6914-91-6Relevant academic research and scientific papers
Iodine-Catalyzed Selective Functionalization of Ethane in Oleum: Toward a Direct Process for the Production of Ethylene Glycol from Shale Gas
Bilke, Marius,Zimmermann, Tobias,Schüth, Ferdi
supporting information, p. 21712 - 21719 (2021/01/13)
Direct valorization of ethane, a substantial component of shale gas deposits, at mild conditions remains a significant challenge, both from an industrial and an academic point of view. Herein, we report iodine as an efficient and selective catalyst for the functionalization of ethane in oleum at low temperatures and pressures. A thorough study of relevant reaction parameters revealed iodine to be remarkably more active than the previously reported Periana/Catalytica catalyst under optimized conditions. As a result of a fundamentally different catalytic cycle, iodine yields the bis-bisulfate ester of ethylene glycol (HO3SO-CH2-CH2-OSO3H, EBS), whereas for state-of-the-art platinum-based catalysts ethionic acid (HO3S-CH2-CH2-OSO3H, ETA) is obtained as the main product. Our findings open up an attractive route for the direct conversion of ethane toward ethylene glycol.
A mechanistic change results in 100 times faster CH functionalization for ethane versus methane by a homogeneous Pt catalyst
Konnick, Michael M.,Bischof, Steven M.,Yousufuddin, Muhammed,Hashiguchi, Brian G.,Ess, Daniel H.,Periana, Roy A.
supporting information, p. 10085 - 10094 (2014/08/05)
The selective, oxidative functionalization of ethane, a significant component of shale gas, to products such as ethylene or ethanol at low temperatures and pressures remains a significant challenge. Herein we report that ethane is efficiently and selectively functionalized to the ethanol ester of H2SO4, ethyl bisulfate (EtOSO3H) as the initial product, with the PtII "Periana-Catalytica" catalyst in 98% sulfuric acid. A subsequent organic reaction selectively generates isethionic acid bisulfate ester (HO3S-CH 2-CH2-OSO3H, ITA). In contrast to the modest 3-5 times faster rate typically observed in electrophilic CH activation of higher alkanes, ethane CH functionalization was found to be ～100 times faster than that of methane. Experiment and quantum-mechanical calculations reveal that this unexpectedly large increase in rate is the result of a fundamentally different catalytic cycle in which ethane CH activation (and not platinum oxidation as for methane) is now turnover limiting. Facile Pt II-Et functionalization was determined to occur via a low energy β-hydride elimination pathway (which is not available for methane) to generate ethylene and a PtII-hydride, which is then rapidly oxidized by H2SO4 to regenerate PtII-X2. A rapid, non-Pt-catalyzed reaction of formed ethylene with the hot, concentrated H2SO4 solvent cleanly generate EtOSO3H as the initial product, which further reacts with the H2SO4 solvent to generate ITA.
