1563-80-0Relevant articles and documents
Unexpected, Latent Radical Reaction of Methane Propagated by Trifluoromethyl Radicals
Zargari, Nima,Winter, Pierre,Liang, Yong,Lee, Joo Ho,Cooksy, Andrew,Houk,Jung, Kyung Woon
, p. 9820 - 9825 (2016)
Thorough mechanistic studies and DFT calculations revealed a background radical pathway latent in metal-catalyzed oxidation reactions of methane at low temperatures. Use of hydrogen peroxide with TFAA generated a trifluoromethyl radical (?CF3), which in turn reacted with methane gas to selectively yield acetic acid. It was found that the methyl carbon of the product was derived from methane, while the carbonyl carbon was derived from TFAA. Computational studies also support these findings, revealing the reaction cycle to be energetically favorable.
Synthesis of acetic acid from CO2, CH3I and H2using a water-soluble electron storage catalyst
Yatabe, Takeshi,Kamitakahara, Kazuki,Higashijima, Kaede,Ando, Tatsuya,Matsumoto, Takahiro,Yoon, Ki-Seok,Enomoto, Takao,Ogo, Seiji
supporting information, p. 4772 - 4774 (2021/05/25)
This paper reports a possible mechanism of acetic acid formation from CO2, CH3I and H2in aqueous media and the central role played by a water-soluble Rh-based electron storage catalyst. In addition to water-solubility, we also report the crystal structures of two presumed intermediates. These findings together reveal (1) the advantage of water, not only as a green solvent, but also as a reactive Lewis base to extract H+from H2, (2) the role of the metal (Rh) centre as a point for storing electrons from H2and (3) the importance of an electron-withdrawing ligand (quaterpyridine, qpy) that supports electron storage.
Catalytic conversion of glucose into alkanediols over nickel-based catalysts: A mechanism study
Tan, Zhichao,Miao, Gai,Liu, Chang,Luo, Hu,Bao, Liwei,Kong, Lingzhao,Sun, Yuhan
, p. 62747 - 62753 (2016/07/13)
The conversion of isotope-labeled glucose (d-1-13C-glucose) into alkanediols was carried out in a batch reactor over a Ni-MgO-ZnO catalyst to reveal the C-C cleavage mechanisms. The unique role of the MgO-ZnO support was highlighted by 13C NMR and GC-MS analysis qualitatively and the MgO-ZnO favored isomerization of glucose to fructose. 13C NMR, GC-MS and HPLC analysis demonstrated that the C1 position of ethylene glycol, the C1 and C3 positions of 1,2-propanediol and the C1 position of glycerin were labeled with 13C, which is attributed to a C-C cleavage at d-1-13C-glucose's corresponding positions through retro-aldol condensation. A hydrogenolysis followed by hydrogenation pathway was proposed for glucose converted into alkanediols at 493 K with 6.0 MPa of H2 pressure over Ni based catalysts.
