Physical Sciences and Mathematics Commons^™

Rearrangements In The Synthesis Of Β-Ketoallyl Amines, Richard P. Rebman

Open Access Master's Theses (through 2010)

The work reported in this thesis is part of an integrated research program in progress at the University of Nebraska dealing with the mechanisms of addition, elimination, and substitution in α, β – unsaturated ketones and their halogen derivatives.

The essential scope of this research is the investigation of the mechanism(s) of substitution by amines on α – (bromomethyl)-chalcone.A knowledge of the mechanism(s) involved would be useful in elucidating some of the factors determining the structure of reaction products observed in other similar systems.

Advisor: Norman H. Cromwell

The Preparation Of 5-Arylazopyrimidines, Frederic Edwin Dutton

Masters Theses

Introduction

The synthesis of 5-arylazopyrimidines was undertaken in search of potential anticancer agents.

While many azo compounds have carcinogenic activity, it has been shown by several workers in this area that some 5-arylazopyrimidines have anticancer properties. S. Hibino(1) has shown that p-(2,4,6-triamino-5-pyrimidinylazo) benzene-sulfonic acid shows promise as an effective anticancer agent when used in conjunction with 6-mercaptopurine and adrenal steroidal hormones. When tested clinically, total remission of the leukemic process was achieved in 85.7% of the cases treated. In comparison, total remission was achieved in only 57.5% of the cases treated with a mixture of 6-MP and the hormone which …

Plant-Derived Pigments And Dyes Used By Artists, Samuel C. Rizzetta

Masters Theses

History

Uses of Biologically-derived Products in Painting

Throughout history man has relied heavily on plant-derived materials in the production of paintings. Plant products have been used to fulfill each of the material requirements of painting. The ground or surface upon which an artist applies paint -is usually of plant origin, such as woven fabrics and paper. The ancient Egyptians painted on canvas (from Linum usitatissimum L.), papyrus, (from Cyperus papyrus L.), and wood (Lucas, 1934:149-150, 201-203; Laurie, 1910:17, 31-32).

At the time of Theophilus leather parchment, preferably of horsehide, was popular for painting (Bazzi, 1960:13). After parchment, walls and wooden …

The Synthesis Of Some Decahydronaphthoic Acid Lactones, Robert C. Matejka

Open Access Master's Theses (through 2010)

The diterpenoid acids, dehydroabietic acid, podocarpic acid, abietic acid, and palustric acid, have been synthesized. This thesis records the successful completion of this task which involves a selective epimerization of C.8a. It is hoped that keto lactone on alkylation will give an intermediate of the type C.l epimers which is required for the synthesis of the abietic acid series.

Advisor: D. M. S. Wheeler

The Reaction Of Metal Hydrides With Azoacetates, Thomas H. Althuis

Masters Theses

Introduction

The term aliphatic azo compound refers to those azo compounds in which at least one of the two nitrogen atoms is linked to a tetrahedral, that is, sp³ -hybridized carbon atom. Di-imides, RN=NH, however, are not being considered. Mixed aliphatic-aromatic azo compounds are those in which one nitrogen atom is linked to an sp³ -hybridized carbon atom and the other to an aromatic sp² -hybridized carbon atom. If present, a symmetry element (point or plane) is determined by the mid-point between the two nitrogen atoms.

Study Of The Stereochemistry Of A Carbanion Generated From An Azoacetate, Nguyen Thanh Buu

Masters Theses

Introduction

The reaction of lead tetraacetate with ketohydrazones to form azoacetates has been reported recently by Iffland, Salisbury and Schafer (13) and may be represented by the following equation:

R₂C=N-NH-R' + Pb(0Ac)₄ → R₂C-N=N-R' + Pb(OAc)₂ + HOAc OAc

Of principal interest has been the base-catalyzed decomposition of an azoacetate in a protonic solvent to give a ketone, a hydrocarbon, nitrogen and an acetate salt. The following sequence of steps has been proposed to account for these products (11).

Aminomethylation And Hydroxymethylation Of 6-Mercaptopublne And 6-Alkylthiopubines, Charles P. Bryant

Masters Theses

Introduction

The Mannich reaction and hydroxymethylation were used to prepare analogs of 6-mercaptopurine as possible antimetabolites. Physical and chemical methods were used to elucidate the structures of the compounds prepared.

Scaling In Isoelectronic Molecules, Jerry Goodisman

Chemistry - All Scholarship

A modification of a scaling method introduced for atoms by Ellison enables one to use expectation values calculated for one molecule in calculations of the energy of a second molecule isoelectronic to the first. In going from Hz to Hez2+t,h e results are only fair, but in going from LiF to BeO, the results are suffeciently good to allow prediction of equilibrium distance and several expectation values as well as energy. The dipole moment is a notable exception, which reveals one basic dissimilarity between the two molecules, the ionic character. LiF dissociates to ions, Be0 to neutral atoms, causing our …

Thermodynamics Of Proton Ionization In Aqueous Solution I. A Precision Thermometric Titration Calorimeter ; Ii. Entropy Titration : A Calorimetric Method For Equilibrium Constant Determinations ; Iii. H And S Values For Carboxylic Acid Proton Ionization At 25c ; Iv. Site Of Proton Ionization From Adenosine, Lee D. Hansen

Theses and Dissertations

The design, construction, and calibration of a precision thermometric titration calorimeter is described. This calorimeter was tested by determining the enthalpy change for ionization of water. The result, 13.34 ±0.03 kcal/mole (standard deviation), is in exact agreement with the best literature values. This standard deviation indicates that, using this calorimeter, ΔH values can be determined with an accuracy of ±0.0.5 kcal/mole. A calorimetric procedure has been developed for the, simultaneous determination of the equilibrium constant, the enthalpy change, and the entropy change for a chemical reaction from a single titration (Entropy Titration). This procedure has been tested by determining pK, …

Liquid Scintillators: Some 3-Aryl-L,2-Dihydronaphthalenes, 3-Aryl-1,2-Dihydro-4-Methylnaphthalenes, 3-Aryl-1,2-Dihydrophenanthrenes And 3-Aryl-1,2-Dihydro-4-Methylphenanthrenes: Steric Effects Of The Methyl Group, Lavinel G. Ionescu

Chemistry and Chemical Biology ETDs

scintillation and Fluorescence

There are two methods commonly employed for the measurement of radiation: the ionization chambers, such as the various types of Geiger­Mliller tubes, and the scintillation counters.

The scintillation process involves the emission of discrete light flashes when a substance called phosphor or scintillator is struck by radioactive or other energetic particles. In fact, the word scintillator, comes from the Latin scintilla which means spark. Scintillation is related to fluorescence. The emission spectra for the two phenomena are almost identical, the difference between the two processes lying mostly in the method of excitation. In the case of fluorescence …

Potential Neoplasm Inhibitors, Andrew G. Bachmann

Master's Theses

The historical portion of this paper is designed to show the value of mustard compounds in the treatment of cancer and the methods used to take advantage of various exploit­ able variants between normal tissue and cancerous tissue.

The experimental section is an effort to evaluate and take advantage of the variant of pH.

The Polarizing Effects Of Inhibitors Upon The Reaction Of Iron With Hydrochloric Acid, Duane L. Mickelson

Masters Theses

Introduction

Corrosion inhibitors have been widely studied. Electrical methods of study have been utilized (7) (10) (24) and polarization curves (2) (6) (18) (26) have been plotted by many observers in studying different aspects of corrosion. In this research the measured polarizing currents a.re used strictly in an effort to find out how the corrosion inhibitors affect the anodic and the cathodic reactions.

Reaction Of Dihydropyran With Substituted Benzenesulfonyl Azides, Douglas L. Rector

Masters Theses

Introduction

The intent of this investigation was to study the addition of arylsulfonyl azides to vinyl ethers, specifically 2,3-dihydro-4H-pyran, and to establish by chemical and physical methods the structure of the adduct.

Water Chemistry Survey Of Boulder Basin, Lake Mead, P. R. Tramutt, Bureau Of Reclamation

Publications (WR)

The survey results indicate that the impoundment of water behind Hoover Dam has not adversely affected the dissolved oxygen (DO) content and that water quality and DO content were uniform regardless of depth. The study made in April-May 1964 will provide water quality data of Lake Mead prior to releases from Lake Powell as a basis for evaluating Lake Powell's effect on water quality and limnology of Lake Mead. The performance of a DO analyzer was tested and found unsatisfactory at depths below 150 ft. Parameters tested by standard chemical analyses of water samples in the Denver Laboratory and by …

Synthesis Of Potential Anti-Tumor Agents Related To Ethanolamine. I. Phenoxyacetic Acid Derivatives, Kenneth Wayne Rodarmer

Masters Theses

Introduction

Derivatives of phenoxyacetic acid (PAA), because of their activity as synthetic auxins, have long been of interest in the botanical sciences. PAA itself was noted (29) to have some auxin activity. However, real interest in PAA derivatives awaited the establishment of 2,4-dichlorophenoxyacetic acid (2,4-D) as a powerful, selective herbicide (12). An enormous number of PAA analogs and homologs have been investigated for their potential in the herbicide industry, and the statistical evidence from these investigations has been used as the basis for several interesting and sometimes conflicting theories of auxin mechanisms (17, 26, 23, 27).

Physiological effects of PAA …

Helianthus Annuus - The Separation And Identification Of A New Fatty Acid, Donald C. Gruber

Masters Theses

Introduction

The term "fatty acids" was first applied principally to saturated, monobasic carboxylic acids and especially to long chain acids derived from animal and vegetable oils. As time passed and the knowledge of natural fats increased, polyunsaturated, hydroxy, keto and branched chain acids were also found as constituents of these fats and oils and these also came under the heading of fatty acids. Even acids containing alicyclic substituents were found.

More recently the term 11 fatty acid" has been applied to include saturated and unsaturated monobasic carboxylic acids and several other series of substituted acids having carbon skeletons similar to …

Cleavage Of Organosiloxanes By Metal Halides, Alvin Joseph Alekna

Honors Theses

The aim of the present research is therefore to investigate the clevage of organosiloxanes by several metal halides that were omitted from consideration in previous experminetal work.

Studies Of Aryl Hypochlorites, Edwards Stengle Atwood

Honors Theses

Of all the reactions of the esters of hypohalous acids, those least documented are the reactions and characteristics of the phenolic esters. This includes the reactions of hypohalites in the presence of a strong Lewis acid, such as aluminum trichloride. Only one reaction has been published in which an organic hypohalite is reacted in the presence of a strong Lewis acid; this dealt with an alkyl hypochlorite. Berman and Lowy (1) reacted tertiary butyl hypochlorite with benzene in the presence of aluminum trichloride, reporting tertiary butylbenzene as the product.

A Study Of The Kolbe Electrolysis Using Mixed Mono-Ethyl Glutarate And Mono-Ethyl Malonate, Richard John Gilbert

Honors Theses

The study of electrolytic reactions of organic compounds was first attempted soon after the discovery of the electrolysis if water in 1800. These reactions were not used in synthesis until after 1847 when Kolbe discovered that aliphatic acids. The field has greatly increased since then, and it is now possible to carry out synthesis by electrolytic reduction, oxidation, cathodic coupling, anodic coupling, and substitution. It was the purpose of this work to attempt one mixed Kolbe reaction and analyze its products qualitatively not quantitatively. If time permitted, quantitative analysis would be attempted.

A Study Of Stable Ion-Pairs, James Carlton Garrison

Honors Theses

A study was made of the ion-pair that forms when the commercial surfactant, Ethoquad 18/25, is mixed with azo dyes such as methyl orange or methyl red. The study determined some of the physical characteristics of the ion-pair, and two attempts were made to determine the structure. Through a series of titrations it was found that the ion-pair is sensitive to pH and can be dissociated in strong acid solution. An attempt to determine the structure of the complex by infra-red analysis failed. The equilibrium constants for the Ethoquad and two different dyes were determined. On the basis of the …

A Polarographic Analysis Of The Tetracyanoaurate (Iii) And The Dicyanoaurate (I) Complexes, Richard Joseph Klimowski

Honors Theses

A method for determination of the dicyanoaurate and tetracyanoaurate complexes using polarography has been investigated. Whereas distinct wave forms (current-voltage plots) are obtainable, many interference problems exist. Previous work has been confirmed and new data added. Dicyanoaurate I (Au(CN)2) has been satisfactorily investigated and may be classified as a stable complex. Tetracyanoaurate III (Au(CN)4) has been investigated and must be classified as unstable. This a polarographic method of quantitative analysis for a simultaneous determination of these complexes seems remote.

The Cyclization Of A Diazoketone With Boron Trifluoride Etherate, Stephen Joseph Isser

Honors Theses

Normally, a diazoketone reacts with an acid to form a substituted methyl ketone. When a nucleophilic center is present at an α or β position of R, this reaction may lead to the formation of a cyclic ketone (11). It was the purpose of this research to investigate the cyclization of the aliphatic methoxydiazoketone, 1-diazo-4-methoxy-4-phenyl-2-butanone (I), when treated with BF3 in ether, to give the five-membered ring 5-phenyltetrahydrofuranone-3 (II).

The D O Acidity Function For Aqueous Sodium Hydroxide Solutions, James T. Macgregor

Honors Theses

The H o acidity function developed by Hammett and Deyrup is well known, and values for this function are established for solutions of various acids.

Studies Of The Reactions Of 1-Diazo-3-Methoxy-3-Phenyl-2-Propanone With Boron Trifluoride Etherate, Ross Grant Mackinnon

Honors Theses

Normally the reaction of diazo ketones wih acids yields straight chain-substituted ketones. The product can be a cyclic compound if within the diazo ketone there lies a nucleophilic center at the α or β position.

The Preparation Of 2-Aryl-3-Methyl-4-Metathiazanones And 2-Aryl-3-Methyl-4-Thiazolidones, John Charles Wilson

Honors Theses

It had been found that 3-mercaptopropanoic acid would react readily with ammonia or primary amines yielding Schiff bases which when reacted aryl aldehydes would give 2 and 2,3 disubstituted 4-metathiazanones. The report included a variety of substituted benzaldehydes, pyridyl and thienyl carboxaldehydes, ammonia, and alkyl and aralkylamines.

Photochemical Reactions Of Benzophenone And Cyclohexene, Michael I. Goldberg

Honors Theses

Aldehydes and ketones absorb weakly in the 290 mμ region of the ultraviolet spectrum, and also at 200 mμ (this wavelength region being analogous to that occurring in the spectra of olefinic compounds). This weak absorption band in the carbonyl absorption spectrum can be attributed to an n → π* transmission of a non-bonding electron on the oxygen atom to an anti-bonding π orbital in the multiple bond to give a singlet state. It is this absorption and consequent formation of an energized state which appears responsible for most of the photochemical transformation of saturated ketones in condensed (liquid) phases. …

Kinetic Study Of The Autocatalytic" Photodeboronation Of Benzeneboronic Acid In Phosphoric Acid Media, Bradley C. Bockrath

Honors Theses

Kinetic studies are often valuable in the investigation of reaction mechanisms. They can reveal the molecularity of a reaction and perhaps give an indication of possible intermediate steps. Comparisons of rate studies, such as kinetic isotope effects, can indicate the rate determining step of a reaction. Finally, rate studies can reveal when changes in reaction mechanism accompany changes in one or more kinetically significant variables. This study investigates the possibility of a new or altered reaction mechanism as one kinetic variable is changed. The reaction of interest is the hydrolysis of benzeneboronic acid in concentrated phosphoric acid media.

Thermochemistry Of Cyclophanes, Chyi-Feng Shieh

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The syntheses and properties of various cyclophanes have been extensively investigated by Cram and others. The paracyclophanes are compounds in which benzene rings are linked to each other by two saturated chains at the para positions, as in structure I. When they are joined to the meta positions, they are called metacyclophanes.

The Kinetics And Mechanism Of The Reaction Of Molybdenum(V) With Iodine, Oxygen And Nitrate, Ervin Park Guymon

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Molybdenum compounds present a series of baffling chemical puzzles. By no means are all of these yet even clearly defined and many may never be. This complexity results from the ability of molybdenum to form six different oxidation states, which can possess three different coordination numbers. Furthermore, molybdenum compounds readily disproportionate to yield mixed valence compounds; and finally, molybdate ions readily aggregate in solution to form a variety of polyions by polymerization-condensation reactions which are controlled by pH and the concentration of the system. Molybdenum's complexity can best be summed up in the words of the late Edgar Smith who …

Properties Of Chlorophyll Derivatives Bonded To Polymers, Richard Grant Jensen

Theses and Dissertations

Two types of water-soluble complexes of chlorophyll a with organic polymers have been investigated: chlorophyll a coordinately bonded to poly 4-vinylpyridine and a chlorophyll derivative, Mg-chlorin e_6 phytyl methyl ester, covalently bonded to GANTREZ AN (poly (methyl vinyl ether/maleic anhydride) ). The first complex was observed upon dissolving chlorophyll a and poly 4-vinylpyridine in aqueous ethanol solutions. The Mg-chlorin e_6 diester-GANTREZ AN complex (chlorophyll a/polymer) was made by aminolysing the chlorophyll ring V with 1, 6-hexanediamine to give an intermediate product, Mg-chlorin e_6 -6-N-(6' -aminohexyl) carboxamide, phytyl methyl ester. This was attached to GANTREZ AN by linkage of the 6'-amine …