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An Approach Towards the Total Synthesis of Clonostachydiol

Description: 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.
Date: August 1995
Creator: Maiti, Tushar B. (Tushar Baran)
Partner: UNT Libraries

Studies in regiospecific oxidation reactions of 1-methyl-pentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione.

Description: Baeyer-Villiger oxidation of 1-methylpentacyclo[5.4.0.02,6.03,10.05,9] undecane-8,11-dione, performed by using m-chloroperbenzoic acid in 1:1 molar ratio, resulted in the formation of monolactone. The corresponding dilactone, was synthesized by reacting 1-methyl-PCU-8,11-dione with m-chloroperbenzoic acid in 1:2 molar ratio. 6-Methyl-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione was converted into the corresponding exo-6,7-monoepoxide via treatment with 30% aqueous hydrogen peroxide. Epoxidation of this monoepoxide by using m-chloroperbenzoic acid afforded the corresponding bis-epoxide. Ceric ammonium nitrate (CAN) promoted oxidation of 1-methyl-PCU-8,11-dione afforded "methylated lactones" and a "methylated alkene."
Date: May 2004
Creator: Vappala, Indu
Partner: UNT Libraries

Lactonization and protonation of gluconic acid: a thermodynamicand kinetic study by potentiometry, nmr and esi-ms

Description: In acidic aqueous solutions, gluconate protonation is coupled with lactonization of gluconic acid. With the decrease of pC{sub H}, two lactones ({delta}/{gamma}) are sequentially formed. The {delta}-lactone forms more readily than the {gamma}-lactone. In 0.1 M gluconate solutions, if pC{sub H} is above 2.5, only the {delta}-lactone is generated. When pC{sub H} is decreased below 2.0, the formation of the {gamma}-lactone is observable although the {delta}-lactone predominates. At I = 0.1 M NaClO{sub 4} and room temperature, the deprotonation constant of the carboxylic group, using the NMR technique, was determined to be log K{sub a} = 3.30 {+-} 0.02; the {delta}-lactonization constant, by the batch potentiometric titrations, was obtained to be log K{sub L} = - (0.54 {+-} 0.04). Using ESI-MS, the rate constants of the {delta}-lactonization and the hydrolysis at pC{sub H} {approx} 5.0 were estimated to be k{sub 1} = 3.2 x 10{sup -5} s{sup -1} and k{sup -1} = 1.1 x 10{sup -4} s{sup -1}, respectively.
Date: January 10, 2007
Creator: Zhang, Z.; Gibson, P.; Clark, S.B.; Tian, G.; Zanonato, P. & Rao, L.
Partner: UNT Libraries Government Documents Department

Baeyer-Villiger Oxidation of 1,7- & 1,9-dibromopentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione

Description: Baeyer-Villiger oxidation of 1,9-dibromopentacyclo[5.4.0.02,6.03,10.05,9]undecane-8,11-dione (1,9-dibromo-PCU-8,11-dione) was performed by using an excess amount of m-chloroperbenzoic acid (3 equivalents) and resulted in the formation of the corresponding monolactone. The reaction would not proceed to the dilactone stage. The structure of the reaction product was established unequivocally via single crystal X-ray diffraction. Baeyer-Villiger oxidation of 1,9-dibromo-PCU-8,11-dione using ceric ammonium nitrate (CAN) was also performed and afforded a mixture of lactones. Only one of these lactones, which also contained an alkene functionality, could be isolated and characterized. 1,7-dibromo-PCU-8,11-dione was also reacted with CAN, yielding the mono-lactone, which has also been characterized.
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Date: May 2004
Creator: Akinola, Adeniyi O.
Partner: UNT Libraries

[Energies of organic compounds]

Description: The enthalpy of reduction of lactones to the corresponding diols has been determined, allowing the enthaipies of formation of the lactones to be determined. Results of this study agree well with data obtained for enthalpies of hydrolysis of the lactones. We have begun the measurement of the enthalpies of reduction of norbornanones, and we have shown that it is possible to determine the difference in energy between the exo and endo forms of the product alcohols by measuring the equilibrium constant as a function of temperature. The study of the enthalpies of hydration of carbonyl compounds has continued, and the enthalpies of hydrolysis of the corresponding ketals is being determined. The study of the enthalpies of hydration of alkenes is nearly completed, and the rearrangement reactions which were uncovered are being investigated.
Date: December 31, 1991
Creator: Wiberg, K.B.
Partner: UNT Libraries Government Documents Department

Bacterial quorum sensing and nitrogen cycling in rhizosphere soil

Description: Plant photosynthate fuels carbon-limited microbial growth and activity, resulting in increased rhizosphere nitrogen (N)-mineralization. Most soil organic N is macromolecular (chitin, protein, nucleotides); enzymatic depolymerization is likely rate-limiting for plant N accumulation. Analyzing Avena (wild oat) planted in microcosms containing sieved field soil, we observed increased rhizosphere chitinase and protease specific activities, bacterial cell densities, and dissolved organic nitrogen (DON) compared to bulk soil. Low-molecular weight DON (<3000 Da) was undetectable in bulk soil but comprised 15% of rhizosphere DON. Extracellular enzyme production in many bacteria requires quorum sensing (QS), cell-density dependent group behavior. Because proteobacteria are considered major rhizosphere colonizers, we assayed the proteobacterial QS signals acyl-homoserine lactones (AHLs), which were significantly increased in the rhizosphere. To investigate the linkage between soil signaling and N cycling, we characterized 533 bacterial isolates from Avena rhizosphere: 24% had chitinase or protease activity and AHL production; disruption of QS in 7 of 8 eight isolates disrupted enzyme activity. Many {alpha}-Proteobacteria were newly found with QS-controlled extracellular enzyme activity. Enhanced specific activities of N-cycling enzymes accompanied by bacterial density-dependent behaviors in rhizosphere soil gives rise to the hypothesis that QS could be a control point in the complex process of rhizosphere N-mineralization.
Date: October 1, 2008
Creator: DeAngelis, K. M.; Lindow, S. E. & Firestone, M. K.
Partner: UNT Libraries Government Documents Department

[Energies of organic compounds]

Description: The first part of our study of the enthalpy of reduction of carbonyl compounds has been completed and includes four aldehydes, acetone, a series of cyclic ketones and ethyl acetate. Results suggest that some of the literature data for these compounds are significantly in error. Equilibrium constants have been measured for the reaction of carbonyl compounds with water to give hydrates as well as with methanol to give either hemiacetals or acetals. They cover a wide range, and studies are underway to determine the reasons for the differences. Studies of the enthalpies of hydration of some alkenes which yield tertiary alcohols have been completed, as well as a study of the hydrolysis of lactones. The ``gauche effect`` has been studied, and has been shown to result from the formation of bent bonds when atoms of much different electronegativity are joined.
Date: July 1, 1995
Partner: UNT Libraries Government Documents Department

Energies of organic compounds

Description: The studies included hydrolysis of ketals, hydration of alkenes, barrier to rotation about C-O bonds in esters and acids, hydrolysis of lactones, reduction of ketones, non-bonded interactions, and enthalpies of vaporization of ketones, ketals, and other compounds.
Date: July 1, 1995
Creator: Wiberg, K.B.
Partner: UNT Libraries Government Documents Department

Studies of spin alignment in ferrocenylsilane compounds and in regiospecific oxidation reactions of 1,9-dimethylpentacyclo [5.4.0.02,6.03,10.05,9]undecane-8,11-dione.

Description: Part I. The syntheses of a series of stable ferrocenylsilane compounds and their corresponding polyradical cations are reported. Electron spin properties of these molecules were investigated by cyclic voltammetry, ESR, and magnetic susceptibility measurements. All the compounds presented, showed significant electronic communication (>100 mV) between the redox centers by CV. Part II. Baeyer-Villiger oxidation of (1,9-dimethyl-PCU-8,11-dione) was performed using m-chloroperoxybenzoic acid in 1:2 molar ratios. The product obtained was the corresponding dilactone 113. The structure of the reaction products was established unequivocally via single crystal X-ray diffraction methods. The reaction of the 1,9-dimethyl-PCU-8,11-dione with 1:1 molar ratio of m-chloroperoxybenzoic acid produced again the dilactone 113, and not the expected monolactone 114. Ceric ammonium nitrate (CAN) promoted oxidation reaction of 1,9-dimethyl-PCU-8,11-dione afforded a mixture of dimethylated lactones, which indicated unique reaction mechanism pathways. These individual isomers, 115 and 116, have been isolated from these mixtures via column chromatography by using silica gel as adsorbent followed by fractional recrystallization of individual chromatography fractions. Structures of these pure products have been established unequivocally by application of single crystal X-ray crystallographic methods.
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Date: August 2006
Creator: Atim, Silvia
Partner: UNT Libraries

Energies of organic compounds. Technical progress report

Description: A procedure was developed for carbonyl group reduction using triethylborohydride. Esters and lactones are readily reduced and are suitable as substrates. Some enthalpies of hydrolysis of lactones and esters were measured. Heats of trifluoroacetolysis of alkenes leading to tertiary alcohols were measured; some cyclic systems were also investigated. In order to study the effect of {alpha}-alkyl substituents on ketones, rotational barriers adjacent to carbonyl groups were studied.
Date: August 12, 1987
Creator: Wiberg, K.B.
Partner: UNT Libraries Government Documents Department

Fast Curing of Composite Wood Products

Description: The overall objective of this program is to develop low temperature curing technologies for UF and PF resins. This will be accomplished by: • Identifying the rate limiting UF and PF curing reactions for current market resins; • Developing new catalysts to accelerate curing reactions at reduced press temperatures and times. In summary, these new curing technologies will improve the strength properties of the composite wood products and minimize the detrimental effects of wood extractives on the final product while significantly reducing energy costs for wood composites. This study is related to the accelerated curing of resins for wood composites such as medium density fiberboard (MDF), particle board (PB) and oriented strandboard (OSB). The latter is frequently manufactured with a phenol-formaldehyde resin whereas ureaformaldehyde (UF) resins are usually used in for the former two grades of composite wood products. One of the reasons that hinder wider use of these resins in the manufacturing of wood composites is the slow curing speed as well as inferior bondability of UF resin. The fast curing of UP and PF resins has been identified as an attractive process development that would allow wood to be bonded at higher moisture contents and at lower press temperatures that currently employed. Several differing additives have been developed to enhance cure rates of PF resins including the use of organic esters, lactones and organic carbonates. A model compound study by Conner, Lorenz and Hirth (2002) employed 2- and 4-hydroxymethylphenol with organic esters to examine the chemical basis for the reported enhanced reactivity. Their studies suggested that the enhance curing in the presence of esters could be due to enhanced quinone methide formation or enhanced intermolecular SN2 reactions. In either case the esters do not function as true catalysts as they are consumed in the reaction and were not ...
Date: April 26, 2006
Creator: Ragauskas, Dr. Arthur J.
Partner: UNT Libraries Government Documents Department

A biological/chemical process for reduced waste and energy consumption: caprolactam production. Final report

Description: A biological/chemical process for converting cyclohexane into caprolactam was investigated: microorganisms in a bioreactor would be used to convert cyclohexane into caprolactone followed by chemical synthesis of caprolactam using ammonia. Four microorganisms were isolated from natural soil and water, that can utilize cyclohexane as a sole source of C and energy for growth. They were shown to have the correct metabolic intermediates and enzymes to convert cyclohexane into cyclohexanol, cyclohexanone, and caprolactone. Genetic techniques to create and select for caprolactone hydrolase negative-mutants were developed; those are used to convert cyclohexane into caprolactone but, because of the block, are unable to metabolize the caprolactone further. Because of a new nylon carpet reycle process and the long time frame for a totally new bioprocess, a limited study was done to evaluate whether a simplified bioprocess to convert cyclohexanol into cyclohexanone or caprolactone was feasible; growth rates and key enzyme levels were measured in a collection of microorganisms that metabolize cyclohexanol to determine if the bioactivity is high enough to support an economical cyclohexanol bioprocess. Although these microorganisms had sufficient bioactivity, they could tolerate only low levels (<1%) of cyclohexanol and thus are not suitable for developing a cost effective bioprocess because of the high cost of dilute product recovery.
Date: May 1, 1996
Partner: UNT Libraries Government Documents Department

A biological/chemical process for reduced waste and energy consumption, Caprolactam production: Phase 1, Select microorganisms and demonstrate feasibility. Final report

Description: A novel biological/chemical process for converting cyclohexane into caprolactam was investigated. Microorganisms in a bioreactor would be used to convert cyclohexane into caprolactone followed by chemical synthesis of caprolactam using ammonia. The proposed bioprocess would be more energy efficient and reduce byproducts and wastes that are generated by the current chemical process. We have been successful in isolating from natural soil and water samples two microorganisms that can utilize cyclohexane as a sole source of carbon and energy for growth. These microorganisms were shown to have the correct metabolic intermediates and enzymes to convert cyclohexane into cyclohexanol, cyclohexanone and caprolactone. Genetic techniques to create and select for caprolactone hydrolase negative-mutants are being developed. These blocked-mutants will be used to convert cyclohexane into caprolactone but, because of the block, be unable to metabolize the caprolactone further and excrete it as a final end product.
Date: August 1, 1995
Creator: St.Martin, E.J.
Partner: UNT Libraries Government Documents Department

D-erythroascorbic acid: Its preparations, chemistry, and metabolism (fungi and plants). Final report

Description: The origin of oxalate in plants has received considerable attention and glycolate metabolism has been generally regarded as a prime precursor candidate although studies on the metabolism of L-ascorbic acid single out that plant constituent as well. Experiments with oxalate-accumulating plants that contain little or no tartaric acid revealed the presence of a comparable L-ascorbic acid metabolism with the exception that the cleavage products were oxalic acid and L-threonic acid or products of L-threonic acid metabolism. A reasonable mechanism for cleavage of L-ascorbic acid at the endiolic bond is found in studies on the photooxygenation of L-ascorbic acid. Presumably, analogs of L-ascorbic acid that differ only in the substituent at C4 also form a hydroperoxide in the presence of alkaline hydrogen peroxide and subsequently yield oxalic acid and the corresponding aldonic acid or its lactone. We became interested in such a possibility when we discovered that L-ascorbic acid was rare or absent in certain yeasts and fungi whereas a L-ascorbic acid analog, D-glycero-pent-2-enono- 1,4-lactone (D-erythroascorbic acid), was present. It has long been known that oxalate occurs in yeasts and fungi and its production plays a role in plant pathogenesis. As to the biosynthetic origin of fungal oxalic acid there is little information although it is generally assumed that oxaloacetate or possibly, glycolate, might be that precursor.
Date: December 31, 1991
Creator: Loewus, F. A. & Seib, P. A.
Partner: UNT Libraries Government Documents Department

Coalification by clay-catalyzed oligomerization of plant monomers

Description: One of the main objectives is to explore the possibility that radical cation Diels-Alder reactions are involved in the biosynthesis of lignans in plants. Two of the most highly sought after classes of lignans are the dibenzocyclooctadienes represented by stegnol and the aryltetralins represented by podophyllotoxin. Both are powerful anticancer agents and have structures that might be assembled from C{sub 6}-C{sub 3} units via radical cation processes. A common feature of both of these molecules is the benzyllic hydroxyl group. The hydroxyl group is cis to the lactone carbonyl carbon. The hypothetical mechanism by which this hydroxyl group might be introduced into the aryltetralins is outlined. We have also begun to study the radical cation Diels-Alder chemistry of cinnamate salts. The preliminary results are described. In an extension of our previous work with tethered cinnamates, we have returned to the tethered molecule and are in the process of reexamining its radical cation Diels-Alder chemistry in the presence of Na{sub 2}CO{sub 3}. We have begun to investigate the radical cation chemistry of polycyclic aromatic hydrocarbons in an effort to find chemistry that will produce the coupling of these aromatic molecules. Our first effort has been to look at naphthalene treated with DBAHA. 2 refs.
Date: January 1, 1990
Creator: Orchin, M. & Wilson, R.M.
Partner: UNT Libraries Government Documents Department

Picosecond studies of temperature and solvent effects on the fluorescence from coumarin 102 and acridine

Description: Hydrogen bonding characteristics of acridine and coumarin 102 are studied in different solutions. Coumarin 102 upon excitation forms a complex in alcoholic solutions, whereas excited acridine relaxes in aprotic and protic solvents by a process involving an activation energy.
Date: January 1, 1980
Creator: Shapiro, S.L. & Winn, K.R.
Partner: UNT Libraries Government Documents Department

D-erythroascorbic acid: Its preparations, chemistry, and metabolism (fungi and plants)

Description: The origin of oxalate in plants has received considerable attention and glycolate metabolism has been generally regarded as a prime precursor candidate although studies on the metabolism of L-ascorbic acid single out that plant constituent as well. Experiments with oxalate-accumulating plants that contain little or no tartaric acid revealed the presence of a comparable L-ascorbic acid metabolism with the exception that the cleavage products were oxalic acid and L-threonic acid or products of L-threonic acid metabolism. A reasonable mechanism for cleavage of L-ascorbic acid at the endiolic bond is found in studies on the photooxygenation of L-ascorbic acid. Presumably, analogs of L-ascorbic acid that differ only in the substituent at C4 also form a hydroperoxide in the presence of alkaline hydrogen peroxide and subsequently yield oxalic acid and the corresponding aldonic acid or its lactone. We became interested in such a possibility when we discovered that L-ascorbic acid was rare or absent in certain yeasts and fungi whereas a L-ascorbic acid analog, D-glycero-pent-2-enono- 1,4-lactone (D-erythroascorbic acid), was present. It has long been known that oxalate occurs in yeasts and fungi and its production plays a role in plant pathogenesis. As to the biosynthetic origin of fungal oxalic acid there is little information although it is generally assumed that oxaloacetate or possibly, glycolate, might be that precursor.
Date: January 1, 1991
Creator: Loewus, F.A. (Washington State Univ., Pullman, WA (United States). Inst. of Biological Chemistry) & Seib, P.A. (Kansas State Univ., Manhattan, KS (United States). Dept. of Grain Science and Industry)
Partner: UNT Libraries Government Documents Department

Novel 7-substituted coumarin compounds and an improved method for their synthesis. [Patent application]

Description: Novel substituted coumarin compounds and an improved method for their synthesis are disclosed. The preferred class of compounds are substituted at the 7-position. The method of synthesis comprises reacting a polyhydroxy benzene or a substituted phenol, with a ..beta..-alkoxy acrylic acid or nitrile, in the presence of a Lewis acid catalyst. By the inclusion of the catalyst in the reaction mixture, the reaction can be carried out under much milder experimental conditions and in increased yields. The method is also applicable to the preparation of substituted amino phenols.
Date: January 20, 1982
Creator: Bissell, E.R.
Partner: UNT Libraries Government Documents Department

Interdisciplinary research and training program in the plant sciences

Description: This document is the compiled progress reports from the Interdisciplinary Research and Training Program in the Plant Sciences funded through the MSU-DOE Plant Research Laboratory. Fourteen reports are included, covering topics such as the molecular basis of plant/microbe symbiosis, cell wall proteins and assembly, gene expression, stress responses, growth regulator biosynthesis, interaction between nuclear and organelle genomes, sensory transduction and tropisms, intracellular sorting and membrane trafficking, regulation of lipid metabolism, the molecular basis of disease resistance and plant pathogenesis, developmental biology of Cyanobacteria and hormonal involvement in environmental control of plant growth. 132 refs. (MHB)
Date: January 1, 1991
Creator: Wolk, C.P.
Partner: UNT Libraries Government Documents Department

Investigation of molecular mechanisms in photodynamic action and radiobiology with nanosecond flash photolysis and pulse radiolysis. Progress report, October 1, 1980-September 30, 1981

Description: Laser flash photolysis experiments have led to a new mechanism for the ultraviolet photolysis of aqueous tryptophan (Trp), indole (Ind) and certain indole derivatives. Excitation at 265 nm leads to photoionization via a pre-fluorescent state with thermal activation. A new formula is proposed for predicting enzyme inactivation quantum yields. The predictions are in good agreement with measurements on six important enzymes at 254 nm and 280 nm. Kinetics models have been developed and tested for important stages in the photosensitization of DNA to near-ultraviolet radiation by furocoumarin compounds currently used for PUVA therapy (psoralen plus UV-A) of psoriasis and other human skin diseases. Experiments on photobinding of psoralen (Ps) and 8-methoxypsoralen (8-MOP) to calf thymus DNA are consistent with the assumption that equilibrium dark complexing of the furocoumarin to the DNA is a precondition for the formation of covalent monoadducts and cross-links. Singlet oxygen generation by furocoumarins has been investigated with liposomes and human erythrocytes (rbc). Results obtained with 3-carbethoxypsoralen (3-CPs), an experimental alternate PUVA sensitizer claimed to be non-tumorigenic, show that 3-CPs interacts with liposome and rbc membranes in the dark. Studies on photosensitization of egg lecithin liposomes by methylene blue (MB) incorporated in the membrane have led to the new result that membrane lysis is a two-stage process. The first stage induced by red light irradiation leads to membrane damage initiated by O/sub 2/*. Membrane lysis takes place in the dark, second stage under the action of mild hydrodynamic stress, such as slow gas bubbling.
Date: June 1, 1981
Creator: Grossweiner, L I
Partner: UNT Libraries Government Documents Department