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Regioselective Coupling Reactions of Diiodophenol Derivatives

Description: Palladium catalyzed reactions of derivatives of 2,4-diiodophenol are explored. Coupling reactions with a series of terminal alkynes and formylation are found to be efficient and regioselective. Coupling with stananne reagents and alkenes do not work. The nature of the oxygen protecting group is critical. The phytotoxic natural product, Eutypine, is synthesized by using regioselective formylation and alkyne coupling. An approach to the plant antimicrobial compound Plicatin B is examined.
Date: December 1994
Creator: Ji, Jianhua
Partner: UNT Libraries

Hydrous pyrolysis of pole treating chemicals: (a) initital measurement of hydrous pyrolysis rates for napthalene and pentachlorophenol; (b) solubility of flourene at temperatures up to 150{degrees}C

Description: The temperature dependencies of the hydrous pyrolysis/oxidation (HPO) aqueous phase oxidation reactions of naphthalene and pentachlorophenol have been determined for phosphate buffered systems using Dickson-type reaction vessels. The HPO experimental temperatures ranged from 114{degrees}C to 148{degrees}C for naphthalene and 114{degrees}C to 137{degrees}C for pentachlorophenol. The loss of the organic species was used to determine activation energies of 95.8 kJ/mole for naphthalene oxidation and 84.8 kJ/mole for pentachlorophenol oxidation. Aqueous concentrations of target compounds and reaction intermediates were determined by gas chromatography and compound identification was verified by gas chromatography - mass spectrometry. During the experiments the pollutants were completely mineralized, as indicated by a stoichiometric production of inorganic carbon in the case of naphthalene and inorganic carbon and chloride in the case of pentachlorophenol. HPO of pentachlorophenol produced 2,3,5,6- tetrachlorophenol as an intermediate, whereas no intermediates amenable by GC were observed during the HPO of naphthalene. Measurements of the aqueous solubility of florin in an unbuffered solution have been made covering the temperature range from 20{degrees}C to 150{degrees}C. There is very good agreement between this data set and data previously published covering the lower temperature range (20{degrees}C to 75{degrees}C). Extension of the solubility measurements to higher temperatures covers the in situ temperatures achievable during field application of HPO and demonstrated a nearly exponential rise in aqueous solubility as a function of temperature, with a 10 fold increase in aqueous florin solubility going from 75{degrees}C to 125{degrees}C and a 20 fold increase in going from 75{degrees}C to 150{degrees}C.
Date: November 15, 1997
Creator: Leif, R. N., LLNL
Partner: UNT Libraries Government Documents Department

High Precision Measurement of Isotope Effects on Noncovalent Host-Guest Interactions

Description: Isotope effects (IEs) are a powerful tool for examining the reactivity of, and interactions between, molecules. Recently, secondary IEs have been used to probe the nature of noncovalent interactions between guest and host molecules in supramolecular systems. While these studies can provide valuable insight into the specific interactions governing guest recognition and binding properties, IEs on noncovalent interactions are often very small and difficult to measure precisely. The Perrin group has developed an NMR titration method capable of determining ratios of equilibrium constants with remarkable precision. They have used this technique to study small, secondary equilibrium isotope effects (EIEs) on the acidity of carboxylic acids and phenols and on the basicity of amines, measuring differences down to thousandths of a pK{sub a} unit. It occurred to us that this titration method can in principle measure relative equilibrium constants for any process which is fast on the NMR timescale and for which the species under comparison are distinguishable by NMR. Here we report the application of this method to measure very small EIEs on noncovalent host-guest interactions in a supramolecular system.
Date: June 23, 2009
Creator: Mugridge, Jeffrey S.; Bergman, Robert G. & Raymond, Kenneth N.
Partner: UNT Libraries Government Documents Department

A Study of the Friedel-Craft Reactions of Phenolic Ethers

Description: The original purpose of this investigation was to prepare a series of diketones. However, since considerable difficulty was encountered in the preparation of these diketones, attention was shifted to a study of the Friedel-Craft reactions of phenolic ethers and to the reaction between phenolic ethers and dicarboxylic acids with boron trifluoride as a catalyst.
Date: January 1959
Creator: Roberson, Charles Ray
Partner: UNT Libraries

Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, July 1, 1995--September 30, 1995

Description: Compared to alkoxy complexes, the chemistry of late transition metal aryloxy complexes is expected to reflect somewhat weaker M-O bonds since aryloxides are weaker nucleophiles than alkoxides. To understand the chemistry of the phenoxides, several thiophenoxide derivatives were synthesized. Pt(II) thiolate complexes are obtained either by reaction of Pt(II) chlorides with RSH in presence of base or the reaction of Pt(0) with dialkyl disulfides. NMR was used to study the structure.
Date: December 31, 1995
Creator: Kubiak, C.P.
Partner: UNT Libraries Government Documents Department

A Characterization and Evaluation of Coal Liquefaction Process Streams

Description: This is the Technical Progress Report for the tenth quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period October 1 through December 31, 1996. Described in this report are the following activities: (1) CONSOL characterized two HTI coal/petroleum coprocessing samples for Ni and V concentrations, as requested by DOE. The results are reported in Appendix 1. (2) CONSOL began work to evaluate the potential for producing alkylphenyl ethers, and specifically ethylphenyl ethers, from coal liquefaction phenols. The work includes a literature review and experimentation. The status of this ongoing work is described in this report. (3) A set of samples was requested from HTI Run ALC-2 (Appendix 2). (4) The University of Delaware is conducting resid reactivity tests and is developing a kinetic mechanistic model of resid reactivity. A summary of Delaware`s progress is appended to this report (Appendix 3). (5) A paper was submitted for presentation at the 213th National Meeting of the American Chemical Society, April 13-17, 1997, in San Francisco, CA, (Appendix 4).
Date: March 31, 1997
Creator: Robbins, G.A.; Brandes, S.D. & Winschel, R.A.
Partner: UNT Libraries Government Documents Department

New organic aerogels based upon a phenolic-furfural reaction

Description: The aqueous polycondensation of (1) resorcinol with formaldehyde and (2) melamine with formaldehyde are two proven synthetic routes for the formation of organic aerogels. Recently, we have discovered a new type of organic aerogel based upon a phenolic-furfural (PF) reaction. This sol-gel polymerization has a major advantage over past approaches since it can be conducted in alcohol (e.g., 1-propanol), thereby eliminating the need for a solvent exchange step prior to supercritical drying from carbon dioxide. The resultant aerogels are dark brown in color and can be converted to a carbonized version upon pyrolysis in an inert atmosphere. BET surface areas of 350--600 m{sup 2}/g have been measured, and transmission electron microscopy reveals an interconnected structure of irregularly-shaped particles or platelets with {approximately}10 nm dimensions. Thermal conductivities as low as 0.015 W/m-K have been recorded for PF aerogels under ambient conditions. This paper describes the chemistry-structure-property relationships of these new materials in detail.
Date: September 1, 1994
Creator: Hrubesh, L.W.
Partner: UNT Libraries Government Documents Department

KEROGEN OIL VALUE ENHANCEMENT RESEARCH

Description: Three general categories of products from the Estonia Kukersite kerogen oil were defined: pure compounds, broad range concentrates, and sweet refinery feedstock. Product development and market research center on these three categories. Further attempts were made to identify and test chemical approaches for producing lower alkyl resorcinols (what the market requires) from higher alkyl resorcinols. The approaches and process conditions tested have not yet produced satisfactory results. Progress was made to interest industry in the phenolic products producible. A sample of oil from the Galoter retort was received from Estonia and characterization of this sample was initiated. The sample was batch extracted and results of yields and selectivity are reported.
Date: May 22, 2002
Creator: James W. Bunger, Ph.D.; Christopher P. Russell, Ph.D. & Donald E. Cogswell, M.S.
Partner: UNT Libraries Government Documents Department

SALTSTONE 4QCY11 TCLP RESULTS

Description: The Saltstone Production Facility (SPF) receives waste from Tank 50H for treatment. In the fourth quarter of the 2011 calendar year (4QCY11), Tank 50H accepted transfers of approximately 10 kgal from the Effluent Treatment Project (ETP), approximately 4 kgal from 211H, approximately 573 kgal from the Actinide Removal Process/Modular Caustic Side Solvent Extraction Unit (ARP/MCU) Decontaminated Salt Solution Hold Tank (DSS-HT), and approximately 5 kgal from other sources. The Saltstone Grout Sampling plan provides the South Carolina Department of Health and Environmental Control (SCDHEC) with the chemical and physical characterization strategy for the salt solution which is to be disposed of in the Z-Area Solid Waste Landfill (SWLF). During operation, samples were collected from Tank 50H and grout samples prepared to determine the non-hazardous nature of the grout to meet the requirements of the South Carolina Hazardous Waste Management Regulations (SCHWMR) R.61-79.261.24(b) and R.61-79.268.48(a). Savannah River National Laboratory (SRNL) was asked to prepare saltstone from samples of Tank 50H obtained Oct. 12, 2011 during 4QCY11 to determine the non-hazardous nature of the grout. The samples were cured and shipped to Babcock & Wilcox Technical Services Group-Radioisotope and Analytical Chemistry Laboratory (B&W TSG-RACL) to perform the Toxic Characteristic Leaching Procedure (TCLP) 2 and subsequent extract analysis on saltstone samples for the analytes required for the quarterly analysis saltstone sample. In addition to the eight toxic metals - arsenic, barium, cadmium, chromium, mercury, lead, selenium and silver - analytes included the underlying hazardous constituents (UHC) antimony, beryllium, nickel, and thallium which could not be eliminated from analysis by process knowledge. B&W TSG-RACL provided subsamples to GEL Laboratories, LLC for analysis for the UHCs benzene, phenols and total and amenable cyanide.
Date: January 31, 2012
Creator: Bannochie, C.
Partner: UNT Libraries Government Documents Department

Application of RBS and NRA in the fabrication of carbon based devices

Description: We have used Nuclear Reaction Analysis (NRA) and Rutherford Backscattering Spectrometry (RBS) as well as resonant backscattering as analytical tools in fabricating carbon based drug delivery bio-implants, electrodes for batteries, and devices to entrap or filter specific toxins. Precursor is resol C{sub 7}H{sub 8}O{sub 2} liquid, which converts to fully cured phenolic resin C{sub 7}H{sub 6}O (sp gr 1.25) on heating at 170 C. This resin further transforms with no change in shape to glassy carbon (sp gr 1.45) on heating to 1000 C. Final product consists of long ribbon-like molecules of sp2 carbon atoms aggregated locally to form subcrystalline domains arranged randomly in space. RBS and NRA were used in measuring the porosity before and after activation, in concentration profiling of stored drugs before and after leaching, in detecting low level light element impurities, and in detecting changes in the structure of the device due to fabrication.
Date: June 1, 1995
Creator: Ila, D.; Zimmerman, R.L.; Maleki, H.; Evelyn, A.L. & Poker, D.B.
Partner: UNT Libraries Government Documents Department

Methods development for separation of inorganic anions, organic acids and bases, and neutral organic compounds by ion chromatography and capillary electrophoresis

Description: A novel anion-exchange resin containing three amine groups was prepared by reaction of a chloromethylated polystyrene-divinylbenzene (PS-DVB) resin with diethylenetriamine. After being protonated by contact with an aqueous acid, this resin can be used for ion chromatographic separation of anions. The charge on the resins can be varied from +1 to +3 by changing the mobile phase pH. The selectivity of the new ion exchangers for various inorganic anions was quite different from that of conventional anion exchangers. The performance of this new anion exchanger was studied by changing the pH and the concentration of the eluent, and several different eluents were used with some common anions as testing analytes. Conductivity detection and UV-visible detection were applied to detect the anions after separation. The new resin can also be used for HPLC separation of neutral organic compounds. Alkylphenols and alkylbenzenes were separated with this new polymeric resin, and excellent separations were obtained under simple conditions. This report contains Chapter 1: General introduction and Chapter 6: General conclusions.
Date: April 1, 1999
Creator: Li, J.
Partner: UNT Libraries Government Documents Department

Heteronuclear probes of coal structure and reactivity. Semi-annual report

Description: Efforts toward quantitation of the sulfur removed from coal in the reaction Coal(S) + excess PBu{sub 3} with heat {r_arrow} Coal + SPBu{sub 3}/PBu{sub 3} by column chromatography of the products followed by weighing the SPBu{sub 3} and vacuum distillation of the SPBu{sub 3}/PBu{sub 3} mixture followed by gas chromatographic analysis are described. The first method failed, but the latter is more successful. It has been discovered that para-chloro phenol catalyzes the removal of sulfur from dibenzothiophene by PBu{sub 3} under mild conditions.
Date: May 1, 1996
Creator: Verkade, J.G.
Partner: UNT Libraries Government Documents Department

Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly technical progress report, January 1--March 30, 1996 and April 1--June 30, 1996

Description: Over the course of his studies on catalytic deoxygenation of phenolic residues in coal by carbon monoxide, the author performed preliminary investigations into the removal of other heteroatom groups. This report describes his attempted carbonylation of phenyl amido complexes. These studies resulted in the surprisingly facile formation of amidines. The amidine group is the nitrogen analog of carboxylic acids and esters. This functional group combines the properties of an azomethane-like C=N double bond with an amide-like C-N single bond. This group, like the related allyl (C-C-C), aza-allyl (C-N-C), and carboxylato (O-C-O) groups, form a number of transition metal derivatives, with both early and late transition metals. Various bonding modes of the amidino group have been reported. However, most isolated complexes have the amidino ligand as a chelating ligand or bridging two metals. This is due to the preference of amidines to bond via the nitrogen lone pairs, in contrast to the {eta}{sup 3} {pi} bonding observed in metal-allyl complexes.
Date: May 1, 1997
Creator: Kubiak, C.P.
Partner: UNT Libraries Government Documents Department

Solid-matrix luminescence analysis. Final technical report, June 15, 1986--June 14, 1995

Description: In this report, the major results and conclusions of the research over the last two years and five months will be considered. The report discusses the physicochemical interactions discovered that are important for solid-matrix luminescence (SML), and the development of new interaction models which are very useful for the understanding the phenomena that are relevant for SML. The SML of 4-phenylphenol and 2-phenyl phenol adsorbed on filter paper is described. In addition, some new analytical methodology and applications are discussed.
Date: September 1, 1996
Creator: Hurtubise, R.J.
Partner: UNT Libraries Government Documents Department

Shale oil value enhancement research. Quarterly report, October 1, 1993--December 31, 1993

Description: A major push was made to identify the hydrocarbon and heteroatom types present in raw shale oil. A comprehensive, qualitative picture of the <400{degrees}C material has been obtained. In addition to the expected types, e.g., pyridines, pyrroles, indoles and phenols, the presence of aliphatic carboxylic acids, ketones and nitrites was confirmed. Most importantly, heteroatom types are able to be concentrated nearly quantitatively by liquid-liquid extraction with polar solvents. Compound types characterization of the >400{degrees}C material, as well as rapid, routine analysis of separations fractions, requires new methodologies founded in the Z-BASIC concept. Advances were made in establishing the interface protocol needed to utilize Z-BASIC methodologies for interpretation of gc-ms output data. It is anticipated that all interface protocols will be completed and a computerized reporting system will be in place by the end of the next quarter. Progress reports were made at the Contractor`s Review Meeting (METC), November 16th and at the Eastern Oil Shale Symposium (Lexington), November 17th. Research results continue to be well-received. The concept of a thermodynamically logical map of potential products from shale oil is a sound approach to value-enhancement research. From a commercial perspective, the concept of establishing a demand for raw shale oil at a reasonable purchase price of, say $30/bbl, is increasingly being recognized as the best means of pulling shale oil into the marketplace.
Date: May 1, 1997
Partner: UNT Libraries Government Documents Department

Fouling formation of an olefin in the presence of oxygen and thiophenol

Description: A kinetic model was developed to predict the fouling rate for autoxidation of indene in the presence of thiophenol. The kinetic constants were determined by analyzing the fouling data obtained with and without thiophenol. An initial rapid formation of hydroperoxide was observed in the presence of thiophenol; however, the product(s) formed by thiophenol was found to inhibit further formation of hydroperoxide. The maximum concentration of hydroperoxide and gum were about the same for experiments with and without thiophenol; however, the maximum was reached faster for runs with thiophenol. The effects of bulk temperature, and concentration of thiophenol and oxygen on the fouling rate were analyzed using the fouling model developed previously.
Date: December 31, 1995
Creator: Yap, S.; Dranoff, J. & Panchal, C.B.
Partner: UNT Libraries Government Documents Department

Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly report, January 1--March 30, 1996

Description: Over the course of the studies on catalytic deoxygenation of phenolic residues in coal by carbon monoxide, the author performed preliminary investigations into the removal of other heteroatom groups. This report describes the attempted carbonylation of phenyl amido complexes. These studies resulted in the surprisingly facile formation of amidines. The amidine group is the nitrogen analog of carboxylic acids and esters. This functional group combines the properties of an azomethane-like C=N double bond with an amide-like C-N single bond. This group, like the related allyl (C-C-C), aza-allyl (C-N-C), and carboxylato (O-C-O) groups, form a number of transition metal derivatives, with both early and late transition metals. Various bonding modes of the amidino group have been reported. However, most isolated complexes have the amidino ligand as a chelating ligand or bridging two metals. This is due to the preference of amidines to bond via the nitrogen lone pairs, in contrast to the {eta}3 bonding observed in metal-allyl complexes. The experimental section of the paper describes the synthesis of platinum complexes, X-ray diffraction data for one Pt complex, and its reaction with carbon monoxide. Results are presented on the crystal and molecular structure of a platinum complex.
Date: December 31, 1996
Creator: Kubiak, C.P.
Partner: UNT Libraries Government Documents Department

A characterization and evaluation of coal liquefaction process streams. Quarterly report, January 1--March 31, 1997

Description: Described in this report are the following activities: CONSOL characterized process stream samples from HTI Run ALC-2, in which Black Thunder Mine coal was liquefied using four combinations of dispersed catalyst precursors. Oil assays were completed on the HTI Run PB-05 product blend. Fractional distillation of the net product oil of HTI Run POC-1 was completed. CONSOL completed an evaluation of the potential for producing alkylphenyl ethers from coal liquefaction phenols. At the request of DOE, various coal liquid samples and relevant characterization data were supplied to the University of West Virginia and the Federal Energy Technology Center. The University of Delaware is conducting resid reactivity tests and is completing the resid reaction computer model. The University of Delaware was instructed on the form in which the computer model is to be delivered to CONSOL.
Date: August 1, 1998
Creator: Robbins, G.A.; Brandes, S.D.; Heunisch, G.W. & Winschel, R.A.
Partner: UNT Libraries Government Documents Department

A CHARACTERIZATION AND EVALUATION OF COAL LIQUEFACTION PROCESS STREAMS

Description: This is the Technical Progress Report for the eleventh quarter of activities under DOE Contract No. DE-AC22-94PC93054. It covers the period January 1 through March 31, 1997. Described in this report are the following activities: (1) CONSOL characterized process stream samples from HTI Run ALC-2, in which Black Thunder Mine coal was liquefied using four combinations of dispersed catalyst precursors. These results are described in the Results and Discussion section of this report. (2) Oil assays were completed on the HT I Run PB-05 product blend. Background information is presented in the Results and Discussion section of this report. The results are presented in Appendix 1. (3) Fractional distillation of the net product oil of HTI Run POC-1 was completed. Background information is presented in the Results and Discussion section of this report. The results are presented in Appendix 2. (4) CONSOL completed an evaluation of the potential for producing alkylphenyl ethers from coal liquefaction phenols. Those results are described briefly in the Results and Discussion section of this report. The full report is presented in Appendix 3. (5) At the request of DOE, various coal liquid samples and relevant characterization data were supplied to the University of West Virginia and the Federal Energy Technology Center. These activities are described in Appendix 4. (6) The University of Delaware is conducting resid reactivity tests and is completing the resid reaction computer model. A summary of Delaware's progress is provided in the Results and Discussion section. (7) The University of Delaware was instructed on the form in which the computer model is to be delivered to CONSOL (Appendix 5). (8) The University of Delaware submitted a paper on the resid reactivity work for presentation at the 213th National Meeting of the American Chemical Society, April 13-17, 1997 in San Francisco, California. The ...
Date: April 1, 1998
Creator: Robbins, G.A.; Heunisch, G.W.; Winschel, R.A. & Brandes, S.D.
Partner: UNT Libraries Government Documents Department

Solid-matrix luminescence analysis. Progress report, 15 June 1992--31 October 1994

Description: Interaction models were developed for moisture effects on room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) of compounds adsorbed on filter paper. The models described both dynamic and matrix quenching and also related the Young modulus of filter paper to quenching of phosphor on moist filter paper. Photophysical parameters for lumiphors in solution and on solid matrices were compared. Results showed that for some compounds, solid-matrix luminescence has greater analytical potential than solution luminescence. Also, the solid-matrix systems into one of two categories depending on how the intersystem crossing rate constants change with temperature. The first study was carried out on effects of heavy atom on solid-matrix luminescence. With some heavy atoms, maximum solid-matrix phosphorescence quantum yield was obtained at room temperature, and there was no need to use low temperature to obtain a strong phosphorescence signal. By studying solid-matrix luminescence properties of phosphors adsorbed on sodium acetate and deuterated sodium acetate, an interaction model was developed for p-aminobenzoic acid anion adsorbed on sodium acetate. It was shown that the energy-gap law was applicable to solid-matrix luminescence. Also, deuterated phenanthrene and undeuterated phenanthrene were used to study nonradiative transition of excited triplet state of adsorbed phosphors. Heat capacities of several solid matrices were obtained vs temperature and related to vibrational coupling of solid matrix with phosphor. Photophysical study was performed on the hydrolysis products of benzo(a)pyrene-DNA adducts. Also, an analytical method was developed for tetrols in human lung fractions. Work was initiated on the formation of room temperature glasses with glucose and trehalose. Also, work has begun for the development of an oxygen sensor by measuring the RTP quenching of triphenylene on filter paper.
Date: December 31, 1994
Creator: Hurtubise, R.J.
Partner: UNT Libraries Government Documents Department