CH₂PPh₂)₂. The complexes, which represent the first of this type to be synthesized, have been characterized by ³¹P nmr. From the XAA'X' phosphorus-31 spectra of the …

The Preparation And Study Of Some Bridged Tropones, Sultan T. Abu-Orabi

Masters Theses

No abstract provided.

Studies Toward The Total Synthesis Of A Colchicine Analog, Jacob Shya Tou

Masters Theses

No abstract provided.

Side-Chain Metalations Of Certain Dimethylpyridines By Means Of Organoalkali Metal Reagents, Stephen Bendzunas

Masters Theses

No abstract provided.

Unusual Alkylations Of The 1,1-Diphenyl-2-Propanone Dianion, Ruth E. Tenbrink

Masters Theses

No abstract provided.

The Synthesis And Study Of The Enolate Monoanion Of 2, 4-Di-P-Anisylbicyclo(3.2.1)Oct-6-En-3-One, Phillip D. Reynhout

Masters Theses

No abstract provided.

The Synthesis And Physical Properties Of Some 1-Methyl And 2-Methyl Bridged Cycloheptapyrazolones, Gary R. Larson

Masters Theses

No abstract provided.

Reactions Of 1-Bromo-2-(P-Tolyl)Cyclopropane With Nucleophiles In The Presence Of Crown Ether, Gerald Mccomas

Masters Theses

Reactions of 1-bromo-2-(p-tolyl)cyclopropane with potassium acetate in the presence of crown ether in various solvents (DMSO, t-butanol, and toluene) have been examined. No cyclopropyl products were observed, only ring-opened p-methylsinnamyl acetates. The trans 1-bromo-2-(p-tolyl)cyclopropane isomer reacts about 3.8 times faster than the cis isomer in DMSO, but only about 1.5 times faster in t-butanol, seemingly related to solvation factors in the transition state. Although stability studies indicated that p-methylcinnamyl bromide might be an intermediate, the rate of formation of this compound in the absence of potassium acetate was much lower than rate of product formation even in the presence of …

Stability Constants Of Naco3-, Naso4- And Kco3- In Water At 25°C, Frank Dennis Blum

Masters Theses

A new method for determining ion association constants in aqueous solutions using ion selective electrodes has been developed. This method has been applied to the NaCO₃^-, NaSO₄^- and KCO₃^- ion pairs at 25°C. Association constants for NaCO₃^- and NaSO₄^- were determined at various ionic strengths and extrapolated to zero ionic strength to yield 2.2 ± 0.2 for NaCO₃^- and 5.3 ± 0.4 for NaSO₄^-. Values for the association constants at an ionic strength near sea water (I=0.70) were calculated to be 1.7 ± 0.1 …

Part I. Thermodynamic Acidities Of Substituted Phenylacetylenes. Part Ii. Mercury Accumulation In Trout Of Southern Missouri, Eric T. Lloyd

Masters Theses

"PART I: THERMODYNAMIC ACIDITIES OF SUBSTITUTED PHENYLACETYLENES The thermodynamic acidities (pKa) of phenylacetylene and several para substituted phenylacetylenes in methanol were determined at 25ºC. These acidity constants were determined using a quenching technique which involves converting the phenylacetylenic anion, present at equilibrium as sodium phenylacetylide, to the tritium labelled carbon acid. By liquid scintillation counting techniques, the concentration of the anion was determined and the pKa of the phenylacetylene compound calculated. The resulting pKa's are: p-nitrophenylacetylene, 17.98, p-bromophenylacetylene, 18.10, p-fluorophenylacetylene, 18.14, phenylacetylene, 18.50, and p-methylphenylacetylene, 18.60. The effect of a substituent in the para position on the relative acidities is …

A Study Of The Spectroscopic, Thermodynamic, And Dielectric Properties Of The T-Butylbenzene/Tetracyanoethylene Molecular Complex, Donald W. Mundell

Masters Theses

No abstract provided.

Kinetics Of The Thermal Decomposition Of Pyridine, Tesfaye Biftu

Masters Theses

No abstract provided.