Thesis (Ph. D.)--Virginia Commonwealth University, 2006. / Prepared for: School of Pharmacy. Bibliography: leaves 267-283. Also available online.

No description available.

Thesis. / Includes bibliographical references.

Thesis--University of Florida. / At head of title: Contract no. W-7405-eng-26. Chemistry Division. "ORNL-3057."

Thesis (Ph. D.)--University of Wisconsin--Madison, 1959. / Typescript. Vita. Includes (as Parts I & II) reprints of articles from Applied microbiology: Production and testing of yeast mutants for glycerol formation / R.E. Wright, W.F. Hendershot, and W.H. Peterson. Vol. 5, no. 4 (July 1957), p. 272-279 -- Factors affecting production of glycerol and D-arabitol by representative yeasts of the genus Zygosaccharomyces / W.H. Peterson, W.F. Hendershot, and G.J. Hajny. Vol. 6, no. 5 (Sep. 1958), p. 349-357. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

The relative rates of chromic acid oxidation of eight aryltrifluoromethylcarbinols were determined in 77.2% acetic acid medium. The primary deuterium isotope effects for these alcohols ranged from 7.40 for p-tolyltrifluoromethylcarbinol to 12.93 for 3,5-dinitrophenyltrifluoromethylcarbinol at 25°. The rates fitted a Hammett plot best when modified ϭ⁺ substituent values were used and a modified ̎rho ̎value of -1.01 was observed. The rates of oxidation of several halogenated-2-propanols as well as their corresponding 2-d analogttas were also determined in 77.2% acetic acid and in 50.1% sulfuric acid. Results indicated that while the isotope effect varied with changes in the nature of the alcohol being oxidized, it was constant for a particular alcohol in solutions of varying acidity. The thermodynamic parameters for the oxidation of two different alcohols under a variety of conditions were determined and found to be approximately the same, ΔH# = 9 kcal/mole, ΔS# = -40 cal/mole deg. An extensive investigation of the oxidation of alcohols in sulfuric acid solutions ranging from 5 to 95% was conducted and a spectroscopic study was made of the behavior of chromium VI in this entire region, A ϭ* value was obtained for the CF₃ group and this was used to determine the "true rate constant", k = kobs /K, for the chromic acid oxidation of a series of primary alcohols. A Taft ϭ*- e* plot then yielded a e* value of -0.92 for the rate determining step of this reaction. A spectroscopic investigation of the variation of the pKa of chromic acid with changes in the identity of the mineral acid solvents was made, and the results were applied to explain observed variations in the rate of oxidation of isopropyl alcohol in solutions of different mineral acids all having the same acidity. The H₀ acidity function for nitric and phosphoric acid systems with a 1:1 molar ratio of sodium perchlorate was also determined. / Science, Faculty of / Chemistry, Department of / Graduate

[No abstract submitted] / Science, Faculty of / Chemistry, Department of / Graduate

The mechanism of permanganate oxidation of benzhydrol has been investigated between pH 7.00 and H₀ -2.46. The deuterium isotope effect, kH/kD, obtained by studying the oxidation rate of benzhydrol α-d, was found to fall from 7.3 at pH 7.00 to 1.08 at H₀ -1.22. Between pH 7.00 and H₀ 0.20, the reaction is of second order, first order in each of the reactants. Beyond H₀-0.50 the reaction becomes first order in carbinol and zero order in permanganate, and in this region the reaction is strongly acid-catalyzed. A study of eight substituted benzhydrols shows an excellent Hammett correlation with α⁺,ρ⁺ being -1.02. The rate-determining step at higher acidities is believed to be the scission of protonated carbinol to carbonium ion, which then reacts with permanganate in a fast step. This idea is supported by the results of a study of the rate of ionization of p-methoxybenzhydrol under conditions similar to those of the oxidation reaction. The mechanism of chromic acid oxidation of benzhydrol has been studied between H₀ 0.50 and -4.20. The reaction is acid-catalyzed in this region and was found to be of second order, first order in each of the reactants. The deuterium isotope effect with benzhydrol α-d at H₀ -1.00 is 6.81. A Hammett plot, obtained from the study of five substituted benzhydrols, shows σ to be the operative substituent constant, ρ being -0.54. The rate-determining step is believed to be the unimolecular decomposition of a chromate ester. The permanganate oxidation of triphenylcarbinol has been investigated in the region of acidity of H₀ -0.60 to -1.93. The reaction was found to be acid-catalyzed in this region and to produce benzophenone and phenol. The order of reaction was found to be the same as in the case of benzhydrol, i.e., first order in carbinol and zero order in permanganate. A study of nine substituted triphenylcarbinols gave a good Hammett correlation with σ⁺,ρ⁺+ being -1.39. As in the case of benzhydrol, the rate-determining step is believed to be the ionization of the carbinols. The chromic acid oxidation of triphenylcarbinol has been investigated between HR -2.80 and -7.48. Acid-catalysis was observed for the reaction in this region. The reaction was found to be of second order, first order in each of the reactants, as in the case of benzhydrol. The reaction gave a quantitative yield of benzophenone, phenol also being formed. A Hammett correlation with σ⁺+ was obtained from a study of eleven substituted triphenylcarbinols, ρ⁺+ was found to be -0.879. The rates of oxidation of the triarylcarbinols were also studied in the presence of added manganous ions, which showed an almost uniform reduction in rate for all the carbinols, the value of ρ⁺ in this case being -0.906. The migration aptitudes of the substituted aryl groups were determined and ρ⁺ for migration was found to be -1.44. A chromate ester mechanism, similar to that proposed for benzhydrol and other secondary alcohols, is believed to be operative in this case, except that the decomposition of the ester takes place by migration of the electron-rich ring. It is suggested that the chromic acid oxidation of primary and secondary alcohols may take place by an analogous rearrangement reaction of a chromate ester. In these cases the migrating group would be hydrogen. Permanganate oxidation of benzhydrol was also studied in frozen system between pH 1.50 and 12.40. A large increase in rate, compared to that in the liquid system, was observed. The deuterium isotope effect, kH/kD, of 7.2 to 7.5 was found in this system. The reactions are of second order, as in the liquid system. The acceleration in rate appears to be due to an increase in concentration of the reactants in the liquid phase between ice crystals. / Science, Faculty of / Chemistry, Department of / Graduate

The solution infrared spectra and proton magnetic resonance (PMR) spectra of several series of polyol nitrates have been examined in order to assess the potential of these two spectroscopic methods for the study of the stereochemistry of nitrate esters in solution. This thesis reports the first systematic study of the solution infrared spectra of nitrate esters. Correlations of the frequencies of the three principal nitrato group bands with structure and stereochemistry were observed for 1, 4:3, 6-dianhydrohexitol, benzocycloalkane, cyclohexane, sugar, 1, 2-diphenylethane, and polyhydric alcohol nitrates. The frequencies of the Ʋa(NO₂) and Ʋ (ON) bands were clearly dependent on molecular structure while that of the Ʋs(NO₂) band exhibited a marked steric dependence. On the basis of their solution infrared spectra, configurations were assigned to several 1,4:3,6-dianhydrohexitol mononitrates which were consistent with other properties of these compounds. A rationale of certain aspects of the spectral correlations is presented. Examination of the PMR spectra of the nitrate esters and of other esters of polyhydric alcohols revealed a relationship between molecular symmetry and the multiplicity of methylene resonances. The PMR spectrum of glycerol trinitrate could be classified as that of an (AB)₂X system and a complete spectral assignment was possible for both the methine and methylene resonances. The effect of solvent and substituent on the methylene chemical shifts of pentaerythritol derivatives has been studied on a qualitative basis and the application of PMR spectroscopy to the elucidation of the structure of previously unreported 1,2-O-isopropylidene- α-D- glucofuranose- 3, 5, 6-trinitrate, for which a complete PMR spectral assignment was possible, is described. Thin-layer chromatography (TLC) has been successfully applied to the polyol nitrates and for several groups of these a dependence of Rf value upon stereochemistry has been noted. A stereoselective detection has been found for the 1, 4:3, 6-dianhydrohexitol nitrates and a preliminary study (by TLC) of the reactions of a homologous series of twelve polyhydric alcohol nitrates with pyridine indicated large differences between the rates of reaction of homologues but not of diastereoisomers. The p-toluenesulfonate and p- bromobenzenesulfonate esters of 1, 4:3, 6-dianhydro-D- glucitol- 5-nitrate, 1, 2- O-isopropylidene-α-D- glucofuranose-3, 5, 6-trinitrate, pentaerythritol trinitrate p-bromobenzene sulfonate, allitol hexabenzoate, L-threitol tetrani-trate, L-iditol hexanitrate, and D-talitol hexanitrate are reported for the first time. / Science, Faculty of / Chemistry, Department of / Graduate

The base-induced chemistry of three enone-alcohols, 1,6-di- cyano-8,9-dimethyl-5-hydroxytricyclo[4.4.0.0[sup 5,9]]deca-3,7-dien-2- one (48) , 8 , 9-dimethyl-5-hydroxytricyclo [4.4.0.0[sup 5,9]]deca-3,7- dien-2-one (24), and 1,3,4,6,8,9-hexamethyl-5-hydroxytricyclo- [4.4.0.0[sup 5,9]] deca-3,7-dien-2-one (3) , has been investigated. The inertness of 3 under the reaction conditions (potassium hydroxide, refluxing aqueous dioxane) that converts 1,3,4,6,8,9-hexamethyl- tricyclo[4.4.0.03,10]dec-8-ene-2,5-dione (1) into 1,3,4,6,8,9- hexamethyltricyclo [4 .4.0 .0[sup 3,7]] dec-8-ene-2 , 5-dione (2) indicated that 3 is not a major intermediate in such conversion. Restriction in conformational isomerism due to the bulky bridgehead methyl groups is believed to be the main reason for prohibiting the rearrangement of 3 to 2. Under more vigorous reaction conditions (potassium hydride, refluxing dimethoxyethane (DME)), however, enone-alcohol 3 rearranged to give diketone 2 and twistane deriva- tive 28, 1,3,4,6,8,9-hexamethyltricyclo[4.4.0.0[sup 3,8]]dec-9-ene-2,5- dione, which slowly rearranged under the reaction condition to its exo-methylene isomer 29, 1, 3, 4 , 6, 8-pentamethyl-exo-9-methylene- tricyclo[4.4.0.0[sup 3,8]]decane-2,5-dione. When enone-alcohol 24 was t treated with KH at room temperature in DME, diketone 19, 8,9-di- methyltricyclo[4.4.0.0[sup 3,7]]dec-8-ene-2,5-dione, was produced. Similar treatment of enone-alcohol 48 with KH at room temperature in DME resulted in the formation of 8,9-dicyano-1,6dimethyltri-cyclo [4.4.0.0'[sup 3,7]]dec-8-ene-2,5-dione (50). Although diketones 19 and 50 have identical ring skeletons, the difference in their substituent patterns shows that they are formed by different mechanisms. Ring opening of the corresponding alkoxide is suggested as the initial step in all three reactions, and the divergent results were explicable on the basis of the substituent-controlled direction of ring opening in addition to product control through restriction of rotation of the intermediates so produced. / Science, Faculty of / Chemistry, Department of / Graduate