52195-68-3Relevant academic research and scientific papers
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
, p. 5045 - 5054 (2019)
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.
OXIDATION OF ALKANES TO ALCOHOLS
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Page/Page column 30; 31, (2014/09/03)
The invention provides processes and materials for the efficient and cost- effective functionalization of alkanes, such as methane from natural gas, to provide esters, alcohols, and other compounds. The method can be used to produce liquid fuels such as methanol from a natural gas methane-containing feedstock. The soft oxidizing electrophile, a compound of a main group, post- transitional element such as Tl, Pb, Bi, and I, that reacts to activate the alkane C- H bond can be regenerated using inexpensive regenerants such as hydrogen peroxide, oxygen, halogens, nitric acid, etc. Main group compounds useful for carrying out this reaction includes haloacetate salts of metals having a pair of available oxidation states, such as Tl, Pb, Bi, and I. The inventors herein believe that a unifying feature of many of the MXn electrophiles useful in carrying out this reaction, such as Tl, Pb, and Bi species, is their isoelectronic configuration in the alkane -reactive oxidation state; the electrons having the configuation [Xe]4f145d10, with an empty 6s orbital. However, the iodine reagents have a different electronic configuration.
