I. On the Lifetime of 1,4-Diradicals. Attempted Trapping of Tetramethylene. II. Six-Membered Cyclic Diacyl Peroxides. Thermal Decomposition of 1,2,3,4-Tetrahydrophthaloyl Peroxide

Citation

Morse, Corinne Sue (1979) I. On the Lifetime of 1,4-Diradicals. Attempted Trapping of Tetramethylene. II. Six-Membered Cyclic Diacyl Peroxides. Thermal Decomposition of 1,2,3,4-Tetrahydrophthaloyl Peroxide. Master's thesis, California Institute of Technology. doi:10.7907/tjxn-bg94. https://resolver.caltech.edu/CaltechTHESIS:04212010-111536797

Abstract

Part I. Thermochemical calculations suggest that the depth of the potential well for tetramethylene 1,4-diradical can be probed by trapping the intermediate with sulfur dioxide. This was attempted using N-azacyclopentylmethane sulfonamide (1) as the precursor to tetramethylene. Gas chromatographic evidence for the presence of sulfolane in the decomposition of 1 in sulfur dioxide could not be confirmed by gc/ms and results were not reproducible. It is suggested that a precursor which decomposes more cleanly than 1 will be necessary in order to get quantitative results from a trapping experiment. Part II. 1,2,3,4-Tetrahydrophthaloyl peroxide (13) has been synthesized. Thermal decomposition of 13 gave hydrocarbon yields of 5%. No evidence was found for lactone formation, but the presence of anhydride and epoxide products suggests that bimolecular redox chemistry is occurring. The possibility of ππ^* cyclohexadiene formation in the thermal decomposition of 13 is discussed. Evidence was not found which suggests that this is occurring. Induced decomposition of 13 by rubrene resulted in emission of light consistent with chemically initiated electron exchange luminescence (CIEEL).

Thesis Files