Chemistry Commons^™

A Novel Synthesis Of Cyclic And Acyclic 3-Alkenoic Acids Via Ionization/Elimination Of Β-Lactones, Stephen Lucas Maluleka

Masters Theses

Exposure of spiro β-lactones and 3-substituted 4,4-dialkyl oxetan-2-ones to magnesium bromide in diethyl ether solvent resulted in the smooth generation of β,γ-unsaturated acid derivatives in high yield and isomeric purity. It is believed that this reaction occurs via the formation of a stable tertiary carbocation at the β-carbon resulting from cleavage of the carbon-oxygen sigma bond due to the complexation of magnesium cation with the ring oxygen atom. Rapid loss of an adjacent proton then furnishes the unsaturated acids. The β-lactone precursors were prepared by the dehydration of β-hydroxy acid derivatives (obtained from the condensation of ketones with acetic acid …

Micellar Catalyzed Hydrolysis Of Hydroxamic Acids By Perfluorooctanoic Acid, Mohammad Hashem Akhavan Tafti

Masters Theses

The work reported herein demonstrated that a perfluorocarboxylic acid does indeed behave as a reactive counterion surfactant exhibiting micellar catalysis, this conclusion was further verified by subsequent experimentation.

Rates of acidic hydrolysis of octano-, phenylaceto-, and 4-bromo phenylacetohydroxamic acid have been determined in aqueous perfluorooctanoic acid--a reactive counterion surfactant system. Typical micellar catalysis was observed for the hydrolysis of octanohydroxamic acid but not for the arylacetohydroxamic acids.

Further investigation into finding a more water soluble surfactant which has reactive counter ions is suggested in order to test the theoretical equation (based on the pseudo phase model) appropriate for this surfactant …

Synthesis And Study Of Novel Quinoxaline Di-N-Oxide And 3-Acyl-2-Methylquinoxaline Di-N-Oxides, Cyprian Okwara Ogbu

Masters Theses

This research project consists of two parts. The first involved the synthesis of a novel quininoxaline di-N-oxide via benzofuroxan. The second part was the use of this compound as a synthetic precursor.

It was assumed that 3,4-dimethylaniline would be successfully converted to 5,6-dimethybenzofurazan 1-oxide (5,6-dimethybenzofuroxan) through a sequence of reaction steps. Fortunately, this assumption was correct as the desired compound was produced. This compound was utilized in synthesizing the novel 3-acetyl-2,6,7-trimethylquinoxaline 1,4-dioxide. From the structure of this adduct, it is believed that it will take part in condensation reactions associated with methyl ketones without disrupting the quinoxaline di-N-oxide framework, and …

Synthesis And Reactions Of A-Diketones And Preparation Of Some New Benzimidazoles, Mohamad Reza Agharahimi

Masters Theses

This report will discuss the synthesis of 2,5-dl-(p-chlorophenyl)-3,4-dioxoadiponitrile and its reactions. This compound exists in the form of 4,4'- dichloropulvinic nitrile which is a precursor to 4,4'-dichk>rovulpinic acid. These compounds have been shown to have antiinflammatory activity in rats.

The benzimidazole and pyridazine derivatives of 4,4'-dichioropulvinic nitrile and the benzimidazole derivative of 4,4'-dichk>rovuipinic acid are another group of compounds that are also believed to have useful biological activities. The Pinner synthesis of imidates is used to make the intermediate to the benzimidazole derivative of 4,4'-dichloropulvinic nitrile.

This report will include the methodology of the reactions and …

A Synthetic Approach To Novel Heterocyclic Herbicides, Paul Antony Pathadan

Masters Theses

The purpose of this research study was to prepare novel heterocyclic herbicides. The first phase of the project was to synthesize 1-(nitromethyl)-4-phthalazone.

In the second phase 1 - (nitromethyl)-4-phthalazone was treated with 1,3-propane-dithio-di-p-toluene sulfonate in presence of sodium hydride to get the target compound 4-(1'-nitro-l,3-dithiane)phthalazone.

It is believed that this compound might block the electron transport system of aerobic cells¹ . So further investigation of this compound may lead to novel herbicides.

Thermal, Mechanical And Interfacial Characterization Of A Fiberglass Reinforced Plastic Composite, Theodore J. Williams

Masters Theses

The effects of a glass fiber reinforcer on the properties of poly(methyl methacrylate) were evaluated. A silane coupling agent (M8550 Petrarch Systems, Inc.) was employed to promote adhesion between the materials. FTIR analysis, ESCA/Auger and SEM techniques were used to characterize the silane coating.

The mechanical properties, such as bending strength, improved with an increase in the volume percent of fiber. The addition of the M8550 silane directly into the monomer solution showed the most improvement, 23 percent increase, when compared to the uncoated glass fiber. The glass transition temperature as measured by DSC and the heat distortion temperature (HDT) …

Coal Desulfurization Using Pyrite Conversion Through Dielectric Heating, Daniel C. Cleaveland

Masters Theses

The Illinois State Geological Survey is currently developing a three step coal desulfurization process which depends upon the in-situ generation of catalytic troilite (FeS) by reduction of the pyrite (FeS₂) present in the mineral fraction of coal. After catalyst generation, ethanol is added to the system and is dehydrogenated to acetaldehyde and hydrogen which removes organic sulfur as hydrogen sulfide. The research reported in this thesis shows that the process can be improved by the use of dielectric heating in place of thermal heating for catalyst generation and perhaps organic sulfur removal. It is found that pyrite reduction …

Characterization Of The Lipopolysaccharides From Rhizobium Phaseoli Symbiotic Mutants, Francisca Garcia

Masters Theses

The lipopolysaccharides (LPSs) of the Rhizobium phaseoli CE3 and its mutants CE109, CE309 and the transconjugate Rhizobium leguminosarum LB2/109.11 were isolated and analyzed by gas chromatography (GC) and ¹H nuclear magnetic resonance (NMR) spectroscopy. CE3 is the wild type strain which is nodulation-proficient (Nod⁺). Strain CE109 and CE309 have a transposon, Tn5, inserted into Region I and Region III of their respetive chromosomes. Mutants CE109 and CE309 are defective in nodule development (Ndv^-). Transconjugate R. leg. LB2/109.11 has the DNA of the R. leg. LB2 wild type and also Region I portion of the CE109 …

Kinetics Of The Metal-Exchange Reaction Between N-(2-Pyridylmethyl)Iminodiacetatonickel(N) And Copper(Ii), Kassahun W. Beyene

Masters Theses

The reaction between N-(2-pyridylmethyl)iminodiacetatonickel(II) and copper(II) was studied spectrophotometrically between pH 2.30 and 3.30 over a 10-fold variation in copper concentration at an ionic strength of 1.25M, and a temperature of 25.0+0.1^oC. The reaction is first order in both NiPyIDA and copper(II). Terms involving proton attack and a copper dependent dissociation of the nickel complex were resolved from the data. Evidence is given for a stepwise unwrapping mechanism PyIDA from the nickel complex, followed by copper attack to give a dinuclear intermediate. A general mechanism is presented which is consistent with the kinetic data.

Comparisons to analogous nickel-aliphatic …

The Preparation And Reaction Of Novel Glycosyl Ureas And Thioureas, Robert Scott Johnson

Masters Theses

No abstract provided.

Sequential Solvent Extraction Of Argonne Premium Coal Samples, Wanping Mai

Masters Theses

Five coals from the Argonne Premium Coal Sample program, ranging in rank from sub-bituminous to low volatile bituminous, before and following artificial weathering, were exhaustively extracted with solvents in the sequence: toluene, tetrahydrofuran, N,N-dimethyl-formamide, and pyridine.

Sequential solvent extraction reveals more insight into the coal structure than single solvent extraction because fractions are isolated on the basis of both molecular size and polarity. The recovered extracts and residue from the extraction are monitored by FT-IR spectroscopy, elemental analysis, phenol content, solvent swelling, and Gel Permeation Chromatography analysis (GPC). The extraction results show that for fresh coals, the total extract yields …

Electrochemical Studies Of Iron, Cobalt, And Nickel Complexes Of Bidentate Phosphine Thioether Ligands, Robert L. Turner

Masters Theses

The electrochemical behavior of a series of cationic complexes, [Ni(S-P)₂]²⁺, [Fe(S-P)₂(CH₃CN)_2.5]²⁺ and [Co(S-P)₂CH₃CN]²⁺, where S-P= (C₆H₅)₂PCH₂CH₂SCH₂CH₃, has been examined in acetonitrile on mercury and platinum electrodes. The nickel compound was reduced in two reversible diffusion controlled, one-electron transfers. Addition of PPh₃ (Ph=C₆H₅) and S-P caused a positive potential shift in the nickel(I) to nickel(0) wave. An EC mechanism was postulated to account for this …

The Synthesis And Characterization Of Polycarbonates Based On 1,1'-Dihydroxyethyl-2,2'-Biimidazole, Judith J. Garces

Masters Theses

"The synthesis of polycarbonates formed by the reaction of 1,1'-dihydroxyethyl-2,2'-biimidazole and diphenyl or diethyl carbonates was investigated and the products formed were characterized. The molecular weights of the polymers were dependent on catalyst, ratio of starting materials, nature of carbonate (aromatic or aliphatic) and method of polymerization. Isolated polymers exhibit a linear structure. They have no well-defined melting points (melting pt. range of 280- 330⁰C) indicating low degree of crystallization, and undergo less than 9% decomposition below 200⁰C"--Abstract, page ii.

The Structure Of O-Antigen From Lipopolysaccharide Of Rhizobium Leguminosarum 128c53 And Its Nod-Fix-Mutant, Tong-Bin Chen

Masters Theses

The LPS of R. leguminosarum 128C53 sm^r rif^r (a streptomycin and rifampicin resistant strain of wild type 128C53) and its mutant ANU54 (nod^-, fix^-) were isolated from the bacterial pellet by hot phenol/water extraction followed by gel filtration chromatography. The O-antigen was isolated by mild-acid hydrolysis of the LPS and purified by gel filtration chromatography using a Sephadex G-50 or G-25. The following results were the same for both the parent and mutant. The composition and linkage of the O-antigen were determined by gas chromatography (GC), GC-mass spectrometry, ¹H and ¹³C nuclear …

Isolation And Partial Characterization Of Serogroup Specific Antigens From Bradyrhizobium Japonicum 61a123, Miguel Eduardo Carrion

Masters Theses

Serogroup specific antigens of Bradyrhizobium japonicum 61A123 were isolated using an immunochemical assay. Bacterial antigens were isolated by phenol-water extraction. These antigens were detected by inhibition of an enzyme linked immunosorbant assay (ELISA). Low pressure chromatography and digestion with proteinase K served to purify the antigens. Chemical composition was determined by gas chromatography (GC), mass spectrometry (MS), and colorimetric assays. The antigens were also characterized by sodium dodecyl sulfate (SDS)-polyacrylamide gel electrophoresis, and immunological properties determined by ELISA. These antigens were shown to be lipopolysaccharides (LPSs) containing fucose, a 2-amino-2,6-dideoxy hexose (unidentified), glucose and mannose as the major sugars, along …

High Performance Liquid Chromatographic Determination Of Thromboxane B2 In Human Serum As A Methoxime-Panacyl Ester Derivative, Robert H. Pullen

Masters Theses

No abstract provided.

Reactive Counterion Surfactant Catalysis Of Hydroxamic Acid Hydrolysis With Perfluorooctanoic Acid, Mohamed El-Sayed Ayoub

Masters Theses

A micellar effect upon the rate of hydrolysis of hydroxamic acids in aqueous perfluorooctanoic acid has been demonstrated for hydroxamic acids with chain lengths of six , eight, and ten carbons. In this system the counterion, hydrogenion, is a catalyst. Typical rate constant-surfactant concentration profiles for micellar catalysis were obtained. The results for these hydrolyses are consistent with the pseudo-phase model for micellar effects.

In addition the Arrhenius activation energies were determined for the reaction of octanohydroxamic acid at surfactant concentrations above and below the critical micelle concentration of the surfactant. The activation energy is lower for reaction in the …

Simultaneous Knudsen- And Torsion-Effusion Measurements Of The Vapor Pressures Of Triphenyl Aluminum And Triphenyl Boron, Steven Wayne Govorchin

Masters Theses

The sublimation pressures of triphenyl aluminum and triphenyl boron have been determined from simultaneous measurements of the rate of mass effusion and torsional recoil. For triphenyl aluminum the measured vapor presures are expressed by the equations:

logio (P_k/P°) = (12.76 ± 1.25) - (8214 ± 572) (K/T)

logio (P_t/p °) = (12.83 ± 1.34) - (8206 ± 615) (K/T)

where P_k and P_t are the pressures measured by the Knudsen-effusion and torsional-recoil techniques, respectively, and p° = 101.325 kP_a. For triphenyl boron the measured vapor pressures are expressed by the equations:

log …

Electrochemical Studies Of Transition Metal Carbonyls, Dwayne Edward Cooper

Masters Theses

The electrochemical oxidation of (OC)₅MP-PM'(CO)₅ (M=Cr, Mo, W; M'=Cr, Mo, W; M=M' or M≠M'; P-P=Ph₂PCH₂CH₂PPh₂) and the reduction of the oxidized products in a 0.1 M tetrabutyl-ammonium perchlorate methylene chloride solution at a platinum disc working electrode with a Ag/AgCl reference electrode have been studied. The number of electrons in the oxidation step was determined by comparison with the one electron oxidation of ferrocene which had a peak potential at +0.15 V.

The cyclic voltammograms of the homobimetallic and heterobimetallic complexes display two general chacteristics: quasi-reversible or irreversible one …

Synthesis Of Phosphine Trans-Substituted Derivatives Of Iron Pentacarbonyl, Karl Heinz Hecker

Masters Theses

The synthesis of trans-Fe (CO)₃(PR₃)₂ (PR₃ = PPh₃, PPh₂Me, PPh₂CHCH₂, P(c-C₆H₁₁)₃, P(n-C₄H₉)₃, PPh₂H) can be achieved by refluxing iron pentacarbonyl under reducing conditions in the presence of ligand in 1-butanol. Addition of iron pentacarbonyl to a 1-butanol solution of sodium borohydride at room temperature results in a quantitative conversion of the iron carbonyl complex to the corresponding mononuclear formyl complex. Upon heating the initially formed formyl species decomposes to form the …

Syntheses And Electrochemistry Of Monosubstituted Carbonyl Complexes Of Low Valent Ruthenium, Nor Azowa Ibrahim

Masters Theses

The reactions of Ph₂MeP and PhMe₂P with (PPh₃)₄RuCl₂ yield (PPh₂Me)₄RuCl₂ and (PPhMe₂)₄RuCl₂, respectively. These complexes have been shown by conductivity studies to be dissociated in acetonitrile and exist as [(PPh₂Me)₄RuCl(CH₃CN)]Cl and [(PPhMe₂)₄RuCl(CH₃CN)]Cl. When carbon monoxide was bubbled into these solutions, monocarbonyl complexes were obtained. Elemental analyses, ¹H NMR, ³¹P NMR, infrared spectroscopy, conductivity measurements, and polarography were used to analyse the products, (PPh₂Me)_{2 …}

Enhancement Of Ether Cleaving Reactions By Intramolecular Hydrogen Bonding, Nobumi Takemura

Masters Theses

Rate constants of cleavages of fourteen alkyl-aryl ethers with HI, KI, or LiI in pyridine at 50-150°C were determined under pseudo first order conditions. The following ethers which have a six-membered ring intramolecular hydrogen bond underwent a bimolecular nucleophilic displacement by iodide ion in pyridine: 8-methoxy-1-naphthalenol, 8-ethoxy-1-naphthalenol, 2-methoxybenzoic acid, and 2-hydroxybenzyl methyl ether. The following ethers which lack a six-membered ring hydrogen bond were not cleaved or underwent cleavage slowly compared with the hydrogen bonded compounds: 1,8-dimethoxynaphthalene, 1,8-diethoxynaphthalene, 1-methoxynaphthalene, 4-methoxybenzoic acid, methyl 2-methoxybenzoate, 2-methoxybenzyl methyl ether, and 4-methoxybenzyl methyl ether. The pattern of ether reactivity indicated that a six-membered ring …

Empirical Equations For Activity And Osmotic Coefficients, N. Ragunathan

Masters Theses

A system of equations for fitting the experimental activity and osmotic coefficients of single and mixed electrolytes in aqueous solutions has been empirically developed in the present research. The results obtained through the equations developed here are comparable to the Pitzer equations in terms of accuracy and range of fitting. The equation for activity coefficient developed in the present research compared to the Pitzer activity coefficient equation has a form which is conveinient for computational purposes. The equation for activity coefficients is ln g = -╎Z_mZ_x╎A_D[I^1/2/(1 + bI^1/2)] + E …

Studies Of Sodium Dodecylbenzenesulfonate-Water-Electrolyte Interactions, Xiaoxiang Zhu

Masters Theses

A surfactant selective electrode using a PVC membrane was constructed. A surfactant (sodium dodecylbenzene-sulfonate)-H₂O system was studied at 15°, 19°, 25°, and 40°C with the PVC electrodes, a Na⁺ selective electrode, and a conductivity bridge. Pre-micelle regions at the above temparatures were observed. The critical micelle concentrations (CMC^b) obtained by the PVC electrodes in salt-free systems are: 1.63x10^-3 M at 15°C, 1.48x10^-3 M at 19.1°C, 1.52x10^-3 M at 25°C, and 1.73x10^-3 M at 41.6°C. The CMC'c obtained by the Na⁺ electrode are: 1.62x10^-3 M at 15°C, 1.37x10^-3 M …

Characterization Of The Capsular Polysaccharides On Cell Membranes Of Rhizobium Trifolii And Three Of Its Nod- Mutants, Jesse Ardosa

Masters Theses

The ever-present specter of the inavailability of food production to increase in direct proportion to population growth haunts practically every nation of the world. As more and more tracts of land are incorporated to accommodate expanding cities, they become less available for food production. Emphasis, therefore, is placed on obtaining a higher yield per acreage planted. Since fertilization is not reliable in the long term due to an eventual depletion of raw materials for fertilizers, the ability of plants like legumes to assimilate free soil nitrogen on their own has become increasingly important [1,11,14,17]. However, the mechanisms involved are still …

Isolation And Partial Analysis Of Proteins And Polysaccharides Of Rhizobium Trifolii, Manuelito M. Ordonez

Masters Theses

The outer membrane and periplasmic proteins of Rhizobium trifolii ANU 843 and its mutants ANU 851 and ANU 845(pRt150) were isolated and analyzed by polyacrylamide gel electrophoresis (PAGE). ANU 843 is the wild type strain which possesses all the characteristics necessary for nitrogen fixation. ANU 851 has a transposon (Tn5) inserted into the nodD gene of the root hair curling region of the symbiotic plasmid. It has lost its ability to cause root hair curling and therefore can not form nodules and can not fix nitrogen. ANU 845(pRt150) harbors only the 5.5 kb root hair curling region of the …

The Design And Construction Of Microprocessor-Computer Controlled Rapid Scanning Fiberoptic Spectrophotometer, Kathleen Marie Tobin

Masters Theses

Conventional spectrophometers require the transfer of a sample to a cuvette for obtaining spectra. The measurement of absorbance in situ can be accomplished using a fiber optic probe which can be placed directly in the sample. The fiber optic probe also minimizes environmental factors such as thermal or vibrational which may affect the absorbing species. A rapid scanning speed allows for essentially simultaneous wavelength monitoring.

The effect of coupling a rapid scanning spectrophotometer with a fiber optic probe provides for an extremely versatile system. When used in comjunction with a microprocessor or computer, this approach offers advantages such as data …

Reactions Of Supercritical Water With Quinoline And Related Compounds, Zhuangjie Li

Masters Theses

One function which coal processing can perform is the removal of heteroatoms to yield a less polluting product. The removal of nitrogen atoms from the model compounds quinoline and aniline, which are believed to be representative of the nitrogen functional groups found in coal, was studied using supercritical water (SW) as the fluid. Water at these conditions serves as a reactant, helping to promote the rupture of the heterocyclic ring and in the removal of nitrogen attached to an aromatic ring. Heterocyclic ring rupture leads to the formation of several methylated products, methyl and dimethyl anilines, phenols and quinolines. The …

Synthesis Of Pyridine Nucleosides By Cycloaddition Reactions And Synthesis And Condensation Reactions Of 4-Aryl-2-Oxytetronimides, Glenn L. Heise

Masters Theses

Experiment 1: The reaction of various glutaconaldehyde salts (Na⁺ or K⁺) with glycosyl isothiocyanates has resulted in the formation of a novel class of compounds. Relatively mild conditions were utilized for the synthesis which occurs in four steps, and in good yield, starting from glucpseptentaacetate. These reactions were found to be regiospecific. The unique physical and spectral properties of the model compound 1-(2,3,4,6-tetra-0-acetyl-β-D-glycopranosyl)-2-thiono-3-pyridine carboxaldehyde are also discussed.

Experiement 2: Early synthetic methodologies have recently been utilized in the synthesis of 4-aryl-2-oxytetronimides. These compounds have been found to participate in condensation reactions with various substituted o-phenylene diamines. A …

Cobalt (Iii) Complexes With (R) - 1, 2-Diaminopropane And Its Derivatives, Christopher John Rudy

Masters Theses

(R)-1, 2-Diethylaminopropane (N,N' -Etlpn) was prepared by LialH₄ reduction of (R)-1-2-diacetamidopropane (m.p. 153.5°C). The [∝]_D of N, N'-Melpn and N,N'-Etlpn was related to that of 1pn and was concentration dependent. (R)-1, 2-Dibenzylaminopropane was prepared. Complexes of trans, trans- and trans, cis-dinitrobis ((R)- 1, 2-diethylaminopropane) cobalt (III) were perpared. The hexadecadal rule was used to help assign the nitro oxygens of the complexes to sectors adjacent to the axial amine hydrogens and within the boundaries of the λ- chelate rings. The CD spectra was solvent dependent. The instability of trans-[Co (III)N₄X₂]⁺ complexes was related …