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Selective Photo‐Oxygenation of Light Alkanes Using Iodine Oxides and Chloride
Author(s) -
Liebov Nichole S.,
Goldberg Jonathan M.,
Boaz Nicholas C.,
Coutard Nathan,
Kalman Steven E.,
Zhuang Thompson,
Groves John T.,
Gunnoe T. Brent
Publication year - 2019
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201901175
Subject(s) - chemistry , alkyl , photochemistry , chlorine , catalysis , trifluoroacetic acid , aqueous solution , chloride , radical , inorganic chemistry , yield (engineering) , propane , organic chemistry , materials science , metallurgy
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 .