Digital Commons Network^™

Dimethyl Sulfoxide Oxidation Of Primary Alcohols, Carmen Vargas Zenarosa

Masters Theses

Historical

A method of selective oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones has been developed recently, namely the use of dimethyl sulfoxide (DMSO) as the oxidizing agent, either alone or with dicyclohexylcarbodiimide (DCC)¹⁴, acid anhydrides¹, or alkyl chloroformates¹⁰. The negatively polarized oxygen atom of the sulfoxide group in DMSO is ideally situated for a transfer to many electron-deficient substrates. The oxygen of the alcohol coordinates with the sulfur atom of DMSO through its oxygen atom; this is followed by β-elemination of dimethyl sulfide, thereby resulting in oxidation of the …

Synthesis Of A Substituted Tetrahydropyrimidopyrimidine, Jack Lee Parsons

Masters Theses

Introduction

The purpose of this research was to develop a generalized synthesis of substituted tetrahydropyrimidopyrimidines. It was also of interest to prepare related compounds for the purpose of structure determination.

We were interested in tetrahydropyrimidopyrimidines as possible folic acid antagonists.

Studies On The Preparation Of Tetrasubstituted Hydrazones, William Kao

Masters Theses

Introduction

In a recent study of the ultraviolet spectra of substituted hydrazones, it was concluded that a sterio effect existed in tetrasubstituted hydrazones that significantly hindered complete rotation about the nitrogen-nitrogen bond. Weber¹⁶ noted that di- and tri-substituted hydrazones exhibited similar spectra with three strong absorption bands at approximately 235, 300, and 340 mu. In acid solutions, the spectra of these compounds showed a marked decrease in intensity of the long wavelength band. It has been postulated that this change was a consequence of the protonation of the non-bonding electron-pair on the amino nitrogen atom, and thus correlated the …

The Application Of The Verwey-Overbeek Theory To The Relative Sediment Volume Of Kaolin-Water Dispersions, James E. Kline

Masters Theses

Introduction

This paper describes an investigation intended to: 1. observe the effect of electrolyte concentration on the stability of kaolin-water systems, 2. evaluate the relative sediment volume measurement as a tool for determining the stability of such systems, 3. assess the applicability of the Verwey-Overbeek theory of stability of lyophobic colloids for predicting the observed effects, and 4. determine if any correlation exists between the effects predicted by the theory and observed through the relative sediment volume measurement.

The relative sediment volume measurement will be shown to be dependent upon the efficiency of packing of the pigment particles, which in …

A Study Of The Base Catalyzed Decompositions Of Azoacetates, David V. Herman

Masters Theses

Introduction

The formation of a benzyne intermediate has been shown by several investigators ^(2,5,6) to be developed in at least four different reactions; the reaction of o-dihalobenzenes with magnesium or lithium, aryl halides with strong nucleophiles, o-halobenzophenones with potassium amide in liquid ammonia, and the decomposition of benzenediazonium-2-carboxylate.⁽¹³⁾ The mechanism propsed for one of the above most relevant to the following study, the reaction of o-halobenzophenones with potassium amide in liquid ammonia, is outlined in the following sequence:

Studies On The Ribosomal Ribonucleic Acids From Mesophilic And Thermophilic Bacteria, Alice A. Holazo

Masters Theses

Introduction

Certain organisms have been known to live at temperatures at which cellular constituents ordinarily sensitive to heat are destroyed. These organisms. called thermophiles (heat-loving), normally live at higher temperature range of the biokinetic zone (10^o-45^oC).

Hydrolysis Of Benzohydroxamic Acid, Robert L. Fuller

Masters Theses

Introduction

The hydroxamic acids were discovered in 1869 by H. Lossen¹. The nomenclature, structure, and chemistry of these compounds have been summarized in an excellent review article by Yale².

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 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.

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.

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 …

Carcinostatic Sulfonic Acid Esters Of Selected 1,4-Diols, Robert A. Earl

Masters Theses

Introduction

The purpose of this research was to prepare the bisarylsulfonic acid esters of 1,4-butanediol and 1,4-but-2-ynediol.

This series of compounds is of interest because of the antitumor activity exhibited by the bismethanesulfonates of 1,4-butanediol and 1,4-but-2-ynediol. The compounds which were prepared were submitted to Cancer Chemotherapy National Service Center for evaluation in their anticancer program.

It was hoped that the compounds synthesized would be of pharmacological value. It was further hoped that the biological test data of these compounds would demonstrate a correlation between types of substituents on the aromatic nucleus and the degree of activity of the compounds. …

The Reaction To Ketoacylhydrazones With Lead Tetraacetate, Lavern M. Weisenberger

Masters Theses

Introduction

It has been shown that ketohydrazones react with lead tetraacetate to give azoacetates in good yields (11) according to the following equation:

R₂C=N-NH-R + Pb(OAc)₄ → R₂C(OAc)-N=N-R + Pb(OAe)₂ + HOAc

The reaction of the structurally related 4,4- disubstituted ketosemicarbazones with lead tetraacetate quite unexpectedly gave carbamates in good yields (10) presumably according to the following equation:

R₂C=N-NH-Co-NR₂ + Pb(OAc)4 → R₂C-O-CO-NR₂ + N₂ + Pb(OAc)₂ + HOAc

CO

ı

CH₃

The Reaction Of Ketosemicarbazones With Lead Tetraacetate, Thomas M. Davies

Masters Theses

Introduction

It has been demonstrated that lead tetraacetate will oxidize ketohydrazones to azoacetates in good yields (11).

R₂C=N-NH-R + Pb(OAc)₄ ------> R₂C(OAc)-N=N-R + Pb(OAc)₂ + HOAc

Since ketosemicarbazones are structurally equivalent to ketohydrazones, it was thought that the reaction of ketosemicarbazones with lead tetraacetate would proceed in a similar manner. Originally the object of this research was to prepare a series of new azo compounds related to semicarbazones by lead tetraacetate oxidation.

Pachycereus Marginatus Alkaloids, John M. Brewer

Masters Theses

Introduction

Serturner's paper, 1817, "Morphis, a New Salt-forming Substance, and Meconic Acid, as the Chief Constituents of Opium", opened a new era of discovery in organic plant chemistry. His isolation of the first alkaloid was soon followed by the isolation or narcotine by Robiquet and strychnine by Pelletier and Caventou. These basic compounds were at first called vegetable alkalies, but were later renamed alkaloids, meaning alkali-like¹¹.

A Modified Procedure For The Quantitative Determination Of Fluoride And The Application Of This Procedure To A Fluoride Balance Study In Children, Beatrice Shuang Wu

Masters Theses

Introduction

This research problem was done in connection with the fluoride balance studies on twelve children at Plymouth State Home. The retention balance studies of fluoride by children can be studied indirectly by measuring the amounts of fluoride excreted in the urine and feces after administration of the fluoride in water or in vitamins as sodium fluoride. The fluoride balance study was repeated, because in the previous study (19), there were no samples collected for a base day in which the fluoride was not given. The previous data also indicated that fluoride retention was merely a function of the interval …

Preparation And Properties Of 3, 3’ -Disbubstituted-2, 2’ – Three-Carbon-Atom Bridged Biphenyls, Allan E. Nader

Masters Theses

Introduction

The configuration of biphenyl has been treated in numerous articles and reviews (1, 5, 6, 7, 8, 16, 22, 23). In particular the configuration of 2,2'-bridged biphenyl derivatives has obtained attention. The synthesis of an optically active 2,2'-three-carbon-atom-bridged biphenyl possessing an ultraviolet absorption maximum at 250 mμ has been reported by Iffland and Siegel (15). These properties require first, a non-planar configuration for the molecule and second, significant inter-ring conjugation as demonstrated by ultraviolet spectra.

Several 2,2'-three-atom-bridged biphenyls have been prepared by Ahmed and Hall (2, 3) in order to obtain some measure of their specific rotation. The use …

Preparation Of The Cis And Trans Isomers Of Methylcyclohexanecarboxylic Acids And Their 2-Diethylaminoethyl Esters, Paul Allen Meulman

Masters Theses

Introduction

The purpose of this research is to prepare the CIS and TRANS isomers of the 2, 3 and 4-methylcyclohecanecarboxylic acids and their 2-diethylaminoethyl esters.

This series of compounds is of interest because of the anti-tumor activity shown by some ethanolamine derivatives. The compounds to be prepared in this study represent modifications of these structures to determine if further investigation in this area is worthwhile. A pharmacological evaluation of these compounds will be made since many esters of amino alcohols have demonstrated pharmacological activity. The cancer chemotherapeutic and pharmacological test results are not included in this paper, but will be …

The Correlation Of Spectra And Steric Effects In Alkyl And Aryl Hydrazones, Dennis J. Weber

Masters Theses

Introduction

The correlation of spectra, especially ultraviolet spectra, of hydrazones with their structure has resulted in considerable confusion because of the variations in spectra obtained from apparently the same basic chromophore.

Attempts In The Synthesis Of T-Alkylhydrazines, Richard A. Evans

Masters Theses

Introduction

Interest in t-alkyhydrazines has developed from the recent preparation of azoacetates (5) by the leadtetra-acetate oxidation of hydrazones

Studies Involving Modification Of The Megregian Method Of Fluoride Determination And Application To Fluoride Balance Studies In Infants, Gene R. Wright

Masters Theses

Introduction

At the request of Dr. Frederick Margolis, M.D., and in association with The Upjohn Company, this research problem was initiated as a participation in the investigation of whether or not fluoride ingested as a constituent of the Upjohn 47-M liquid vitamin preparation is retained in an infant's body to the same extent as is fluoride ingested as the sodium salt by itself--either in solution or in tablet form. The retention patterns may be studied indirectly by measuring the amounts of fluoride excreted in the urine and in the feces during each of a series of equal time intervals after …

The Reaction Of N-Magnesium Halides On Nitriles In The Synthesis Of Amidines, Robert Bauer

Masters Theses

Introduction

Compounds of the amidine class have long been of interest because of their therapeutic and pharmacological properties. Members of this class of compounds have been shown to be effective in combating pathological conditions ranging from virus (11), bacterial (12), and protozoal infections (7) to diseases of the circulatory system (6), neoplasms (5) and hyperglucemia (21), Since many basic nitrogen compounds have been of interest in cancer chemotherapy, such as a variety of amino alcohols shown by the Upjohn Company to have anti-tumoral activity, it was felt that additional investigations into the use of amidines and amino amidines in this …

Buttressing Effect In 3, 3' -Disubstituted-2, 2' -Three-Carbon-Atom Bridged Biphenyls, Yunn Hui Chiang

Masters Theses

Introduction

The configuration of biphenyl has been the subject of much investigation and many recent reviews (1, 5, 6, 7, 8, 17, 21, 22). Of particular interest has been the configuration of 2,2' -bridged biphenyl derivatives. The preparation of an optically active 2,2' -three-carbon-atom-bridged biphenyl having an ultraviolet absorption maximum at 250 mμ, has been recently described (14). Although the compound was easily racemized, this property requires that a non-planar configuration be assigned to this biphenyl (I). Furthermore, this ultraviolet spectra indicates that inter-ring conjugation must exist in the non-planar configuration.

The Reaction Of N, N-Disubstituted Ketohydrazones With Lead Tetraacetate, Elisabeth Cerda

Masters Theses

Introduction

The reaction of lead tetraacetate with compounds of the following general structure (not able to enter here) was first reported by Iffland and Criner (12). In the case of ketoximes (A = oxygern), a nitrosoacetate was produced which was oxidized to the more stable acetoxy-nitrocompound as follows: (not able to enter here)

The generality of the reaction was established by preparation of a series of acetoxy-nitrocompounds from alicyclic and aliphatic ketoximes. The apparently similar reaction of cyclohexanonephenylhydrazone (A = N-¢) with lead tetraacetate was reported, but the reaction product was not identified.

The Apparent Effects Of Rh Hapten Ingestion On The Circulating Blood Phosphorus, Barbara Lyke

Masters Theses

The purpose of this work carried on at Western Michigan University during the past year is an attempt to elucidate further the action of Rh hapten within the body, or more specifically, the effect of its ingestion on the circulating blood phosphorus.