Thesis--University of Wisconsin--Madison. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 256-273).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1985. / Typescript. Vita. Description based on print version record. Includes bibliographical references (leaves 200-206).

Thesis (Ph. D.)--University of Wisconsin--Madison, 1970. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.

Thesis (Ph. D.)--Catholic University of America, 1942. / Reproduced from type-written copy. Bibliography: p. 25.

Allyl and cyclopropyl radicals were generated in the gas phase at a mean temperature of 140°C by new methods which promise to be of general application. Thus the radical R• may be generated by either of the two sequences: [formulas omitted] The addition-dismutation sequence was used to generate the allyl radical from allyl 3-butenoate and from diallyl oxalate, and the cyclopropyl radical from allyl cyclopropyl-carboxylate and from cyclopropyl 3-butenoate. The meta-thesis-dismutation sequence was tested for the generation of methyl radicals from the methyl ester of cyclohexa-1,4-diene-3-carboxylic acid, and applied to the generation of allyl radicals from the corresponding allyl ester. The Arrhenius parameters of the generating sequence reactions for every system were measured and discussed. These methods generate R• radicals in the presence of an excess of the sensitizing radicals, so that the present systems allow the observation of the patterns of R•/C₂H•₅ interaction. Allyl radicals were generated in the absence of appreciable amounts of other radicals, in the gas phase, by the u n s e n s i t i z e d thermal decomposition: C₃H₅OOCCOOC₃H₅ → 2C₃H•₅ + 2CO₂ log k(sec.⁻¹) = (14 ± 1) - (37 ± 2)10³/2.3RT Allyl radicals were also generated in the presence of an equal amount of cyclohexadienyl radicals in the gas phase by the unsensitized thermal decomposition: [formula omitted] log k(sec.⁻¹) = (14 ± 1) - (38 ± 3)10³/2.3RT The Arrhenius parameters of these two decompositions indicate that all the bonds which are finally broken are significantly extended in the transition state. The combination, disproportionation, isomerization, and metathesis reactions were investigated for the allyl and cyclopropyl radicals. Typical results include: [formulas omitted] / Science, Faculty of / Chemistry, Department of / Graduate

The radical anions of 1,2-dinitrobenzene, 1,3-dinitro-benzene, 1,3-dinitrobenzene-d₄, 1,4-dinitronaphthalene, 1,5-dinitronaphthalene, 1,8-dinitronaphthalene, 1,3,5-trinitrobenzene, 2,2', 4,4',6,6'-hexanitrobiphenyl, 1,2-dicyanobenzene, 1,4-dicyanobenzene, 1,2,4,5-tetracyanobenzene, and 7,7',8,8'-tetracyanoquinodi-methane have been generated by electrochemical means, and the electron spin resonance spectra recorded. The spectra have been analyzed completely in terms of the various coupling constants consistent with the symmetry of the paramagnetic species. In the isomeric dinitrobenzenes, evidence is presented which indicates that the spin density at the N¹⁴ nuclei is positive. A very large anomaly in the ESR spectrum of 1,3-dinitrobenzene radical anion is explained by assumption of rotational isomerism. A relation is presented, expressing the nitrogen coupling constants of the nitro group N¹⁴ nuclei in terms of the spin density distribution of the radical anion, calculated by the simple Huckel M.O. method. Anomalous behaviour of the 1,3,5-trinitrobenzene system is explained in terms of an electron-donor-acceptor complex between radical anion and neutral molecule. The results obtained for the cyanoaromatic anions have been compared with those of Fraenkel et al. with the exception of 7,7',8,8'-tetracyanoquinodimethane anion radical, for which a more detailed discussion is presented. C¹³ splittings have been calculated theoretically and found to agree reasonably well with experimentally determined values. For the TCNQ¯ species, evidence is also present which indicates a positive spin density at the N¹⁴ nuclei. / Science, Faculty of / Chemistry, Department of / Graduate

A one-electron transfer from the hydroxide ion to the electron acceptor p-nitrotolan was studied in aqueous dimethylsulfoxide by means of visible spectroscopy and electron spin resonance techniques. The possibility of initial nucleophilic attack followed by electron transfer from the carbanion so formed was eliminated. The analogous reaction of methoxide with p-nitrotolan was briefly examined. / Science, Faculty of / Chemistry, Department of / Graduate

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A series of new 1,5-dimethyl-6-0x0-verdazyl radicals were prepared bearing either a hydroquinone or the 3,5-di-tertiary-butyl phenol substituent in the 3 position of the verdazyl ring as precursors to verdazyl 1 semiquinone diradical anions or verdazyl 1 phenoxyl diradicals. All radical precursor tetrazanes were characterized by 'H / 13c NMR and FTIR spectroscopies, MS, and elemental analysis. Oxidation of the tetrazane precursors with NaI04 or A ~ + gave verdazyl radicals as microcrystalline solids. All verdazyl radicals were characterized by EPR, UV-visible, and FTIR spectroscopies, and high-resolution MS or elemental analysis. All attempts to oxidize the hydroquinone or phenol moieties were unsuccessful as was coordination chemistry with those verdazyls bearing a chelating ortho-hydroquinone. Several molecules were synthesized as building blocks towards tris(2,6- disubstituted-4-pyridy1)methyl radicals where the substituents were ether chloro- or methoxy- groups. All of these building blocks (aldehydes, ester, alcohol, and ketone) were characterized by 'H / 13c NMR and FTIR spectroscopies, MS, and elemental analysis. All attempts to insert a third ring onto bis(2,6-dichloro-4-pyridy1)ketone to give the radical precursor triarylmethanol have been unsuccessful. Supervisor: Dr. R. G. Hicks (Department of Chemistry)