Chemistry Commons^™

The Discovery And Characterization Of Novel Potent 5-Substituted 3, 3’, 4’, 7-Tetramethoxyflavonoid Dna Triplex Specific Binding Ligands, Vanessa Marie Rangel

University of the Pacific Theses and Dissertations

Chemotherapy works by killing fast dividing cells. Unfortunately, these drugs are not specific to cancer tissue and can damage normal cells. Chemotherapy is like taking poison and hoping it kills the cancer cells before it kills you. As an alternative, many researchers have investigated the use of antigene therapy to selectively target cancer causing genes to avoid off target effects. Although promising, the theory is limited by the stability of the triplex structure. Here, we report the discovery of potent triplex binding ligands derived from the natural product quercetin. Chemical derivatives of 5-substituted 3, 3’, 4’, 7-tetramethoxyquercetin derivatives were characterized …

Exploration Of Cis-1,2-Diaminocyclohexane-Based Conformationally Locked Chiral Ligands In Asymmetric Synthesis, Carim Van Beek

University of the Pacific Theses and Dissertations

Natural products have been demonstrated to be of great significance to the pharmaceutical industry in the development of new drugs and medicine. Unfortunately, synthetic approaches to obtain these natural products often prove increasingly challenging due to the complexity of synthesizing the target drug in the proper stereochemistry. The availability of enantioselective reactions can play a pivotal role in overcoming this challenge, yielding access to optically pure intermediates and products. Chiral ligands based on a trans-1,2-diaminocyclohexane motif are often employed for this purpose and their complexes with transition metals have been demonstrated to act as efficient chiral catalysts in asymmetric reactions. …

Studies On The Size And Non-Planarity Of Aromatic Stacking Moiety On Conformation Selectivity And Thermal Stabilization Of G-Quadruplexes, Mandeep Singh

University of the Pacific Theses and Dissertations

Targeting DNA has the advantage over proteins for cancer remediation because of the fewer copies of the ligands required for the desired therapeutic effect. Traditionally, covalent DNA binders like alkylating agents have been used to induce genetic instability through the formation of DNA lesions and strand breaks, leading to cellular apoptosis. The primary drawback of this treatment is the non-specific binding that affects both cancerous and non-cancerous cells. G-quadruplexes are the DNA secondary structures that are present in abundance near the promoter regions of the oncogenes and are involved in the regulation of their activities. A ligand-mediated stabilization of G-quadruplexes …

Glycals : An Extended Study Of The Ferrier-Dimerization, Andreas H. Franz

University of the Pacific Theses and Dissertations

C-linked disaccharides were synthesized from 3,4,6-tri-O-acetyl-D-glucal 1 (1,5- anhydro-3,4,6-tri-O-acetyl-1,2-dideoxy-D-arabino-hex-I-enopyranose), 3,4,6-tri-O- acetyl-D-galactal 2 (1,5-anhydro-3,4,6-tri-O-acetyl-1,2-dideoxy-D-lyxo-hex-1- enopyranose) and 3,4-di-O-acetyl-L-fucal 3 (1,5-anhydro-3,4-di-O-acetyl-1,2,6-tri-deoxy- L-lyxo-hex-1-enopyranose) under Lewis acid catalysis (Scheme 1) and compound 4 was further derivatized at the double bond. Dihydroxylation of the glucose dimer 4 gave high allo-diastereoselectivity. The reactions used in the derivatization of 1 were subsequently applied to 2 and 3. The overall yield of 3 was improved to 70 %. All three glycals (10% solution in toluene) reacted quickly with boron trifluoride to give dimerization products in 40-60% yield. Futile attempts at de-O-acetylation of the 2',3'-unsaturated dimer revealed the necessity of …

Kinetics And Stoichiometry Of The Aquation Reaction Of Pentaaquodihalomethyl Chromium(Iii) Ions, Mohammad Javaid Akhtar

University of the Pacific Theses and Dissertations

This study was designed to provide information about the mechanisms of pentaaquodihalomethyl chromium(III) ions (halo chloro, bromo and iodo).

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Mechanisms based on carbonium ion, carbeno and carbenoid type intermediates are proposed. A mechanism based on the nucleophillic attack (S_N2) of water on the carbon center leading to a metal-formyl type intermediate is suggested as best fitting all the criteria observed in these studies.

(see PDF file for additional Abstract as it includes formulas)

Cyclic 4,6-Oxygen-Acetal Derivatives Of D-Glucopyrano-(2,3: 4',5')-2'-Oxazolidinones., Daniel Vernie Robinson

University of the Pacific Theses and Dissertations

No abstract provided.

3,3-Diphenyl-2-Morpholinone Derivatives Of 2-Amino-2-Deoxy-D-Allose., Ram Babu

University of the Pacific Theses and Dissertations

A new cyclic protective group has been fused to the cis amino alcohol group of benzyl 2-amino-3,5-o-benzylidene-2-deoxyβ-D-Allopyranoside, by way of a unique rearrangements mechanism. To establish the 2-morpholinone structure, chemical studies, such as reduction and acetylation were conducted.

Comparative spectroscopic studies using ir, pmr, and C-13 nmr confirmed the assigned structures.

The 2-morpholinone ring was cleaved by mild alkaline hydrolysis and could be closed again with acetic anhydride in pyridine. An oxazolidinone derivation of benzyl 2-amino-4,6-o-benzylidene-2-deoxyβ-D-allopyranoside was prepared in a quantitative yield by a modification of a known method.

Protective group properties of the oxazolidinone were studied prior to the …

Attempted Synthesis Of 1-Methyl-4-Isopropyl-Hydroxy Bicyclo (3.1.0) Hexane, Kenny Uzoma Acholonu

University of the Pacific Theses and Dissertations

The purpose of this work was to investigate a general synthetic route to 1-Methyl-4-Isopropyl-Hydroxy Bicyclo (3.1.0) Hexane.

Birch Reduction Of Benzamide, N-Substituted Benzamides And Biphenylene, Luther Dickson

University of the Pacific Theses and Dissertations

The Birch reduction of benzamide with sodium and absolute ethanol. 95% ethanol, or tert-butanol in liquid ammonia gave 1,4-dihydrobenzamide in varying amounts. The amide group was not reduced. The two most important variables encountered were the alcohol used and whether or not ammonium chloride was added after the reduction was completed. Without this addition of ammonium chloride, little or no 1,4-dihydrobenzamide was present after workup, while with its addition some 1,4-dihydrobenzamide formed whether the proton source was absolute ethanol, 95% ethanol, or tert-butanol. The highest yield was obtained with tert-butanol with ammonium chloride being added. Addition of ammonium chloride apparently …

The Thermal Rearrangement Of Triarylacetonitrile Oxides., Leslie Wayne Gibbs

University of the Pacific Theses and Dissertations

This research is a detailed study of the rearrangement of triarylacetonitrile oxides to the corresponding triarylmethylisocyanates. The kinetics of the rearrangement of triphenylacetonitrlle oxide was followed by infrared absorption spectroscopy using the peak due to the N-0 stretching (1307cm^-1). A study, both, using the differential method (i.e., a plot of the logs of the initial slopes vs. the log of the concentration) and a check of the integrated forms of the rate expressions to determine which gave a constant value for the rate constant showed that the reaction is first order.

From measurements of the rate constant, k, …

The Preparation Of Coordination Compounds Of Rhodium (Iii) And Glutamic Acid And Substituted Glutamic Acids, Herman William Kalberer

University of the Pacific Theses and Dissertations

The father of coordination chemistry was Alfred Werner (1866- 1919). Werner's theory was largely responsible for the renewed interest in, and rapid growth of, inorganic chemistry around the turn of the century. He postulated that there were two types of valence, primary and secondary, which correspond, in modern terminology, to oxidation state and coordination number. The primary valences must be either negative ions, neutral molecules or, occasionally even, positive ions (11). He also postulated that the secondary valences are directed in space about the central ion, not only in the solid state, but also when the complex is in solution. …

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.

A Study Of The Effect Of Temperature Upon Reactions Between Stannous And Arsenate Ions In Silicic Acid Gels, Ellis Elder

University of the Pacific Theses and Dissertations

Chapter I: Statement of the Problem

The purpose of this investigation was to determine to what extent the reaction between stannous and arsenate ions in silicic acid gels is influenced by temperature.

This was to be done by observing (1) the rate of crystal growth; and (2) the appearance of the crystal growth in sets of gels identical in composition but kept at different temperatures throughout the process of crystal growth.

Reactions Between The Stannous And Arsenate Ions In Silicic Acid Gels, Willard Merle Farr

University of the Pacific Theses and Dissertations

Observation of crystal growths resulting from the chemical interaction of stannous chloride and sodium arsenate in silicic acid gels revealed the following very interesting fact. Gels identical in every respect except acidity, contained crystal growths varying greatly in appearance.

The purpose of this investigation was, therefore, to allow stannous and arsenate ion to combine in a series of accurately prepared gels, identical in all respects except the acid content, and to observe the effect upon crystal growth of: (1) varying the acid concentration; and (2) varying the kind of acid