Catalytic Disproportionation of Formic Acid to Generate Methanol

Miller, Alexander J. M.; Heinekey, D. Michael; Mayer, James M.; Goldberg, Karen I.

doi:10.1002/ange.201208470

Cited by 29 publications

(2 citation statements)

References 30 publications

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“…A control reaction confirmed that methanol, produced from the excess of FA, 42 is not a methylating agent, because very slow methylation of aniline occurred even at 140°C for 10 h (see ESI † Supplementary Figure S9, step 2). A series of control reactions (see ESI † Supplementary Figure S9, steps 4-10) revealed that FA undergoes dehydrogenation during the earlier stages of methylation and in parallel serves as a formylation agent to yield the corresponding formamide in a competitive manner.…”

Section: Resultsmentioning

confidence: 90%

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

2015

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The methylation of amines for the synthesis of methylamines and dimethylamines as platform chemicals has been attempted mostly by homogeneous catalysts with acid additives. However, there are scarcely any reports on heterogeneous catalytic methylation reactions except for a routine approach under high temperature and high pressure of CO 2 and H 2 gases for extended reaction times. Here we report a heterogeneously catalyzed selective methylation of aromatic amines using reactive and nontoxic formic acid as the only source for the construction of methyl groups, under ambient pressure in an additive-free one-pot reaction condition. Equal proportions of Pd and Ag in the PdAg/Fe 3 O 4 /N-rGO catalyst deliver highly selective amine methylation without aromatic ring hydrogenation, as the strained Pd in the alloy is combined with the graphene-derived support, preventing nanoparticle agglomeration and the action of magnetite as a promoter. Both N-methylation and N,N-dimethylation of various substituted aromatic amines were performed with complete conversion and excellent 90-97% selectivity by controlling the reaction times in the range of 10-24 h at 140°C without unwanted aromatic ring hydrogenation. Furthermore, the developed bimetallic catalyst provided high yields (88-91%) of methylation with CO 2 +H 2 gas under high pressure, which are as good as the results of homogenous catalysts with an acid additive. To the best of our knowledge, our use of this environmentally friendly methodology is the first time that this durable heterogeneous catalyst has readily performed highly selective methylation at ambient pressure, which is attractive for industrial applications.

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Section: Resultsmentioning

confidence: 90%

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

2015

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“…In the series of C 1 molecules derived from CO 2 , formaldehyde is the missing link. Despite its importance as a C 1 building block,13 H 2 CO has not been isolated, or even observed, in any homogeneous catalytic reduction of CO 2 14. More than 20 years ago, Cutler et al.…”

Section: Methodsmentioning

confidence: 99%

Trapping Formaldehyde in the Homogeneous Catalytic Reduction of Carbon Dioxide

Bontemps

Sabo-Étienne

2013

Angewandte Chemie

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Mechanism of Formic Acid Disproportionation Catalyzed by an Iridium Complex Immobilized on Bipyridine‐Periodic Mesoporous Organosilica: A Case Study Based on Kinetics Analysis

Yamaguchi

Hashimoto

2019

Asian J Org Chem

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This work investigated the kinetics of formic acid (FA) disproportionation using an Ir complex immobilized on bipyridine-periodic mesoporous organosilica (BPy-PMO). The selectivity for methanol (MeOH) is increased using this catalyst compared to conventional homogeneous Ir complexes. This enhanced selectivity is attributed to the retention of H 2 and CO 2 generated by the competing FA dehydrogenation in PMO mesochannels having a high aspect ratio.However, no direct evidence for this process was previously obtained. The present work clarified the unique catalysis mechanism associated with a PMO catalyst exhibiting higher MeOH selectivity based on a hypothesis that the generation of MeOH via FA hydrogenation is promoted by the confinement of H 2 in the PMO pores. The results obtained from the present kinetics study and data regarding H 2 diffusion in the PMO pores strongly support this hypothesis. [a] Dr. Scheme 1. The disproportionation of formic acid. Scheme 2. The dehydrogenation of formic acid. Scheme 3. The hydrogenation of formic acid.

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Catalytic Disproportionation of Formic Acid to Generate Methanol

Cited by 29 publications

References 30 publications

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

Heterogeneous PdAg alloy catalyst for selective methylation of aromatic amines with formic acid under an additive-free and solvothermal one-pot condition

Trapping Formaldehyde in the Homogeneous Catalytic Reduction of Carbon Dioxide

Mechanism of Formic Acid Disproportionation Catalyzed by an Iridium Complex Immobilized on Bipyridine‐Periodic Mesoporous Organosilica: A Case Study Based on Kinetics Analysis

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