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

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

doi:10.1002/cctc.201901175

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

Journal Article · Wed Sep 25 00:00:00 EDT 2019 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201901175· OSTI ID:1571528

Liebov, Nichole S. ^[1]; Goldberg, Jonathan M. ^[2]; Boaz, Nicholas C. ^[3]; Coutard, Nathan ^[1]; Kalman, Steven E. ^[4]; Zhuang, Thompson ^[2]; ^[2]; ^[1]

Department of Chemistry University of Virginia Charlottesville VA 22904 USA
Department of Chemistry Princeton University Princeton NJ 08544 USA
Department of Chemistry Princeton University Princeton NJ 08544 USA, Department of Chemistry North Central College Naperville IL 60540 USA
Department of Chemistry University of Virginia Charlottesville VA 22904 USA, Chemistry Program School of Natural Sciences and Mathematics Stockton University Galloway NJ 08205 USA

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 .

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1571528

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 20 Vol. 11; ISSN 1867-3880

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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