545793 Conversion of Methane, Ethane and Propane to Form Alkyl Esters: Oxy-Esterification As a Strategy for Selective Partial Oxidation

Tuesday, June 4, 2019: 2:09 PM
Republic ABC (Grand Hyatt San Antonio)
T. Brent Gunnoe1, John Groves2, William A. Goddard III3, Nichole Schwartz4, Nicholas Boaz5, Steven Kalman6, Jonathan Goldberg7, George Fortman6, Ross Fu8 and Robert Nielsen8, (1)Department of Chemistry, University of Virginia, Charlottesville, VA, (2)Princeton U., Princeton, NJ, (3)Chemistry and Chemical Engineering Division, California Institute of Technology, Pasadena, CA, (4)University of Virginia, (5)Department of Chemistry and Princeton Institute for the Science and Technology of Materials, Princeton, Princeton, NJ, (6)Department of Chemistry, University of Virginia, (7)Princeton University, (8)California Institute of Technology

The selective and low temperature conversion of light alkanes (methane, ethane and propane) to functionalized products has been a long-standing challenge. In protic media, the reaction of light alkanes with iodine oxides results in the conversion to mono-functionalized products with alkyl trifluoroacetates as the primary products. The transformations are effective over a broad range of temperatures (100 - 235 ºC) and pressures (240-6900 kPa) in non-superacidic media. Alkane conversions between 15% and 40% with selectivity for mono-functionalized products between 85% and 95% have been achieved. The presentation will focus on mechanistic studies that incorporate selectivity patterns and kinetic isotope effects for conversion of light alkanes and model hydrocarbons (e.g., adamantane), spectroscopic identification of reaction intermediates, and computational modeling. In addition, preliminary efforts to extend the reaction to photo-mediated conversions as well as thermal processes with non-iodine based oxidants will be presented.

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See more of this Session: Alkane Halogenation and Oxyfunctionalization
See more of this Group/Topical: General Submissions