Chemistry Commons^™

Synthesis Of Potential Agrochemicals And Reactions Of Vinamidinium And Azavinamidinium Salts With Organometallic/Borane Reagents And Activated Nitrales, Charles N. Moorefield

Retrospective Theses and Dissertations

This report discusses research which was conducted in two areas: the synthesis of potential agrochemicals and the study of vinamidinium and azavinamidinium salt chemistry. Four classes of compounds were synthesized and characterized in the study of new potential agrochemicals. These compounds include diacylhydrazines, semicarbazides, 2,5-disubstituted-1,3,4-oxadiazoles and bis-2,5-disubstituted-1,3,4-oxadiazoles. The reaction of [3-(dimethylamino)-2-azaprop-2-en-1-ylidene] dimethylammonium chloride (Gold's reagent) with organometallic/borane reagents was examined in efforts to find convenient syntheses for N,N-dimethylamino substituted alkyl and aryl compounds. Additionally, the reaction of 1,5-diazapentadienium chloride (Nair's reagent) with nitrile activated alkanes was examined to find a convenient synthesis of 3-substituted pyridines. Subsequent intramolecular ring closure of …

Solvents For Use In The Extractive Distillation Of Piperylene Concentrate, Abdulhadi Sagga

Retrospective Theses and Dissertations

This report describes an evaluation of the effectiveness of different solvents and solvent-organometallic compound mixtures for use in the extractive distillation of a piperylene mixture, consisting of five carbon olefins and diolefins obtained as a byproduct from an ethylene feedstock production plant. The most effective solvent is judged to be the one which gives the best separation of the lowest boiling and highest boiling points of the key components in the mixture. In this study twenty solvents and solvent mixtures were tested. Acetonitrile was found to be the most effective solvent and nitromethane the next most effective.

Preparation Of 2,5-Diaryl-1,3,4-Oxadiazoles, Joachim D. Dobe

Retrospective Theses and Dissertations

This report regards the research conducted in the synthesis of 2,5-disubstituted-1,3,4-oxadiazoles as potential insecticides which are closely related to the known insecticide DOWCO 416^R, 2,5-bis(2,4-dichlorophenyl)-1,3,4-oxadiazole. The following compounds were synthesized: 2-(2,4-dichloro-5-nitrophenyl)-5-(2,4-dichlorophenyl)-1,3,4-oxadiazole, (2-(2,4-dichloro-5-nitrophenyl)-5-phenyl-1,3,4-oxadiazole, 2-(2,4-dichloro-5-aminophenyl)-5-aminophenyl)-5-(2,4-dichlorophenyl)-1,3,4-oxadiazole and 2-(2,4-dichloro-5-aminophenyl)-5-phenyl-1,3,4-oxadiazole.

From the commercially available starting material, 2, 4-dichlorobenzoic acid, preparation of the above compounds involved nitration, reduction, esterification, preparation of monoacylhydrazines, preparation of substituted diacylhydrazines and preparation of 2, 5-disubstituted-1, 3, 4-oxadiazoles. All these compounds were characterized via NMR and infrared spectroscopy. In addition, this report includes discussion and recommendations concerning the experimental procedures and conditions for the preparation of these compounds.

Separation Of Piperylene Concentrate Via Metathesis Catalysis, Donald R. Allred

Retrospective Theses and Dissertations

Diolefin metathesis, using a Re2O7 catalyst, failed to show a reactivity difference due to conjugation of double bonds. However, the same system allows reaction of pentadiene while not affecting cyclopentene yielding a successful reaction ΓÇô separation scheme for a piperylene concentrate mixture.

Synthesis Of Potential Insecticides And New Synthetic Applications Of Vinamidinium And Azavinamidinium Salts: Reactions With Reducing Agents And Nitro Compounds, Michael J. Lizzi

Retrospective Theses and Dissertations

This report discusses the research conducted in two areas: the synthesis of potential insecticides and the investigation of vinamidinium and azavinamidinium salt chemistry. Firstly, four classes of compounds were synthesized and characterized in the investigation of new potential insecticides. These classes of compounds include a-formamidine methyl esters, amidines, diacylhydrazines and 2,5-disubstituted-1,3,4-oxadiazoles and were characterized via NMR and infrared spectroscopy. This account also reveals and discusses the experimental conditions and procedures necessary for the preparation of these potential insecticides. Secondly, the reaction of [ 3-(dimethyl amino)-2-azaprop-2-en-1-ylidene] dimethyl ammonium chloride (Gold's Reagent) with nucleophiles such as activated (nitro) methylene compounds was examined …

Synthesis And Evaluation Of Polymeric Ether Glycol Derivatives For Use As Transducer Fluids, Cynthia K. Mccurry

Retrospective Theses and Dissertations

A series of end-capped PAG (n-butyl, n-alkyl substituted polypropylene glycol) and PPGs (bis-di-alkyl-,bis-di-halo-, bis-di-fluoroalkylpolypropylene glycol) were synthesized. Optimum reaction conditions were determined in regard to time, temperature, reaction ratios, and solvents for each of the PAG and PPG derivatives. An investigation of the named PAG and PPG derivatives as potentially new sonar transducer fluids was carried out. Density, viscosity and sound speed measurements with regard to temperature, as well as water solubility measurements, were carried out for several of these derivatives. The desirable properties possessed by several of these derivatives make them of potential value in application as transducer fill-fluids.

Synthesis And Evaluation Of Polymer Supported Homogenous Oxidation Catalysts, Raymond J. Riley

Retrospective Theses and Dissertations

Polystyrene bis(salicylaldehyde)-propylene-1,3-diiminato Cobalt (II) [salen] and Polystyrene bis(2,4-pentanedione)-propylene-1,3-diiminato Cobalt (II) [BAE] were prepared stepwise from chloromethylated polystyrene. In addition, a new preparation of a Schiff base was attempted resulting in Polystyrene bis(salicylaldehyde)-isobutylene-1,3-diiminoato Cobalt (II) being produced. Optimum reaction conditions were determined with regard tot ime, temperature, reaction ratios and solvent for each step for the reaction. The ability of the above named Cobalt (II) Schiff bases to oxidize 3-methyl indole to give the corresponding o-formylaminoacetophenone was also studied. One polymer-bound Schiff base cobalt catalyst (co-salen) demonstrated a very small amount of catalytic activity resulting in a minimum amount of o-formylaminoacetophenone …

Reactions Of (3-(Dimethylamino)-2-Azaprop-2-En-1-Ylidene) Dimethylammonium Chloride (Gold's Reagent) With Carboxylic Acid Derivatives And Grignard Reagents, Dale E. Polk

Retrospective Theses and Dissertations

An azavinamidium salt, [3-(Dimethylamino)-2-azaprop-2-en-l-ylidene] dimethylammonium chloride was reacted with primary amides, esters containing an ╬▒-methylene group and Grignard reagents. The reaction of this azavinamidium salt with amides and esters produced respectively, acyl amidines and enamino esters. Both of these products were produced in high yields by using relatively mild conditions. Reaction of the salt with Grignard reagents resulted in a novel synthesis of aldehydes. This aldehyde synthesis was shown to be of general utility and to proceed in high yields.

Evolution Of A Cooling Water Treatment Program At A Chemical Processing Plant, Lawrence P. Everson

Retrospective Theses and Dissertations

During the construction of a chemical processing plant, a polyphosphate product was selected for use as a corrosion inhibitor in the open recirculating cooling tower system. After several months of operation, problems in the system made evident the fact that polyphosphate as a corrosion inhibitor was not acceptable. An organic corrosion inhibitor was substituted for the phosphate, resulting in improved corrosion protection and the elimination of phosphate fouling.

The Separation Of Piperylene Concentrate By Extractive Distillation, Mary Jane Curnutte

Retrospective Theses and Dissertations

Piperylene concentrate, the five-carbon olefin and diolefin by-product of ethylene production, is being produced in increasing quantities as liquid feedstocks become more prevalent. At present, the concentrate is used primarily in resin production for the adhesives industry. Since this use is economically unattractive, a separation of the concentrate into pure compounds is industrially desirable. The evaluation of the effectiveness of several solvents for extractive distillation of piperylene concentrate was performed. This study resulted in the selection of acetonitrile as the most effective and most economical solvent investigated. Various distillation conditions were studied and optimization was based on these results.

A Study On The Concentration Of Citrus Essential Oils By Adsorption, Albert Joseph Kruger

Retrospective Theses and Dissertations

Deterpenation by concentration of the flavor bearing oxygenated compounds present in Citrus Essential Oils using the column chromatographic method and the parameters affecting the adsorption of these oxygenated compounds at maximum economy versus reasonable efficiency in separation from the non-oxygenated compounds have been studied. Particular attention was given to the maximum number of adsorption-desorption-regeneration cycles that a single column charge could be subjected to before the adsorbent should be replaced. The results of this study suggested the following conditions are of importance with regard to the development of an efficient and economic operation: 1) deactivation of the silica gel column …

Ruthenium-Catalyzed Hydrogenation Of Aqueous Sodium Bicarbonate, Duane P. Covino

Retrospective Theses and Dissertations

This research report investigated the ruthenium-catalyzed hydrogenation of aqueous sodium bicarbonate. Subjects of the investigation included: the "blank" effect of the 316 stainless steel reactor in the batch mode; the catalytic activities at 150°C for unsupported ruthenium, including ruthenium purge and the metal produced from the in situ reduction of RuCl3·1-3H2O and Ru(IV)O2·H2O; the catalytic activities at 150°C for supported ruthenium including 4.05% w/w ruthenium on alumina, 5.25 and 20.85%w/w ruthenium on molecular sieve SK-41 (ammonium - substituted Y-type), 3.34 and 17.48% w/w ruthenium on SK-41 (prepared by the in situ reduction of the RuCl3·1-3H2O exchange sieve); orders of reaction …

Cyclodimerization Of 1,3-Pentadiene With Homogeneous Nickel Catalyst, Morteza Soltani

Retrospective Theses and Dissertations

Piperylene concentrate is a complex mixture of 5-carbon unsaturated hydrocarbons obtained as by-products when naptha or gas oils are cracked. The major component in this mixture is 1,3-pentadiene. The cyclodimerization of 1,3-pentadience in piperylene concentrate by using a nickel catalyst was studied. Various types of ligands were used in the preparation of the nickel catalyst. The effect of each ligand on activity of the catalyst in dimerization of diene, on conversion, and on yield of reaction were investigated. The effect of reaction conditions, such as temperature, pressure, and reaction time, on conversion of monomer, yield of dimer, and selectivity of …

Separation Of 1,3-Pentadiene From A Five-Carbon Olefin Mixture By Use Of 13x Molecular Sieves, Samuel G. Maller

Retrospective Theses and Dissertations

Piperylene concentrate is a complex mixture of 5-carbon unsaturates. The major components are trans-1,3-pentadiene and cyclopentene. The object of this work is to form a product high in cyclopentene and a product high in the pentadienes, through the use of 13X zeolite molecular sives. Separation by molecular sieves is difficult because of the tendency of trans and cis pentadience to polymerize o the sieve and to thus decrease the adsorptive capacity of the sieve. Nitrogenous bases (dimethylamine, pyridine, and piperidine) were used in an attempt to neutralize any acid sites on the sieve. Dealumination by EDTA was used to decrease …

Isomerization And Dehydrocyclization Of 1,3-Pentadiene, Thomas E. Marcinkowski

Retrospective Theses and Dissertations

Piperylene concentrate is a complex mixture of 5-carbon unsaturated hydrocarbons obtained as a by-product when naphtha or gas oils are cracked. The major component in this mixture is 1,3-pentadiene. During the course of this study, a number of trials, utilizing liquid phase reaction conditions, were made to investigate the geometric isomerization of 1,3-pentadiene and its separation from the piperylene concentrate. Isomerization was accomplished employing catalytic amounts of iodine at temperatures ranging from 0°C to reflux. Using this method, the maximum amount of trans-1,3-pentadiene obtained was 70% as compared to 51% in the piperylene concentrate. Recovery of the product was 90%, …

Preparation Of A Polymer Supported Cobalt (Ii) Schiff Base Catalyst, Susan L. Fuhrman

Retrospective Theses and Dissertations

Polystyrene bis(salicylaldehyde)-propylene-1,3-diiminato Cobalt (II) (salen) and Polystyrene bis(acetylacetone)-propylene-1,3-diiminato Cobalt (II) (BAE) were prepared stepwise from polystyrl chloride. The reaction series included substitution of the chloride with a malononitrile carbanion, reduction to a diamine, condensation to form a Schiff base, and complexation with Co(II) acetate to form the active polymeric material. Optimum conditions with regard to time, temperature, reaction ratios, and solvent were determined for each reaction. The ability of the polymer bound cobalt complex to oxidize 3-methyl indole was measure. The BAE catalyst yielded a large amount of the corresponding o-formylaminoacetophenone. However, the exact yield is not known because product …

Stripping Platinum Metals From Catalytic Converter Units By Use Of Promoted Gas Phase Chlorine Attack, James Harold Finckbone

Retrospective Theses and Dissertations

A gas-phase system to oxidize and remove the platinum and palladium from automotive catalytic converter units was studied. The effects of varying reaction temperature, time and reactant gas concentration upon yields were monitored using a colorimetric procedure based on the regent p-nitroso-N, N-dimethyl amiline. Chlorine plus carbon monoxide at 700°-900°C. displayed the most promise for commercial application.

Separation Of 1,3-Pentadiene With Molecular Sieves, Steven R. Schwinn

Retrospective Theses and Dissertations

The feasibility of separating piperylene (1,3-pentadiene) from a mixture of five-carbon olefins and diolefins with Linde 5A Molecular Sieves was investigated. Olefins and especially diolefins are very reactive and tend to polymerize on the highly polar adsorptive surface thereby clogging the pores of themolecular sieve. It is believed that the acid sites within the zeolite cages catalyze this polymerization reaction and that poisoning of these sites by adsorption of a nitrogenous base (ethylenediamine, dimethylamine or ammonia) or hydrogen sulfide inhibits the formation of polymers. Two criteria were used in the evaluation of the polymerization inhibitors tested. First, a series of …

The Vapor Phase Oxidation Of 1, 3-Pentadiene, David E. Sasser

Retrospective Theses and Dissertations

The vapor phase oxidation of 1.3-pentadiene, over heterogeneous catalysts, was investigated with the objective of producing 2,4-pentadienal and 2,4-pentadienoic acid. Copper and cobalt-molybdenum catalysts, both supported and unsupported, were utilized at various reaction temperatures, residence times and feed ratios. The matter of 1,3-pentadiene vaporization and introduction into the reactor system proved to be critical. Low temperature vaporization of the hydrocarbon and dilution with the oxidant, air, was found to be necessary to avoid polymerization of the feed. Alumina-supported catalysts were found to be very active, leading to severe cracking of the hydrocarbon feed and subsequent carbonization of the catalysts. Silica-supported …

Synthesis And Flame Retardant Studies Of Bromoester Of 2,4-Pentadienoic Acid, Hessam Ghane

Retrospective Theses and Dissertations

The synthesis and fire retardancy of several bromoesters of 2,4-pentadienoic acid were investigated. The synthesis of 2,4-pentadienoic acid was accomplished by liquid phase reaction of acrolein and malonic acid in the presence of pyridine. The conversion of the acid to bromoesters was performed by two different procedures. In the first procedure, the corresponding acid chloride was prepared from the acid via reaction with SOCl2 in the presence of powdered (3A°) molecular sieves. The molecular sieves serve as an internal trap for by-product HC1 and inhibit the competing polymerization reaction of the acid chloride. Reaction of the acid chloride with various …

Quantitative Analysis Of Thin Films By Dc Arc Optical Emission Spectroscopy, Arnold W. Hogrefe

Retrospective Theses and Dissertations

The use of DC arc optical emission spectroscopy (OES) for quantitative analysis of thin films deposited on graphite electrodes was investigated as a process control tool. Three binary systems were evaluated: nickel-chromium, phosphorous-silicon, and silicon-aluminum. Sampling by direct deposition onto graphite electrodes placed in the deposition chamber with product runs proved to be a rapid, representative, and non-disruptive technique. Standard electrodes were prepared for each system either by evaporation of solutions of known concentration onto the tips of electrodes or by weighing out powdered standards of the appropriate concentrations. Standard curves were then prepared by burning multiple sets of standard …

The Liquid Phase Conversion Of Carbon Dioxide To Hydrocarbons Over Ruthenium Catalyst Systems, Mohammad M. Akbarnejad

Retrospective Theses and Dissertations

The purpose of this research project was to evaluate the feasibility of producing hydrocarbons by liquid phase hydrogenation of carbon dioxide. Initial studies dealt with the evaluation of ruthenium (III) chloride over a wide range of reaction conditions. High conversions were observed and were found to vary with catalyst concentration, temperature and time. Conversion of carbon dioxide reached 73% after twenty-four hours at a catalyst concentration of 0.75g/mole of CO2 feed. The hydrogen to carbon dioxide ratio was found to have a significant effect on product distribution and amount of methane produced. For example, low ratios of H2/CO2 gave large …

Catalytic Fluorination Of Dichloromethane With Hydrofluoric Acid, Michael O. Myers

Retrospective Theses and Dissertations

The catalytic, vapor-phase fluorination of dichloromethane to chlorofluoromethane with 38% hydrofluoric acid was investigated as a model system for possible direct utilization of hydrofluoric acid in the production of fluorocarbons and chlorofluorocarbons. Catalysts consisting of Cr or Ni supported on alumina and Ni, Cr, Ag, Co, La, Sn, Hg(I), Hg(II), Cu, Fe, Ru, Zn, Na, or Ca supported on activated charcoal were utilized at various reaction temperatures and reactor residence times. Alumina-supported catalysts were found to have low activities for fluorination in comparison to catalysts utilizing anhydrous HF reported in the patent literature. The low activities were attributed to low …

The Liquid Phase Oxidation Of 1,3-Pentadiene, Carl B. Reaves

Retrospective Theses and Dissertations

The liquid phase autoxidation of 1,3-pentadiene to 2,4-pentadienoic acid utilizing gaseous oxygen at atmospheric pressure was investigated as a possible route for direct utilization of piperylene obtained during the cracking of naptha to ethylene. Catalyst system consisting of cobalt, manganese, and iron salts promoted by sodium, potassium and hydrogen bromides, were used under a variety of condition of catalyst concentration, temperature, oxygen flow and piperylene purity. Under all conditions studied, a large number of oxidation products were formed. Maximum yields of 2,4-pentadienoic acid were obtained using a cobalt acetate bromide catalyst at 85°C.

Vapor Phase Oxidation Of Chloropropenes Over Heterogeneous Catalyst Systems, Tim Ellis Owen

Retrospective Theses and Dissertations

Propylene Dichloride (PDC) is a byproduct of several Dow processes. The thermal cracking of PDC produces 1-cis-chloropropene, 1-trans-chloropropene, 2-chloropropene, and allyl chloride . By oxidizing the l- and 2-chloropropenes to 3- and 2- chloroacrylic acids, respectively, a potentially valuable product could be made. The chloropropenes, air, and steam were passed over various heterogeneous oxidation catalyst systems to attempt this oxidation. Contact time was varied between 0.0951 to 0.915 sec. Temperature was varied between 275C to .25C. The air content of the feed was varied between .1 to 75%. The chloropropene content of the feed was varied between 2.9% to 5.0% …