Physical Sciences and Mathematics Commons^™

The Synthesis And Decomposition Of O-Substituted Phenylhydroxylamines, Helen Carol Kennicott

Honors Theses

0-(phenyl)hydroxylamine and its p-nitrated derivative were synthesized for use in a study of substitution reactions at an sp3 hybridized nitrogen atom. The 0-(phenyl)hydroxylamine was decomposed thermally in several nonnucleophilic solvents and in water, with base present. It is proposed that in organic solvents, the decomposition proceeds by a radical mechanism involving a solvent cage intermediate. Ammonia and aminophenols are the major products. In water, it appears that an SN1 reaction producing phenoxide may compete with the radical mechanism.

The Synthesis Of 2, 11-Dithiabenzo - [3.3] - Paracyclophane And An Octadeutero Derivative, Paul M. Begley

Honors Theses

The purpose of this work was the synthesis of 2, 11 -dithia-benzo- [3.3] -paracyclophane and its octadeutero derivative 2,11-dithia- 3,3, 5, 6, 8, 9, 10, 10-octa­deutero-benzo - [3.3] paracyclophane. A comparison of their nuclear magnetic resonance spectra as well as their mass spectra will unequivocably provide proof of their successful synthesis.

Ozone Complexes With Substituted Aromatic Compounds, David C. Eaton

Honors Theses

Ozone has been observed to complex with aromatic compounds at low temperatures. The ability of an aromatic system to complex with ozone appears to be due to the inductive effect of the substituent on the pi system. The experimental work was done in the solid phase at temperatures of -175° C to -186° C. Under these conditions all the substituted aromatics with electron withdrawing groups did not complex including benzene. The complexes are highly colored. To insure the reversibility of the pi complex, infrared spectra were taken of some of the aromatic species before and after complexing.

A Facile One Step Synthesis Of Some New 2-Hydroxy-4,6-Bis Aryl S-Triazines And Related Compounds, Howard Steven Grossberg

Honors Theses

In the past few years the symmetrical triazines have developed extreme importance in biochemical research as well as importance in industrial applications. In our research we have developed a facile, one-step synthesis of a number of 2-hydroxy-4, 6-bis aryl symmetrical triazines based upon the addition of the anion of urea and an aromatic nitrile, with the aryl group including a number of halogenated benzenes, pyridine, or benzene itself. The structure of these compounds had been proved by microanalysis and by both infra-red and mass spectroscopy. The further versatility of the synthesis has also been explored, and by replacing the urea …

The Preparation And Kinetic Studies Of Two Sterically Hindered Gold (Iii) Complexes, James Forrest Stevens

Honors Theses

Previous studies indicate substitution of bromide ion for chloride ion in [Au(Et4dien~H)c.i] +occurs at a rate almost independent of the bromide ion concentration, while similar reactions with [Au(dien-H)Cl]+, [Au(Me2dien-H)c!]+ and [Au(Me4dien-H)c~+ show rates dependent on bromide ion concentration as usually encountered for square planar complexes. There is retardation of the reaction by steric and electronic effects with increased N-alkyl substitution of the triamine. It has also been postulated that substitution of [Au(Et2dien-H)cJ]+ proceeds via a ring-opening mechanism. The purpose of this research was to study further the effect of steric hindrance on rates of substitution of two additional gold(III) complexes. …

Effect Of Solvent Polarity On The Singlet-Triplet Energy Gap Of Methyl-2-Anthroate, William Gregg Hawkins

Honors Theses

Nonradiative processes cause the fluorescence quantum yield to be less than one. Elucidation of nonradiative decay mechanisms without knowing the location of triplet states is difficult. Determination of the fluorescence quantum yield (Øf) as a function of temperature can provide valuable information about relative location of triplet states and the nonradiative processes which result from having a triplet near the energy of the first excited singlet state. Methyl-2-anthroate is very sensitive to solvent polarity. The Øf values and S1 energies vary greatly, depending on the solvent environment. Temperature studies on Øf have indicated the intersystem crossing (ISC) to a nearby …

Photochemistry Of Beta-Methyl-Beta-Nitrostyrene And Its Derivatives, Mohammad Z. Kassaee

Masters Theses & Specialist Projects

o-CH₃, o-CH₃O, m-CH₃O and p-CF₃-β-methyl- β-nitrostyrene (compounds not previously reported) were synthesized using the method of Lappin¹³ and Robertson.¹⁴ These styrenes were irradiated in the U.V. region. The yield of corresponding oximes varied from 85 to 100% in aqueous ethanol. This variation in yield of the oximes was attributed to the effect of the substituent on the phenyl rings of the corresponding styrenes. Electron donating substituents promoted the nitro-nitrite rearrangement and electron-withdrawing groups inhibited this rearrangement. A mechanism is proposed for this reaction which unifies and includes ideas proposed by …

Some New Metallocenes, Larry Warfield

Masters Theses & Specialist Projects

The synthesis and characterization of some new metallocenes is discussed. These organometallic compounds contain some of the first reported pi-complexes between an aromatic ylid, triphenylphosphoniumcyclopentadienvlide. and some transition metals.

Also reported is the synthesis of some new mercury halide metallocenes involving dimethylsulfoniumcyclopentadienylide as the sigma bonded organic substrate.

Effect Of Angular Momentum On The Relaxation Time In A Multicomponent Gas Mixture, Louis Biolsi Jr.

Chemistry Faculty Research & Creative Works

The effects of molecular angular momentum (spin polarization) on the bulk viscosity and relaxation time in a multicomponent gas mixture are considered. Formal theoretical results are obtained, using the Wang Chang-Uhlenbeck approach to the kinetic theory of gases with internal states. The results are given in terms of integrals over the weighted quantum mechanical degeneracy averaged cross section.

New Applications Of The Mannich Reaction, Yu-Fang Wang

Masters Theses & Specialist Projects

French chemists found that the reaction of trifluoroacetic anhydride with the N-oxide of trimethlyamine leads to the methylenedimethylimmonium trifluoroacetate. This salt is considered to be the actual reagent in the Mannich reaction conducted with dimethylamine and formaldehyde. Indeed use of this salt gives higher yields than those obtained via the classical Mannich procedure. This salt could be distilled under vacuum (5 x 10^-2 mm) and reacted with phenylmagnesium bromide to give an 80% yield of benzyldimethylamine. The trimethlsilyl ethers of ketones were employed as intermediates and exhibited regioselectively. For unsymmetrical ketones, the more stable enol was formed thermodynamically and …

Preparations And Reactions Of Two Aldoketenes: T-Butyl And Benzyl, Donna E. Loeffler

Chemistry Honors Papers

This 25 page thesis examines preparations and reactions of aldoketenes.

An Inexpensive Differential Thermal Analyzer: Construction, Qualitative And Quantitative Applications, Kenneth T. Miller

Chemistry Honors Papers

This 33 page thesis examines the process of constructing an inexpensive, versatile differential thermal analysis instrument which can be easily modified and adapted to many applications.

The Chemistry Of Chromium (Vi) And Chromium (V) Oxide Fluorides, Patrick Jay Green

Dissertations and Theses

New preparative routes to chromyl fluoride were sought. It was found that chlorine monofluoride reacts with chromium trioxide and chromyl chloride to produce chromyl fluoride. Attempts were made to define a mechanism for the reaction of ClF and Cr0₃ in light of by-products observed and previous investigations. Carbonyl fluoride and chromium trioxide react to form chromyl fluoride and carbon dioxide. A mechanism was also proposed for this reaction. Chromium trioxide with MoF₆ or WF₆ reacts to produce chromyl fluoride and the respective oxide tetrafluoride.

The Synthesis Of Analogs Of Toxoflavin And Fervenulin As Potential Antimetabolites, Bernadette Kuo Billings

Theses and Dissertations

The synthesis of analogs of toxoflavin: 1,3,4,6-tetramethyl-1,5,6, 7-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 1,6-dimethyl-3,4-diphenyl-1,5,6,7-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 3,5,7-trimethyl-8-phenyl-2,3,4,8-tetrahydropyrido[2,3-d]-2,4-pyrimidinedione are discussed. The synthesis of analogs of fervenulin: 3,4,6-trimethyl-5,6,7,8-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 6-methyl-3,4-diphenyl-5,6,7,8-tetrahydropyrimido[4,5-c]-5,7-pyridazinedione; 2-hydroxy-3,5,7-trimethyl-4(3H)pyrido[2,3-d]-2,4-pyrimidinone are discussed. Several intermediates have been prepared: 6 -methylamino-3-methyluracil by a new method; 6-n-propylamino-3-methyluracil: 6-n-butylamino-3-methyluracil and 3-ethyl-2-ethylthio-2-hydroxy-4(3H)pyrimidinone.

Hard And Soft Nucleophilic Substitution Patterns In Amino-Methylsulfonylazines, Calvin Wilson Mccausland

Theses and Dissertations

The selectivity observed with 2,4,7-triamino-6-methylsulfonyl-pteridine when reacted with "hard" aliphatic amines and "soft" aryl-thiols resulting in amine exchange at the 2-, 4-, and 7-positions and displacement of the 6-methylsulfonyl moiety, respectively, was further investigated in other ring systems. The substrates tested were disubstituted with amino- and methylsulfonyl- moieties, and included the benzene, pyridine, pyrazine, quinoxaline, quinazoline and pteridine ring systems. The methylsulfonyl moiety is preferentially displaced by both thiols and amines with quinoxaline and quinazoline substrates, and is more reactive towards displacement by thiol than amine nucleophiles. Amine exchange occurs with the quinoxaline substrate subsequent to displacement of the methylsulfonyl …

A Systems Study Of Oil Pollution Abatement And Control For Portland Inner And Outer Harbor, Casco Bay, Maine, Arthur D. Little, Inc.

Maine Collection

A Systems Study of Oil Pollution Abatement and Control for Portland Inner and Outer Harbor, Casco Bay, Maine

to State of Maine, Department of Environmental Protection, State House Augusta, Maine 04330

Appropriation Number 4320-4001

by Arthur D. Little, Incorporated, 20 Acorn Park, Cambridge, Massachusetts 02140 (March 15, 1976).

Contents: Executive Summary / 1. Introduction / 2. Identification of Vulnerable Resources / 3. Potential Oil Spill Locations / 4. Oil Spill Movement / 5. Containment and Disposal Systems / 6. Oil Monitoring Systems / 7. Marine Navigation In Portland Inner and Outer Harbors / Appendices

Van Der Waals Interactions Of Carbon Monoxide, Gregory A. Parker, Russell T. Pack

Faculty Publications

Pade approximant methods and experimental frequency dependent polarizabilities are used to calculate reliable van der Waals C6 coefficients for the interaction of CO with He, Ne, Ar, Kr, Xe, H, Li, Na, K, Rb, Cs, H2, N2, O2, CO2, and CO. Error bounds are given for the C6 coefficients and for the CO oscillator strength sums.

Van Der Waals Interactions Of Ii-State Linear Molecules With Atoms. C6 For No(X 2Π) Interactions, Glen C. Nielson, Gregory A. Parker, Russell T. Pack

Faculty Publications

Formulas are derived for the van der Waals Cn coefficients for the interaction of a diatomic molecule in a II electronic state with an S-state atom. Two triatomic states arise from the degenerate IIstate. The average of the two energies has the usual Legendre polynomial (PL) angular dependence, but the difference in energies of the two states is shown to have associated Legendre polynomial (PML with M=2) angular dependence. Procedures for including spin orbit coupling are included, and the extension to interactions of Delta- and Phi-state molecules is discussed. Values of the spherical part of the C6 coefficients for the …

Comment On ''Inelastic Scattering In Atom-Diatomic Molecule Collisions. I. Rotational Transitions In The Sudden Approximation'', Russell T. Pack

Faculty Publications

It is argued that conflicting approximations in a recent paper [J. R. Stallcop, J. Chem. Phys. 61, 5085 (1974)] render the resulting theory invalid.

A Study Of Some Tetraarylborate-Pvc Membrane Electrodes, Boonrod Hirunmitnakon

Master's Theses

No abstract provided.

The Synthesis Of Some Potential Antimalarials : The 3-(4- Choloropheny1) -5, 7- Dichloronaphthylaminoalcohols, Dwight Allen Shamblee

Master's Theses

A new scheme is presented for the preparation of 3~(4-chlorophenyl)-5,7-dichloro-l-methylnaphthalene, from which, four derivatives, 3~(4-chlorophenyl)-~-di(n-butyl)aminomethyl~5,7-dichloro-l-naphthalene-methanol hydrochloride, 3-(4-chlorophenyl)-5,7-dichloro-~-(2-piperidyl)-1-naphthalenemethanol acetate, l-[3-(4-chlorophenyl)-5,77dichloro-lnaphthyl]-3-di(n-butyl)aminopropanol hydrochloride, and 1-[3-(4-chlorophenyl)-5, 7-dichloro-l-naph,thyl]-2-(2-piperidyl) ethanol hydrochloride, were prepared. These four derivatives were submitted to Walter Reed Army Institute of Research for. the determination of their potential as antimalarial agents.

Here Is Where We Are, M. H. Baker

Journal of the Minnesota Academy of Science

Industrial chemistry in the Upper Midwest consists principally of compounding, formulating and specialty manufacturing rather than the production of basic chemicals. The economic position of industrial chemistry is, nevertheless, significant because many of the region's major corporations are employers of technically-trained personnel and are substantial chemical users. This paper provides a non-quantitative overview of chemical technology applications and developments in some of the area's key industries as a record of the past, a measure of current activity, and as a possible indicator for the future. The paper also notes that the large investment demands, complexity of regulations and distance from …

The Internal Chemical Shift - A Key To Bonding In Aromatic Molecules. 2. Substituent Effects On The Carbon-13 Magnetic Resonance Spectra Of The 1,4-Disubstituted Benzenes, Donald W. Beistel, W. Dan Edwards

Chemistry Faculty Research & Creative Works

Carbon-13 magnetic resonance shifts were determined for six families of 1,4-disubstituted benzenes. Linear least-squares correlations between the internal shifts of the families suggest an additivity relationship for 13C substituent effects at all four nonidentical ring carbons and at the α position when one of the substituents has a central carbon. The correlation of 1H and 13C shifts for these compounds is also linear, implying that the additivity relationships derived in a previous 1H study can be generalized to 13C.

Planning A Kinetic And Mechanistic Study With Cerium (Iv), Samir B. Hanna, Robert R. Kessler, André Merbach, Steve Ruzicka

Chemistry Faculty Research & Creative Works

No abstract provided.

Vapor Phase Oxidation Of Chloropropenes Over Heterogeneous Catalyst Systems, Tim Ellis Owen

Retrospective Theses and Dissertations

Propylene Dichloride (PDC) is a byproduct of several Dow processes. The thermal cracking of PDC produces 1-cis-chloropropene, 1-trans-chloropropene, 2-chloropropene, and allyl chloride . By oxidizing the l- and 2-chloropropenes to 3- and 2- chloroacrylic acids, respectively, a potentially valuable product could be made. The chloropropenes, air, and steam were passed over various heterogeneous oxidation catalyst systems to attempt this oxidation. Contact time was varied between 0.0951 to 0.915 sec. Temperature was varied between 275C to .25C. The air content of the feed was varied between .1 to 75%. The chloropropene content of the feed was varied between 2.9% to 5.0% …

Semiquantitative Infrared Analysis Of Diketones And Anhydrides In A Reaction Mixture, Dominic T.C. Yang, F. H. Watson Jr., J. O. Lay, R. Getty

Journal of the Arkansas Academy of Science

The ozonolysis of a hydroxymethylene ketone yields a mixture of diketone and anhydride. Treatment of hydroxymethylene camphor with ozone affords, in addition to the expected camphor quinone, a surprisingly large amount of camphoric anhydride (56%) via Baeyer-Villager reaction. Use of infrared absorption to analyze the relative amounts of camphor quinone and camphoric anhydride in a reaction mixture was studied by comparing peak heights of their carbonyl stretching bands.

Synthesis Of Tcne And Tcnq Derivatives And The Preparation Of Conducting Polymers, Michael L. Runge

Theses and Dissertations

Tetracyanoethylene and tetracyanoquinodimethane were reacted with various N,N-dimethyl-a, w-alkyldiamines to produce TCNE and TCNQ diamino and monoamino derivatives. NMR and ir spectra of the monoamino derivatives, 1-(N,N-dimethyl-a,w-alkyldiamino)-1,2,2-tricyanoethylenes and 7-(N,N-dimethyl-a,w-alkyldiamino)-7,8,8-tricyanoquinodimethans, indicated that these compounds exhibited strong nitrogen-hydrogen-nitrogen intramolecular hydrogen bonding. This phenomenon was corroborated by molecular weight and preliminary x-ray analyses.

The 1,1-bis(N,N-dimethyl-a,w-alkyldiamino)-2,2-dicyanoethylene and 7,7-bis(N,N-dimethyl-a,m-alkyldiamino)-8,8-dicyanoquinodimethan derivatives were polymerized with a,m-alkyldibromides containing two to six methylene groups to produce the corresponding ionene polymers. Viscosity measurements of the polymers indicated that the TCNE copolymers were generally of higher molecular weight than the corresponding TCNQ copolymers.

The two polymer series were treated with lithium …

The Mechanism Of The Meyer-Schuster Rearrangement, Carol Virginia Roane

Dissertations, Theses, and Masters Projects

No abstract provided.

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

Masters Theses

No abstract provided.

Interactive Pace Approach To Learning In Physics : Method And Materials, Mario Amézquita

University of the Pacific Theses and Dissertations

This study has the following general objectives: first, to present in detail the techniques that the author has developed and used in designed the course and the final materials produced for am introductory physics course in Mechanics; second, to state and examine the important blended ingredients used to get a new strategy for teaching-learning in which and individualized pace together with a group interaction is used; third, to analyze a combination of structural and operational course where concept, structure formation, and problem solving are emphasized.