Selective Photo-Oxygenation of Light Alkanes Using Iodine Oxides and Chloride

Nichole S. Liebov, Jonathan M. Goldberg, Nicholas C. Boaz, Nathan Coutard, Steven E. Kalman, Thompson Zhuang, John T. Groves, T. Brent Gunnoe

Research output: Contribution to journalArticle

1 Scopus citations

Abstract

Partial oxidation of light alkanes to generate alkyl esters has been achieved under photochemical conditions using mixtures of iodine oxides and chloride salts in trifluoroacetic acid (HTFA). The reactions are catalytic in chloride and are successful using compact fluorescent light, but higher yields are obtained using a mercury lamp. In this photo-initiated oxyesterification process, the robust alkyl ester products are resistant to over-oxidation, and under optimized conditions yields for alkyl ester production of ∼50 % based on methane, ∼60 % based on ethane (with a total functionalized yield of EtX (X=TFA or Cl) of 80 %) and ∼30 % based on propane have been demonstrated. The reaction also proceeds in aqueous HTFA and dichloroacetic acid with lower yields. Mechanistic studies indicate that the process likely operates by a chlorine hydrogen atom abstraction pathway wherein alkyl radicals are generated, trapped by iodine, and converted to alkyl trifluoroacetates in situ.

Original languageEnglish (US)
Pages (from-to)5045-5054
Number of pages10
JournalChemCatChem
Volume11
Issue number20
DOIs
StatePublished - Oct 18 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Keywords

  • C−H functionalization
  • catalysis
  • methane
  • oxidation
  • photochemistry

Fingerprint Dive into the research topics of 'Selective Photo-Oxygenation of Light Alkanes Using Iodine Oxides and Chloride'. Together they form a unique fingerprint.

Cite this