Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringer Weg 2, 52074, Aachen, Germany.
Max-Planck-Institut für chemische Energiekonversion, Stiftstraße 34-36, 45470, Mülheim a. d. Ruhr, Germany.
ChemSusChem. 2022 Aug 19;15(16):e202201006. doi: 10.1002/cssc.202201006. Epub 2022 Jul 20.
The synthesis of acetic acid by formal isomerization of methyl formate (MF) was investigated using molecular catalysts. The base-catalyzed decarbonylation of MF, yielding CO and methanol in situ, was integrated with their palladium-catalyzed recombination for the synthesis of acetic acid and methyl acetate in a one pot reaction. The complex [Pd(Cl) (dppe)] [dppe=1,2-bis(diphenylphosphino)-ethane] in combination with NaI as iodide source and NaOMe as base were identified as promising molecular components to enable the overall conversion. Sequential application of the statistical methods design of experiments and simplex optimization was used in combination with thermodynamic analysis of the competing reaction pathways for experimental planning and data analysis. Starting from a proof-of-principle with a turnover number (TON) of 11, the catalytic system could thus be optimized to allow quantitative conversion of MF with a TON of 43000, whereby a yield of 83 % of acetate groups and a yield of 74 % for free acetic acid was obtained.
采用分子催化剂研究了通过甲酸盐（MF）的醛式异构化合成乙酸。MF 的碱催化脱羰作用，原位生成 CO 和甲醇，与钯催化的重组反应相结合，在一锅反应中合成乙酸和乙酸甲酯。确定了[Pd(Cl)(dppe)] [dppe=1,2-双（二苯基膦基）乙烷]与碘化钠作为碘源和甲醇钠作为碱的组合作为有前途的分子成分，以实现整体转化。统计方法实验设计和单纯形优化的顺序应用与竞争反应途径的热力学分析相结合，用于实验规划和数据分析。从初步验证的 11 个周转数 (TON) 开始，即可对催化体系进行优化，使 MF 的转化率达到 43000 的定量转化率，其中乙酸基团的收率为 83%，游离乙酸的收率为 74%。
