Off-campus UNL users: To download campus access dissertations, please use the following link to log into our proxy server with your NU ID and password. When you are done browsing please remember to return to this page and log out.
Non-UNL users: Please talk to your librarian about requesting this dissertation through interlibrary loan.
THE OXIDATION OF HYDROCARBONS CATALYZED BY METALLOPORPHYRINS
Abstract
Iodosobenzene diacetate (IBDA) has been shown to support the hydroxylation of alkanes and the epoxidation of alkenes in the presence of simple metalloporphyrins in appropriate solvent systems at least as well as iodosobenzene. Cyclohexanol was obtained from cyclohexane in yields as high as 65% and cyclohexene oxide from cyclohexene in yields as high as 90%. Porphyrins have been synthesized directly on a polymeric support or prepared separately and attached chemically to a polymer. The metallated porphyrins attached to these supports have shown catalytic activity in the oxygenation reactions. Support materials included organic and inorganic polymers. Electron-withdrawing groups on the phenyl ring in the (alpha),(beta),(gamma),(delta)-tetraarylporphyrins increase the yields in the oxidations. A number of different metalloporphyrins (Mn, Fe, Cr, Cu, Ni, VO) and different oxidants (NaIO(,4), SO(,5)('2-), IBDA, H(,2)O(,2)), and different solvent systems were examined. Several bases (e.g., pyridines) were found to increase the efficiency of the catalysis. At present, the most efficient system among those examined is IBDA in acetone-water with manganese meso-tetrakis-(pentafluorophenyl)-porphyrin as the catalyst. The effects of several axial bases on the rate of epoxidation of cyclohexene and on the rate of "bleaching" of the catalyst were studied briefly.
Subject Area
Organic chemistry
Recommended Citation
LU, FU-LUNG HENRY, "THE OXIDATION OF HYDROCARBONS CATALYZED BY METALLOPORPHYRINS" (1984). ETD collection for University of Nebraska-Lincoln. AAI8509867.
https://digitalcommons.unl.edu/dissertations/AAI8509867