Typescript / 212 leaves & 1 reprint / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1966

Typewritten / Copies of author's previously published articles inserted. / 159 leaves : ill. ; 26 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1960

Thesis (Ph.D.) -- University of Adelaide, Dept. of Organic Chemistry, 1966. / Typescript.

Thesis (Ph.D.)--University of Adelaide, Dept. of Organic Chemistry, 1960. / Typewritten. Copies of author's previously published articles inserted.

Thesis--University of Florida. / Description based on print version record. Typescript. Vita. Includes bibliographical references (leaves 82-85).

A three part study involving aspects of radical properties of various aromatic species was accomplished. Experiments to ascertain the importance of geometric and electronic effects on the intramolecular transfer of a pi-complexed radical to a terminal double bond was performed. Several 4-aryl-1-butenes were reacted in competition with 1-undecene with a variety of radical precursors at 70��C. The reactions were studied in both complexing and noncomplexing solvents. Most of the relative rates varied little from unity and no dependence on solvent was observed. A series of 21 phenacylarenes was subjected to mass spectrometry. The fragmentation process leading to arylmethyl radicals and benzoyl cations was measured by calculating the ratios of parent ion to benzoyl cation signal strength. In the case of the eleven homoaromatic compounds little overall correlation of these values to traditionally accepted arylmethyl radical stabilities was found. The degree of fragmentation for isomers of the same compound were found to be explicable in term of arylmethyl radical stabilities. Degrees of fragmentation of some compounds could be rationalized in terms of the bond order of the bond being broken, as calculated by AM1 methods. The ten heteroaromatic compounds showed little correlation of fragmentation with bond order. The degree of fragmentation was found to be dependent on many different variables of the individual molecules. No correlation with any one factor could be found. The relative rates of benzylic hydrogen atom abstraction from a series of substituted toluenes and cumenes under conditions of bromination by diethyl bromomalonate were determined at 70��C. A range of reactivity of 21.7 and 10.5 was found for the toluenes and cumenes respectively. The relative rates were found to correlate best with Hammett sigma plus constants. Hammett values of -0.89 and -0.73 were calculated for the substituted toluenes and cumenes. Reactivities for several alkyl benzenes having different steric requirements at the reaction site were also studied. The relative rates for these compounds indicate a relatively large radical to be the atom abstracting agent. The results of the Hammett correlations combined with the studies involving the steric properties of the abstracting radical suggest that diethyl malonyl radical is the hydrogen atom abstracting species. / Graduation date: 1997

Thesis (Ph. D.)--University of Texas at Austin, 2005. / Supervisor: John M. White. Vita. Includes bibliographical references.

toc / Chemistry / Master / Master of Science

published_or_final_version / Chemistry / Master / Master of Science

The aroma of Tuber gibbosum, a native Oregon truffle, was characterized using two distinct techniques. Volatile aroma constituents were identified by chemical analysis, and sensory characteristics were determined by examining response of the general populace to the truffle aroma. Truffle samples from four maturity ranges, as determined by microscopic examination of each specimen for spore maturity, were compared for amounts and types of aroma volatiles present. Aroma volatiles of frozen specimens of T. gibbosum were sampled using a headspace concentration technique. Volatile compounds were analyzed by gas chromatography/mass spectrometry/data system (GC/MS/DS) and the total volatile profile was found to contain up to 20 compounds, depending on sample treatment and maturity. Seven compounds were found to be the major aroma constituents and were selected for further investigation. These 7 compounds were identified from their mass spectra and the identities substantiated by determining their Kovats retention indices. Amounts of volatile compounds present in each sample were determined by capillary gas chromatographic (GO analysis using an internal standard of n-tridecane for quantitative determinations. The major aroma constituent for all the samples was oct-l-en-3-ol, representing about 50% of the total aroma profile. The other 7 major components were 8- and 6-carbon alchols, ketones and aldehydes. Quantitative data for all samples and components were analyzed statistically. A descriptive model for truffle maturity was derived based on the amounts of 5 of the 7 compounds, and the sum of the amounts of the 7 major constituents. A comparison of volatiles from ascorbic acid treated and untreated control truffle samples indicated an apparent reduction in the amounts of several compounds. The examination of public response to the aroma of T. gibbosum was conducted as part of a display on truffles at the Oregon Mycological Society Mushroom Show. The aroma of this truffle, and three other native Oregon truffles were rated for desirability and preference. Results indicate T. gibbosum was not the favored sample, but was liked by about 2/3 of the population. Comparison of responses by males and females showed no differences for individuals liking the truffle aromas. However, females rated the truffle aromas of 3 of the 4 species as more unpleasant than did males. / Graduation date: 1986