Chemistry Commons^™

Studies Of The Cleavages And Stabilities Of Carbohydrate Epoxides And Epimines, Curtis Alvin Johnson

University of the Pacific Theses and Dissertations

A novel epoxide ring opening of benzyl 3,4-anhydro-2-benzylox-carbonylamido-2-deoxy-β-D-allopyranoside(I) was affected by phenylboronic anhydride in toluene. One of the products was demonstrated to be benzyl 2-benzyloxycarbonylamido-2-deoxy-4,6-0-phenylboronate-β-D-gulopyranoside. Another product isolated, while not identified, had the properties of an anhydro-sugar different from the starting compound(I). Benzyl 6-0-acetyl-2-benzyloxycarbonylamido-2-deoxy-β-D-allopyranoside(II) also underwent epoxide ring opening in a reaction with phenylboronic acid. An isolated product had the properties of a benzyl 2-benzyloxycarbonyiamido-2-deoxy-D-hexoside different from compounds isolate in the reaction of I with the phenyboronate. This indicated the necessity for an unsubstituted 6-OH group in order for the boron compound to be involved in the ring opening. Supporting …

Palladium(Ii) And Platinum(Ii) Complexes Of 2-Cyanophenyl Diphenylphosphine, David Harrison Payne

University of the Pacific Theses and Dissertations

There has been no successful chelation of any phosphorus-acetylenic or phosphorous-nitrile ligand. The objectives of this study were to synthesize such ligands and to study their chemistry and chelating tendencies. The best choice appeared to be the preparation of ortho-substituted triphenylphosphines similar to the chelating ligand allylphenyldiphenylphosphine. The Grignard reactions utilized in the preparation of the olefinic compound could not be used in most cases due to the high reactivity of the acetylene and nitrile function Bromobenzene and iodobenzene have been reacted with alkali metal phosphines under conditions that were probably too drastic for the acetylenic and nitrile functions. There …

Fluorescence Lifetimes And Quantum Efficiencies Of Some 1,10-Phenanthrolines, Paul John Tabakian

University of the Pacific Theses and Dissertations

Fluorescence properties of fourteen substituted 1,10-Phenanthrolines were determined using two different solvent systems. Hour different sets of experiments were performed in order to measure fluorescence lifetimes, quantum efficiencies, absorption and corrected fluorescence spectra, oscillator strengths, and Stoke’s shifts. Two of the phenanthrolines, the 5-Nitro-1,10-Phenanthroline and the 1,10-Phenanthroline-5,6-Dione, did not fluoresce.

A new equation was developed in order to extract the true fluorescence lifetimes τ from the observed fluorescence output f(t), and the lamp decay function I(t). This equation was [see PDF] where “A” was the weight factor or the normalization constant for the appropriate functions. A test of this equation …

The Preparation And Determination Of Some Of The Properties Of The Dicarboxylic Amino Acid Chelates Of Platinum(Ii) And Palladium(Ii), Gordon Harold Williams

University of the Pacific Theses and Dissertations

It is surprising that no one has considered that coordination might have some effect on the strength of the acid group. It is the intent of this study to fill this gap in the knowledge of amino-acid chemistry.

At about the time this study began on the effect of chelation on the strength of the uncomplexed acid group, the next two higher homologs of these dicarboxylic amino acids became commercially available. It was, therefore, decided that the problem of this research should be expanded to include all four of the acidic amino acids.

The research problem was also defined to …

Reactions Of Difunctional Esters With Benzyl 2-Amino-4,6-0- Benzylidene-2-Deoxy-D-Glucopyranosides, Fred Robert Seymour

University of the Pacific Theses and Dissertations

This research is primarily interested in investigating the reactions of benzyl 2-amino-4,6-0-benzylidene-2- deoxy-D-glucopyranoside (I) with various esters. The advantage offered by this sugar is that an alcohol and an amine group are in close proximity, allowing studies of intermolecular vs. intramolecular reactions and observation on anchimeric assistance in intramolecular reactions.

Cyclic Derivatives Of 2-Amino-2-Deoxy-D-Hexopyranoses, Kenji Miyai

University of the Pacific Theses and Dissertations

The purpose of this investigation was to prepare heterocyclic derivatives, bridging C-2 and C-3 of 2-amino-2-deoxy-D-hexopyranoses, useful as blocking groups in the preparation of aminosugar oligosaccharides and polysaccharides. The work reported herein is concerned with oxazolidones of 2-amino-2-deoxy-D-hexopyranoses (Figure 1).)

There are no examples known, in which five or six-membered rings are fused in a trans-arrangement to five-membered furanose ring. However, although synthetic difficulties were observed, sic and five-membered rings were fused in a trans-arrangement to a sic-membered pyranose ring as pointed out before. In the case of our trans-diequatorially fused oxazolidones additional preparative difficulties were expected, because of the …

A Short Route To Benzyl Beta-D-Glycosides Of 2-Amino-2-Deoxy-D-Glucose And -D-Allose And Elimination Of The 3-Sulfonate From Benzyl 4,6-O-Benzylidene-2-Benzyloxycarbonylamido-2-Deoxy-3-O-(Methylsulfonyl)- Beta-D-Glucopyranoside, William Denham Rhoads

University of the Pacific Theses and Dissertations

It is one purpose of this dissertation to introduce a facile method for the preparation of β glycosides of D-glucose and D-allose.

It is the second purpose of this dissertation to investigate the preparation of 2-oxazolidinones forming a bridge between C₂ and C₃ of allopyranose. This preparation, along with the facile preparation of β-benzyl glycosides of D-glucosamine and D-allosamine, should lead to compounds which, in a few steps, can conceivably be used for coupling at positions 1 and 4.

A Polarographic Study Of Substituent Effects In Nickel(Ii)-Complex Ions Of Pyridine And Pyridine Derivatives, Keith Edward Fester

University of the Pacific Theses and Dissertations

The electrochemical technique of polarography was used to study the complexions formed by Ni(II) ion and pyridine compounds. It was of interest to vary the substituent group on the pyridine ring in order to observe the effects on the nickel - nitrogen coordinate bonds.

An Investigation Of The Feasibility Of Making Radiometric Titrations Of Precipitation Reactions, Harold Elmore Hammerstrom

University of the Pacific Theses and Dissertations

The purpose of the present work was to (1) determine the feasibility of performing radiometric titrations using low activity radioisotopes and inexpensive equipment; (2) develop a workable procedure for performing ·radiometric titrations in the classroom; and (3) assemble the basic radioactive concepts needed so the content could be used in a chemistry course of study.

The limited work done previously with radiometric titrations has used solutions of high specific activity and relatively large volumes of solution. The use of high activity radioisotopes creates problems of radioisotope procurement, shielding, handling and disposal. The use of high activity radioisotopes required special training …

Determination Of Flow Curves From Capillary Rise Rate Measurements, Richard Lehr Kissling

University of the Pacific Theses and Dissertations

The measurement of viscosity is a common and useful technique for investigating the mechanical behavior of many real fluids. Theoretical interpretations of viscosity measurements have been important in attempts to elucidate fundamental properties of the liquid state. Brush (6) and Bondi (3) give reviews of the current status of attempts to construct theories of liquid viscosity, and it is quite apparent from these reviews that the molecular theory of rheological phenomena is in its infancy.

In addition to the fundamental aspects of viscometry, there are many practical applications to which viscosity measurements are directed (25). One has only to scan …

Electrocapillary Studies Of Reversible Charge Transfer V(Iii)/V(Ii) Electrode, Mohammad Ali Akhtar

University of the Pacific Theses and Dissertations

Electrocapillary equation for an ideal polarized electrode based on Gibb's adsorption equation is appropriately recast into experimentally measurable quantities in order to apply it to a reversible charge transfer electrode.

To calculate the various parameters of the equation developed, experimental details were worked out. For the measurement of Current-time relationship of a single drop, a fast response potentiostat was built by using transistorized chopped stabilized operational amplifiers and precision components in the circuitry with proper compensation for IR-drop in the cell and the electrical double layer capacity. The analysis of I-t curves was done by taking into account the composite …

Measurement Of Fluorescence Lifetimes Of Biologically Significant Compounds, Irene Adele Petz

University of the Pacific Theses and Dissertations

The purpose of this research was to measure fluorescence decay-times of several biologically significant compounds. Although various equations are available which permit one to calculate fluorescence lifetimes from spectral data, ample evidence exists which indicates such calculations are at considerable variance with experimental results.

A Study Of The Formation Of Cyclic Allenes From 2,3-Dibromocycloalkenes, Michael John Millam

University of the Pacific Theses and Dissertations

This investigation was undertaken in an attempt to form strained cyclic allenes and to study their chemistry. The method chosen for the attempted formation of strained cyclic allenes was the determination of the corresponding 2,3-dibromocycloalkene. 2,3-Dibromocyclononene was synthesized during the course of this investigation so that its debromination to the 1,2-cyclononadiene, which is the smallest stable, 1,2-cycloalkadiene, could be studies as model for the debromination of smaller 2,3-dibromocycloalkenes was initiated. The formation of 1,2-cyclohexadiene was attempted by the debromination of the 2,3-dibromocyclohexene. Evidence for the presence of this unstable intermediate was sought via the use of trapping agents.

Palladium And Platinum Complexes Of Substituted Cycloolefins, Gerald Brady Mccauley

University of the Pacific Theses and Dissertations

Much of the fundamental work on complexation of cycloolefins by platinum metals has been laid down by several workers and ranges from complexes of butadiene those of cyclododecatriene. The work here was chiefly a continuation of research on cycloolefin complexes which appear in papers by Kuljian and Frye (30,31,44). Most of this work on the complexes of cyclic seven, eight, and twelve carbon ligands was repeated here to insure a more complete laboratory background and for verification of previously reported literature data on these compounds. These compounds were used a s basis for comparison to original compounds developed in the …

A Polarographic Study Of Selected Metal Complex Ions Of Several P-Tosyl Amino Acids, Joseph Martin Reyes

University of the Pacific Theses and Dissertations

A polarographic study of the complexes of selected metal ions and the p-Tosyl derivatives of the amino acids; glycine, glutamic acid and lysine has been made to determine their coordination number, formula, dissociation constant and free energy of formation.

Synthesis Of N-Methyl-D-Gulosamine And Methyl Ethers Of N-Methyl-D-Gulosamine, Hazrat Mohammed Noorzad

University of the Pacific Theses and Dissertations

A great variety of amino sugars has been found in antibiotics among these D-gulosamine in the striptomyces group. In the same group, .an N-methylated amino-sugar, N-methyl-L~ glucosamine has been isolated. Although N-methyl-0-gulosamine .has not been found in nature until now, its ultimate discovery would not be surprising in this context. In the present work this amino-sugar and some important derivatives are prepared for the first time, starting from D-glucosamine, a pure benzyl· 3-0-acetyl-2-benzyloxycarbonylamido-2-deoxy-~-D-glucopyranoside (X) was obtained by a series of kno~n processes. Benzyl 3-0-acetyl~-methylsulfonyl-2-deoxy-~-D-glucopyranoside (XIII) and some of its derivatives were obtaine.d from (X). An attempt was made to obtain …

Ternary Phase Diagram Determinations Concerning Potassium Electrolyte Influence On Aqueous Solutions Of Dioxane Or Tetrahydrofuran, John Albert Mcnaney

University of the Pacific Theses and Dissertations

For the graphical representation of the mutual, partial solubilities of a·ternary system, a diagram is generally employed which is based upon the equilateral triangle, whose properties are especially felicitous for this-purpose.

In this study, the phase diagrams for the following systems were determined: potassium acetate-water-dioxane, potassium acetate-water-tetrahydrofuran, potassium benzoate-water-dioxane, potassium benzoate-watertetrahydrofuran, potassium chloride-water-tetrahydrofuran, and potassium hydroxide-water-dioxane.

The systems, potassium acetate-water-dioxane and potassium hydroxidewater-dioxane, were investigated at 25° and 85°. This study indicates that they are, to a slight degree, temperature dependent. When these systems were plotted on a mole-percentage basis, it was found that both potassium compounds have about the …

Synthesis Of Benzyl Beta D-Gulopyranosiduronic Acid-(2',3': 4,5)-Oxazolidone-2, Gerald Duane Shryock

University of the Pacific Theses and Dissertations

Although D-glucosamine has been found as a constituent of some antibiotics (28), very little research has been carried out in the area of synthetic preparations. Dutcher (7) recently reviewed the biochemical importance of this class of amino sugars as a constituent of complex antibiotic substances which compose the streptothricin family. For a complete elucidation of these antibiotics, it becomes necessary to investigate thoroughly the synthesis and reactions of the D-glucosamine compounds. Gross et al. (12) have succeeded in preparing the oxazolidone of α-D-glucosamine as well as some derivatives (13) of this compound. The present work reports an attempt to prepare …

The Synthesis Of Benzyl N-Carbobenzoxy Beta-D-Glucosaminid Uronic Acid Derivatives, Stuart Martin Block

University of the Pacific Theses and Dissertations

The purpose of this research is the preparation and characterization of derivatives of benzyl N-carbobenzoxy-β-D-glucosaminiduronic acid. Previously the derivatives of benzyl N-carbobenzoxy-α-D-glucosaminid-uronic acid have been prepared by H. Weidmann and H. K. Zimmerman (32). The procedure upon which both these uronic acid syntheses is based has been developed with the utilization of platinum in the selective catalytic oxidation of both the benzyl α- and β-D-glucuronosides. The applicability of this research is in the development of new intermediates for the preparation of new diamino sugars or other natural products.

Capillary Behavior Of Viscous Liquids, Marvin De Young

University of the Pacific Theses and Dissertations

A major problem confronting every investigator who works with synthetic organic chemistry is that of the crystallization of the products obtained. This problem necessitates extensive attention both on the experimental and on the theoretical level. In order to gain an understanding of the behavior of substances in the liquid state, so as to be better able to manipulate them in procedures intended to induce crystallization from complex mixtures, considerable attention has been given to various models of the liquid state. An understanding of the nature of pure liquids would seem to be an essential prelude to any attempt to understand …

A New Two-Position Protecting Group: Preparation And Properties Of Glucopyranosido-(1,2: 4',5')-2'-Oxazolidone And Syntheses Of D-Glucosaminides, Sharad Ramchandra Kulkarni

University of the Pacific Theses and Dissertations

The present work consists of two parts. The first part contains the synthesis of 3,4,6-tri-o-benzoyl-D-glucopyranosido-[1,2:4¹,5¹]-2¹-oxazolidone (III) and the study of its chemistry in order to determine whether it could be used as a simultaneous protecting group for C₁ and C₂ in the preparation of new aminosugars. The second part covers the synthesis and de-o-benzoylation of β-D-glucosaminides. The products thus obtained can be used to prepare new disaccharides. In addition new aminosugar derivatives have been prepared.

The Binary Halides Of Molybdenum(Iv) And Tungsten(Iv) And The Oxochlorides Of Tungsten(Vi), Edward Roy Epperson

University of the Pacific Theses and Dissertations

It was the purpose of this study to investigate the reaction of molybdenum and tungsten dioxides with carbon tetrachloride and bromoform (via the method of Knox and Tyree) to produce anhydrous molybdenum and tungsten tetrachlorides and bromides and to determine whether the method is a reliable one for the synthesis of these compounds. Out of this grew an investigation into the preparation of the oxochlorides of tungsten(VI) using the same preparative technique.

The results of this study are here set forth. An attempt is made to systematize the published material on the synthesis and properties of the binary halides of …

Polarography Of Selected Metal Ions In Anhydrous Aliphatic Diamines, Frederick William Foss Jr.

University of the Pacific Theses and Dissertations

A search of the literature revealed that no study has sought to measure and compare the polarographic solvent properties of the anhydrous aliphatic diamines. In fact, there has been no reported instance of the use of anhydrous 1,3-propanediamine or 1,4-butanediamine in any electro- chemical system.

Some Spectrophotometric Studies Of Molecular Complexes For Phenanthrene, Anthracene, Pyrene, Chrysene, And Benzanthracene With Iodine Monochloride, Joe Boyd Coacher

University of the Pacific Theses and Dissertations

The principal purpose of the present study was to prove the existence of the weak interaction between the halogenoid iodine monochloride and the condensed polycyclic aromatic hydrocarbons, phenanthrene, anthracene pyrene, chrysene, and benzanthracene (see Figure 1).

The Synthesis Of 2,6-Diamino-2,6-Dideoxy-D-Galactose., Lester Vern Smith Jr.

University of the Pacific Theses and Dissertations

The objectives of this research problem were divided into several parts. The first objective was to develop a practical method of preparing 2,6-diamino-2,6-dideoxy-galactose. A second objective was to investigate the derivatives of benzyl-N-carbobenzoxy-α-D-galactosaminide. FInally, the third objective was to lay the groundwork for another possible route for the synthesis of 2,6-diamino-2,6-dideoxy-galactose other than the uronic acid route.

Fluorescein As A Reagent In A Spectrophotometric Determination Of Micro-Amounts Of Iodine: Application To Glucose Determination, Donald Eugene Braun

University of the Pacific Theses and Dissertations

The increasing awareness of the close inter-relationships between biological activity and chemical reactions has resulted in a rapidly growing pursuit of biochemical knowledge. Research in the related fields of medicine, virology, pharmacy, and biophysics is expanding at a rapid rate. Problems related to food production for an exploding population, space explorations, world health issues, the utilization of the resources of the oceans, and the proper employment of energy sources have spurred man to delve deeper into the secrets of creation. The mysteries of life itself are slowly being revealed through finding in egentic studies.

With this ever expanding biochemical and …

Polarography As A Measure Of Ionic Environment, James Wilburne Larsen

University of the Pacific Theses and Dissertations

The present work is a polarographic study of the alkali metals and selected first row transition metals in DMSO (dimethylsulfoxide) with tetraethylammonium perchlorate as a supporting electrolyte. DMSO was chosen as a solvent because of its interesting solvent and complexing properties. Tetraethylammonium perchlorate was chosen as a supporting electrolyte because of its lack of complex forming tendencies and because of the wide range of voltages available for polarographic investigation before the supporting electrolyte ions react electrochemically.

One of the problems, particularly in nonaqueous polarography, is the low conductivity of the solutions leading to high cell resistance. As current flows through …

Anomers Of D-Galactosamine Benzoates, Robert Stanley Strong

University of the Pacific Theses and Dissertations

D-Galactosamine has been known as one of the rarer amino sugars, occurring widely distributed in small concentrations in living organisms. The biological importance of D-galactosamine and its derivatives was thought to justify a study of the chemical properties of this group of compounds. As a result of this study the reactions of D-galactosamine have been found to differ more than previously thought from those of D-glucosamine, the more common amino sugar

For this investigation D-galactosamine hydrochloride was isolated from chondroitin sulfate, a polysaccharide obtained from the cartilaginous tissues of animals. This was changed by appropriate reactions to the 1,3,4,6-tetra-0-benzoyl-N-carbobenzoxy-α-β-D-galactosamine (III). …

Thin Layer Chromatography Of The Platinum Metal Ions, Anthony Paul Trujillo

University of the Pacific Theses and Dissertations

Recent work in this laboratory has centered about the platinum metals and their complexes. The current activity in thin layer chromatography, and especially the work of Seiler in using the technique for inorganic applications, led to speculation regarding the separation and identification of the platinum metal ions by thin layer chromatography. Specifically, then, the purpose of this study was twofold: (1) to find a suitable adsorbent and solvent system to separate some or all of the platinum metal ions; (2) to find appropriate locating agents, so that once the separation had been accomplished, the ions could be identified.

The Transition Metal Complexes Of Anthranilic Acid And Its Derivatives, Jesse Smith Decker

University of the Pacific Theses and Dissertations

Part of this investigation was undertaken to determine the effects of functional group substitution on the ring - as well as on the -NH₂ radical - on the formation of metal complexes with the first transition series in the periodic classification of the elements.

The outline of the investigation in this report is as follows: (1) To mind methods for the preparation of the complexes.; (2) To examine the relative ease of formation, and the relative solubility of such chelates in common laboratory reagents.; (3) To determine the relative stabilities by relative molar conductance measurements.; (4) To discover relative …