Periana Roy A, Mironov Oleg, Taube Doug, Bhalla Gaurav, Jones C J
Department of Chemistry, Loker Hydrocarbon Institute, University of Southern California, Los Angeles, CA 90089, USA.
Science. 2003 Aug 8;301(5634):814-8. doi: 10.1126/science.1086466.
Acetic acid is an important petrochemical that is currently produced from methane (or coal) in a three-step process based on carbonylation of methanol. We report a direct, selective, oxidative condensation of two methane molecules to acetic acid at 180 degrees C in liquid sulfuric acid. Carbon-13 isotopic labeling studies show that both carbons of acetic acid originate from methane. The reaction is catalyzed by palladium, and the results are consistent with the reaction occurring by tandem catalysis, involving methane C-H activation to generate Pd-CH3 species, followed by efficient oxidative carbonylation with methanol, generated in situ from methane, to produce acetic acid.
乙酸是一种重要的石化产品，目前通过基于甲醇羰基化的三步法由甲烷（或煤）制得。我们报道了在180℃的液态硫酸中，两个甲烷分子直接、选择性地氧化缩合生成乙酸。碳-13同位素标记研究表明，乙酸的两个碳均源自甲烷。该反应由钯催化，结果与串联催化反应一致，即涉及甲烷C-H活化生成Pd-CH₃物种，随后与由甲烷原位生成的甲醇进行高效氧化羰基化反应以生成乙酸。
