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 Degree Discipline: Chemistry
Conformational Analogs of Some Phytoactive Compounds
In an effort to determine if there is a specific conformational structure which is most effective at the appropriate active physiological site, the synthesis of a group of sterically restricted analogs was undertaken. A portion of the polymethylene carbon skeleton of glutaric acid was replaced by selected aromatic carbons in benzenedicarboxylic acids to produce a series of ridged conformers, and the relative plant growth regulating properties of these derivatives were determined.
Syntheses of Antimetabolites
In these studies several different types of antimetabolites were synthesized, and their biological effects were examined in various assay systems. More extensive investigations were done in microbial systems in which many of the compounds proved to be inhibitory to growth, and attempts were made to determine the mode of biochemical action by adding supplements of the appropriate natural metabolite.
Magnetic Exchange in Oxovanadium(IV) Complexes with N-Salicylideneamino Acids
Copper(II) and oxovanadium(IV) ions resemble one another magnetically in having one unpaired electron in their complexes irrespective of their geometrical structures and bond types involved. Copper(II) complexes with antiferromagnetic exchange are well known. On the contrary, antiferromagnetic exchange in oxovanadium(IV) complexes is rather new and not well established. Very few oxovanadium(IV) complexes have been reported to have this anomalous magnetic property. In the investigation of the magnetic properties of oxovanadium(IV) complexes, we have successfully prepared two series of new oxovanadium(IV) complexes with N-salicylideneamino acids.
An Approach Towards the Total Synthesis of Clonostachydiol
The syntheses of the unsymmetrical 14-membered bismacrolides have been reviewed. A total synthesis of clonostachydiol, the latest to join this family, has been attempted using trimethylsilyl acetylene as the builiding block and palladium catalyzed reactions for the formation of key bonds. The alkyne groups were introduced by Stille coupling of trimethylstannylethynyltrimethylsilane with an acid chloride for one fragment and by addition of lithiotrimethylsilyl acetylene to an aldehyde for the other. Lactic acid derivatives were chosen as starting materials for both fragments, thus introducing two of the chiral centers. The remaining stereocenters were introduced using stereoselective reductions of ketones.
Survey of the Solid State Conformation of Calix[4]arenes
The characteristics of seventy-six calix[4]arene crystal structures derived from the Cambridge Crystallographic Database are presented. This survey is a discussion of the inter and intramolecular effects on the solid state cavity shape and molecular recognition ability of the compounds. In addition to this survey, four new calix[4]arene crystal structures are presented. The conformational characteristics of these four calixarenes are determined by a complicated array of inter and intramolecular interactions in the crystal packing.
Mobile Order Theory as Applied to Polycyclic Aromatic Heterocycles
Experimental mole fraction solubilities of benzil, thianthrene, trans-stilbene, thioxanthen-9-one, diphenyl sulfone and dibenzothiophene sulfone are determined in pure noncomplexing and complexing solvents. Predicted solubility values are calculated for benzil, thianthrene, trans-stilbene and thioxanthen-9-one using expressions derived from Mobile Order theory. Large deviations between experimental and predicted solubilities in alcohol solvents exist, therefore optimized solute - solvent association constants are determined. Previously measured thianthrene solubilities in five binary alkane + cyclohexane solvent mixtures are compared with values predicted from Mobile Order theory using the measured solubility in each of the pure solvents as input parameters. The experimental mole fraction solubility of benzil in eight binary alcohol + 1-octanol solvent mixtures are also measured and compared with predicted values.
Discontinuous Thermal Expansions and Phase Transformations in Crystals at Higher Temperatures
The purpose of this investigation is to make more detailed studies of transformations. Fourteen compounds have been examined by high temperature X-ray diffraction for this purpose. The investigations have been carried out in such a way as to reveal: 1. the existence of transformations, 2. the influence of polarizability on thermal expansion, 3. the anisotropy of expansion, and 4. the discontinuity of thermal expansion.
Investigation of Ultratrace Metallic and Organic Contaminants in Semiconductor Processing Environments
Detection of ultratrace levels of metallic ion impurities in hydrofluoric acid solutions and alkaline hydrogen peroxide solution was demonstrated using a silicon-based sensing electrode. The sensor's operation principle is based on direct measurements of the silicon open-circuit potential shift generated by the interaction between metallic ions and the silicon-based sensing surface. The new sensor can have practical applications in the on-line monitoring of microelectronic chemical processing. The detection of Ag+ content in KODAK waste water was carried out successfully by this novel sensor. Trace levels of organic impurities in the hydrofluoric acid solutions and in the cleanroom air were characterized by multiple internal reflection infrared spectroscopy (MIRIS) using an organics probe prepared directly from a regular silicon wafer.
Investigation of Copper Out-Plating Mechanism on Silicon Wafer Surface
As the miniaturization keeps decreasing in semiconductor device fabrication, metal contamination on silicon surfaces becomes critical. An investigation of the fundamental mechanism of metal contamination process on silicon surface is therefore important. Kinetics and thermodynamics of the copper out-plating process on silicon surfaces in diluted HF solutions are both evaluated by several analytical methods.
Molecular Modeling Study of Oxidative Degradation of Polyperfluoroethers Catalyzed by Iron Fluoride Surfaces : An Extended Hückel Theory Approach
Extended Hückel methods are known to be a useful tool in understanding surface phenomena. Important quantities about atoms and chemical bonds can be obtained from this computationally simple method, although caution must be exercised in interpreting the results. Application of Extended Hückel calculations to large metal clusters reveals the role of d orbitals in solids. Basic ideas of constructing model compounds have been developed. Several model systems for surface chemisorption processes are constructed in order to understand the surface catalyzed oxidative degradation of polyperfluoroethers. The activation of oxygen molecules can be explained. The Lewis acid character of the iron fluoride surface can be predicted. Based on these results, mechanisms of the degradation processes are discussed.
I. On the Mechanism of Acid Promoted Rearrangement of PCU-Derived Pinacols II. Synthesis of a Trimethyltrishomocubyl Helical Tubuland Diol
I. Reductive dimerization of pentacyclo[^2,6.0^3,10.0^5'9]undecane-8-one-(PCU-8-one, 53) affords a mixture of meso and d,l pinacols (55a and 55b respectively). Acid promoted rearrangement of 55a and 55b conceivably can proceed with migration of C(7)-C(8) and/or C(8)-C(9) to form the corresponding pinacolone(s). In our hands, acid promoted rearrangement of 55a and 55b each proceeds with exclusive migration of C(7)- C(8) bond, thereby affording 58a and 59a respectively. Mechanistic features of this rearrangement are discussed. II. 4,7,1 l-trimethylpentacyclo[^2,6.0^3,l0.0^5,9]undecane-exo-4,exo-7-diol (23a) was successfully synthesized. This diol crystallizes in a helical tubuland lattice although its molecular structure does not possess C2 rotational symmetry.
Mixed Alkyllithim/Lithium Alkoxide Aggregates with Less Sterically Crowded Alkyl Groups
Mixed alkyllithium / lithium alkoxide aggregates in the form (RLi)n(ROLi)m were formed by addition of corresponding alcohol compounds at different Li/O ratios. Variable temperature 13C and 6Li NMR spectroscopy were used to verify the formation of the mixed aggregates and to study their behavior in hydrocarbon solution. Spectra for the lithium n-propoxide / n-propyllithium and iso-butyllithium / lithium iso-butoxide systems each indicated at least one mixed aggregate.
Rational Design of Metal-organic Electronic Devices: a Computational Perspective
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Organic and organometallic electronic materials continue to attract considerable attention among researchers due to their cost effectiveness, high flexibility, low temperature processing conditions and the continuous emergence of new semiconducting materials with tailored electronic properties. In addition, organic semiconductors can be used in a variety of important technological devices such as solar cells, field-effect transistors (FETs), flash memory, radio frequency identification (RFID) tags, light emitting diodes (LEDs), etc. However, organic materials have thus far not achieved the reliability and carrier mobility obtainable with inorganic silicon-based devices. Hence, there is a need for finding alternative electronic materials other than organic semiconductors to overcome the problems of inferior stability and performance. In this dissertation, I research the development of new transition metal based electronic materials which due to the presence of metal-metal, metal-?, and ?-? interactions may give rise to superior electronic and chemical properties versus their organic counterparts. Specifically, I performed computational modeling studies on platinum based charge transfer complexes and d10 cyclo-[M(?-L)]3 trimers (M = Ag, Au and L = monoanionic bidentate bridging (C/N~C/N) ligand). The research done is aimed to guide experimental chemists to make rational choices of metals, ligands, substituents in synthesizing novel organometallic electronic materials. Furthermore, the calculations presented here propose novel ways to tune the geometric, electronic, spectroscopic, and conduction properties in semiconducting materials. In addition to novel material development, electronic device performance can be improved by making a judicious choice of device components. I have studied the interfaces of a p-type metal-organic semiconductor viz cyclo-[Au(µ-Pz)]3 trimer with metal electrodes at atomic and surface levels. This work was aimed to guide the device engineers to choose the appropriate metal electrodes considering the chemical interactions at the interface. Additionally, the calculations performed on the interfaces provided valuable insight into binding energies, charge redistribution, change in the energy levels, dipole formation, etc., which are important parameters to consider while fabricating an electronic device. The research described in this dissertation highlights the application of unique computational modeling methods at different levels of theory to guide the experimental chemists and device engineers toward a rational design of transition metal based electronic devices with low cost and high performance.
Synthesis of Some Amine Steroid Derivatives
The preparation of 3B-(2-mercaptoethylamino)-cholestane was set as the goal of this thesis project.
Preparation of Alkoxy Derivatives of 2-Chloro-1,4-Naphthoquinone and 2-Chloro-5(8?)- Nitro-1,4-Naphthoquinone
This paper studies the the synthesis of certain alkoxy compounds of 2,3-dichloro-1,4-naphthoquinone that can be considered chemotherapeutic agents.
Addition Reactions of Some Aromatic Aldazines
The paper explores the conclusion that the addition compound was bicyclic, and that the addition of each of the two moles of cyanic acid was dependent upon the other.
A Study of Synthesis and Stereoisomerism of some Complex Cobalt Compounds
The purpose of this investigation is two-fold. Some new complex compounds, where one of the bidentate molecules is an optically active amino acid, were prepared, and attempts to separate those complex isomers by different methods were made. The replacement of the amino acids by optically inactive ligands was studied.
Synthesis of Polyaldehydes
Part one of this thesis concerns the polymerizability of some α,β-unsaturated monaldehydes and also relates the synthesis of some new polyaldehydes which have not been reported in the literature. Part two concerns the polymerization of glyoxal, the simplest dialdehyde, and the structure elucidation of this new polymer.
Experimental and Theoretical Study of Electronic Transitions in Phosphorus, Phosphoryl, and Thiophosphoryl Trichlorofluorides
This thesis is an investigation of the vacuum uv spectra of the phosphorus, phosphoryl, and thiophosphoryl trichlorofluorides in the region 1250 to 3000A. Assignments for absorption bands are made utilizing results from photoelectron spectra and ab initio calculations, oscillator strengths for absorption bands, and CNDO/2 molecular orbital calculations. Results from CNDO/2 calculations are compared with theoretical calculations, and experimental data are discussed with regard to the bonding in the compounds.
Kinetics of Reactions of Substituted Group VI B Metal Carbonyls with Phosphites
The problem with which this investigation is concerned is twofold. The initial part of the problem was to prepare a non-sterically demanding bidentate phosphine ligand, 1,2-bis-(Phosphino)ethane, (P-en), and to determine the kinetics of (P-en)Mo(CO)4 with phosphites via spectrophotometric methods in an attempt to determine if steric effects are directing the type of mechanism followed.
Studies Concerning the Production of Lactobacillic Acid in Lactobacillus Plantarum
This study is concerned with certain factors affecting the content of lactobacillic acid in Lactobacillus plantarum. Three main areas of investigation are reported herein. The effects of both the oxygen tension and the pH of the culture medium on the accumulation of lactobacillic acid were determined. In addition, monolayer studies were conducted to determine the influence of cyclopropane fatty acid content on the molecular packing of membrane lipids.
Cycloadditions of Ketenes with Allenes
The principle objective of this study is to conduct a definitive investigation into the cycloaddition of allenes and ketenes, with particular emphasis on halogenated ketenes.
Barbituric Acids. V. 5-substituted-mercapto Derivatives of 5-isoamylbarbituric Acid
Since no mention has been found in the literature of any 5-substituted mercapto-5-alkyl derivatives of barbituric acid, it was thought to be of interest to prepare a series of compounds containing sulfur attached directly to the barbituric acid nucleus. 5-substituted mercapto-5-isoamylbarbituric acids were chosen as representative of barbituric acids in which the alkyl group has a fairly high molecular weight.
Naphth [2,3-d] Imidazoline-2,4,9-Triones
The study of some acylurea derivatives of 2-amino-3-alkylamino- and -3-arylamino-1,4-naphthoquinones was undertaken to determine the course of reaction under conditions similar to those used by J. R. Hoover and A. R. Day to prepare 2-alkyl-1H-naphth[2,3-d] imidazole-4.9-diones from 2-acylamino-3-amino-1,4-naphthoquinones.
Nitration of Thiophene Analogs of DDT
Since thiophene very often yields compounds that are analogous to benzene derivatives in general physiological properties, it was decided to attempt to prepare the nitro and amino derivatives of 1,1,1-trichloro-2,2-bis-(2-thienyl)-ethane (V) as well as the nitro and amino derivatives of 2,2,3-trichloro-1,1-bis-(2-thienyl)-butane (VI).
The Dropping Gallium Electrode in Fused Salts
This paper is an attempt to appraise the usefulness of the dropping gallium electrode (DGE) in fused LiNO3-KNO3, to compare it with the dropping mercury electrode (DME), and to study the DGE in fused LiCl-KCl.
A Study of the Bromination Products of Phenylmercaptoacetic Acid
This investigation was begun in order to determine the nature of the 104 degree melting compound prepared by Ashmore and to determine which isomers and their relative amounts are produced during bromination of phenylmercaptoacetic acid.
Nuclear Magnetic Resonance Spectra of Some 1,2,4-triazoles
In the work undertaken here, NMR has been used to ascertain the structure of some 1,2,4-triazoles. The investigation provides information concerning the structure of potentially tautomeric triazoles such as hydroxy- and aminotriazole. Connected with this aspect of triazole chemistry is the larger problem of mesohydric tautomerism. The present study also yields information for a comparison of substituent effects in triazoles, N-heteroaromatic substances and benzene.
Conformationally Stable Cyclohexyllithium Compounds
Organolitnium compounds have been employed in synthetic worK for many years. However only during the last decade has much progress been made in establishing the mechanistic pathways for the reactions of these compounds.
The Electrochemical Properties of the Mercury/lithium Nitrate-potassium Nitrate Eutectic Interface
The original purpose of this investigation was to attempt to apply the coulostatic method directly to a molten salt system. The inability to duplicate the reported capacity data for this system resulted in an investigation of the probable cause of this discrepancy between the data obtained by these different methods (14, 15).
Kinetics and Mechanism Study of Diphenylketene Cycloadditions
From a review of the published work in the field of cycloadditions, it is evident that further research is needed to establish the mechanism of ketene cycloadditions. This work was initiated with the intent of obtaining kinetic data which will contribute to the elucidation of the mechanism of ketene cycloadditions.
The Stereochemistry of the Cycloaddition of Unsymmetrical Phenyl Ketenes to Cyclopentadiene
This dissertation is a study involving the synthesis and chemistry of arylhaloketenes and cyclopentadiene cycloadducts, and a study of the cycloadduct isomer distribution was begun.
High Temperature Enthalpies of the Lead Halides: Enthalpies and Entropies of Fusion
The objectives of this investigation were: 1. To establish calorimetrically the transition temperature for the orthorhombic to cubic transition exhibited by PbF₂ and to determine the enthalpy of this transition. 2. To determine if the solid-solid phase transitions claimed in the literature for PbCl₂, PbF₂, PbBr₂, and PbI₂ were of thermodynamic importance, and if so, to determine the enthalpies of transition. 3. To determine if the discontinuous thermal expansions reported by Hsu for the lead halides were of thermodynamic importance. 4. To obtain reliable heat content data for the lead halides in both the solid and liquid states.
The Photolysis of Ethyllithium and Triethylaluminum
The majority of interest in organolithium and organoaluminum compounds has centered around their potency as polymerization catalysts.
The Crystal and Molecular Structures of Tri-(p-Fluorophenyl)-Amine and Tri-(p-Iodophenyl)-Amine
Because of the need for data on the geometry of nitrogen in arylamines, the determination of the crystal and molecular structures of tri-(p-fluorophenyl)-amine (TFPA) and tri-(p-iodophenyl)-amine (TIPA) was undertaken as the subject of this dissertation.
The Electrochemical Reduction of Methyl Vinyl Ketone in Aqueous Solutions
This work is an in-depth study of a system with an approach designed to determine the electrode processes and the factors or conditions which control them.
Metal Complexes of 2,3-Quinoxalinedithiol
A series of new planar complexes with the dianion of 2,3-quinoxalinedithiol ligand has been prepared. The complexes have been characterized from the study of their analyses, magnetic moment, conductance, polarograms, electron spin resonance spectra, and electronic spectra, and compared with the available data on the corresponding maleonitriledithiolene and toluene-3,4-dithiolene complexes.
The Stereochemistry and Mechanism of Alkylhaloketene-Olefin Cycloadditions
The objectives of this research problem was to employ alkylhaloketene-olefin isomer distributions to aid in understanding the stereochemistry and mechanism of alkylhaloketene-olefin cycloadditions.
Aldohaloketenes and the Stereochemistry of Aldohaloketene Cycloadditions
The objective of this research problem was to synthesize aldohaloketenes and investigate the chemistry of this new class of ketenes.
Kinetic Studies and Vibrational Spectra of Disubstituted Metal Carbonyls
The oxidative elimination reactions of (5-X-phen)Mo(C0)₄ (X = H, CH₃, Cl, NO₂; phen = o-phenanthroline) and (3,4,7,8-(CH₃)₄-phen)Mo(CO)₄ with mercuric chloride in acetone have been investigated. In these reactions, a carbon monoxide group is replaced by two univalent ligands, accompanied by the corresponding increase in coordination number and formal oxidation state of the central metal atom, to give products of the type, (X-phen)Mo(CO)₃(Cl)HgCl. With the exception of (3,4,7,8-(CH₃)₄-phen), the substituted o-phenanthrolines were selected so as to minimize steric differences from one substrate to another while obtaining the widest range of pKₐ of the ligand.
Rearrangement of Alkylhaloketene-Cyclopentadiene Adducts in Basic Solution--A New Synthesis of 2-Alkyltropones
This research is concerned with determining whether the previously reported synthesis of tropolone by the solvolysis of the dichloroketene-cyclopentadiene adduct in sodium acetate and acetic acid could be used to prepare 2-alkyltropones from the adducts of alkylhaloketenes and cyclopentadiene. The information obtained from these rearrangements could be useful in determining the mechanism of the ring expansion of halogenated ketene-cyclopentadiene adducts to tropone derivatives.
Biological Inhibitors
Four isosteric series of plant growth-regulating compounds were prepared. Using an Avena sativa coleptile assay system, derivatives in series I and IV inhibited segment elongation to a greater degree than did comparable derivatives in series II and III.
Bonding Studies in Group IV Substituted n,n-dimethylanilines
The purpose of the present work is to study the effects of the trimethylsilyl and trimethylgermyl substituents on the N,N-dimethylamino ring system. Both ground and excited state interactions were studied and their magnitudes determined. The experimental data were then used in conjunction with molecular orbital calculations to differentiate among, and determine the importance of, d-p bonding, hyperconjugation or polarization of the trimethylsilyl group on the ground and excited state bonding.
The Recombination Rate Coefficient of Molecular Helium Ions in a Pulsed Afterglow at 1.86 Torr
The recombination rate coefficient for molecular helium ions has been measured in a pulsed afterglow at 1.86 Torr as a function of electron temperature and electron density without making a priori assumptions about the functional dependence. The concentrations of the molecular ions and electrons were measured and the source terms for the molecular ions were included in the rate equation.
The Crystal and Molecular Structures of 8-Hydroxyquinoline-N-Oxide and 2-Hydroxymethylpyridine-N-Oxide
This dissertation looked at the crystal structure analysis of 2-hydroxymethylpyridine-N-oxide sine this compound could provide data on both substituent effects and hydrogen bonding.
Electrochemical Dissolution of ZnO Single Crystals
The separation of oxidation-reduction reactions into individual half-cells with a resulting "mixed potential" is well known as a dissolution mechanism for metals; however, the mechanism by which non-conducting crystals lose ions to the solution has been studied only slightly.
Ketene Reactions: I. The Addition of Acid Chlorides to Dimethylketene ; II. The Cycloaddition of Ketenes to Carbonyl Compounds
Part I describes the addition of several acid chlorides to dimethylketene. The resulting 3-ketoacid chlorides were isolated and characterized. Part II describes the cycloaddition of several aldoketenes to chloral. The ketenes were generated in situ by dehydrohalogenation and dehalogenation of appropriately substituted acyl halides.
Aromatic Amino Acid Studies
Pyridine ring analogs of the aromatic amino acids phenylalanine and tyrosine were synthesized and studied in microbiological and mammalian systems.
Ketene Carbodiimide Cycloadditions
It was proposed to study the cycloaddition of ketenes and carbodiimides in some detail. The first objective was to investigate the general applicability of the reaction as a tool for the synthetic organic chemist in the preparation of a new class of substituted β-lactams; i.e., imino-β-lactams. It was proposed for this part of the research problem to look for the intermediate, either directly or indirectly, by trapping experiments. It was further proposed to study substituent effects in the ketene and carbodiimide and also Investigate the effect of solvent polarity on the reaction rate. From these data, it was hoped that the mechanism of the cycloaddition reaction could be elucidated.
Infrared Studies of Group VIB metal Carbonyl Derivatives
With three different proposals for the bonding in metal carbonyls, it was decided to look into the situation more thoroughly in order to see what other evidence was available to support or refute any of these ideas. It became obvious that a definite contradiction existed between the kinetic evidence of various metal carbonyls, and the concept of MC bond strengths as predicted by Cotton's theory.