Facile and Selective Carbonylation of Methane in Superacids

Rege, Peter J.F. de; Gladysz, J. A.; Horváth, István T.

doi:10.1002/1615-4169(200212)344:10<1059::aid-adsc1059>3.0.co;2-o

Cited by 22 publications

(16 citation statements)

References 18 publications

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“…6 Other applications of acids were the platinum catalyzed hydrogenation of aromatics in supported BF 3 ·H 2 O (or rather a very strong acid: H + [BF 3 OH] -) phase, 7 the first observation of the formil cation in solution, 8 and the carbonylation of methane in superacids. 9 Methanol served both as a substrate and a solvent in the copper catalyzed oxidative carbonylation of methanol to dimethyl carbonate 10 and in the cobalt catalyzed methoxyhydrocarbonylation of butadiene. 11 The frustration with the potential over-oxidation of methanol during the oxidation of methane led to the development of fluorous biphasic systems, 12 including the design of the fluorous soluble phosphine modified rhodium hydroformylation catalyst.…”

Section: Introductionmentioning

confidence: 99%

Solvents from nature

2008

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In this perspective, a personal journey from solvent to solvent is presented to demonstrate how environmentally friendly solvents can be part of the solution of various chemical challenges. Solvents are important components of Nature to provide one or more liquid phases for chemical reactions and processes. While some solvents are available from Nature even in large quantities, most of the solvents are man-made. Historically, solvents were developed and/or selected to help the chemical or physical objectives of the user(s) only. With the increasing importance of local and global health and environmental issues, including the introduction of green chemistry and the molecular approach for pollution prevention, the potential impacts of solvents became important selection tools. One of the key principles of green chemistry is the elimination of solvents in chemical processes or the replacement of hazardous solvents with environmentally benign solvents. The development of solvent-free alternative processes is the best solution, especially when either one of the substrates or the product is a liquid and can be used as the solvent of the reaction. However, if solvents are crucial to a process we should select from solvents that will have no or limited impact on health and the environment.

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Section: Introductionmentioning

confidence: 99%

Solvents from nature

2008

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“…Significant research efforts are being directed at more direct methods to generate acetic acid, such as the oxidation of ethane to acetic acid [15,16] or the carbonylation of methane [5,[17][18][19][20][21] but no new processes have yet been commercialized. We now report the observation of the direct, one-step, selective, oxidative coupling of two methane molecules to acetic acid in yields of~8%.…”

Section: Introductionmentioning

confidence: 64%

“…Several new catalyst systems have been reported for the selective conversion of methane to functionalized methyl products such as methanol [8,9], esters [9,10,22,23], sulfonic acid [9,[24][25][26] and acetic acid [5,[17][18][19][20][21]. In the reported cases of methane conversions to acetic acid, the methyl group of the acetic acid is derived from methane while the carboxylic group is derived from various carbon sources such as CO [5,17,19], CO 2 [18] or carboxylic acid [21] reactants.…”

Section: Introductionmentioning

confidence: 86%

“…However, these observations do not fully explain how the acetic acid is formed so efficiently and selectively. Given the unusual selectivity, novelty of the condensation reaction, and consistent reports [5,[17][18][19][20][21] that the conversion of methane to acetic acid requires other carbon sources such as CO, carboxylic groups or CO 2 as precursors to the carboxylic group, we investigated whether some unknown carbon impurity may be present that could be the source of the carboxylic group of the acetic acid produced in our system. To confirm the origins of both carbons of the acetic acid we examined the reaction using >98% isotopically enriched [ 13 C]-methane [30].…”

Section: Introductionmentioning

confidence: 99%

“…This is because, given the high selectivity for formation of acetic acid relative to CO 2 , this reaction must take place without extensive over-oxidation of the methanol to CO 2 and also must be compatible with the activation of methane. CO under superacid conditions without transition metal catalysts has been reported [34]. However, such a mechanism is unlikely in this system as control experiments with mixtures of CH 4 /CH 3 OH/H 2 SO 4 showed that no acetic acid was generated without added Pd(II).…”

Section: Introductionmentioning

confidence: 99%

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Homogeneous, catalytic, oxidative coupling of methane to acetic acid in one step

et al. 2005

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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°C in concentrated sulfuric acid. 13 C isotopic labeling studies show that both carbons of acetic acid originate from two methane molecules in a formal eight-electron redox reaction. 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-CH 3 species, followed by efficient oxidative carbonylation with methanol, generated in situ from methane, to produce acetic acid. Control Experiments suggest that the carbonylation occurs via the in situ oxidation of CH 3 OH to low levels of CO.

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Methane–to–Methanol Conversion

Hashiguchi

Hövelmann

Bischof

et al. 2005

Encyclopedia of Inorganic Chemistry

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Natural gas (NG) is an abundant, clean, underutilized fossil fuel that can augment or replace petroleum as the feedstock to fuels and chemicals. However, given the relatively high transportation costs for this highly volatile gas, utilization of NG will only be possible if inexpensive, efficient, large‐scale technologies can be developed to chemically convert NG to liquids feedstocks (e.g., long chain alkanes or methanol). Current syngas‐based technologies can carry out this chemical conversion with very high carbon yield (∼70%) while utilizing the only economically viable co‐reactant on this enormous scale: dioxygen or ideally air. However, despite these attractive characteristics, these processes are too expensive to displace petroleum primarily due to the high capital costs associated with the high temperatures required to generate syngas. Substantial effort toward the development of less expensive, lower temperature (<250 °C) processes for the selective, high‐yield oxidative conversion of methane, the major component of NG, to functionalized products has yielded a number of potential systems. This article is focused on one very promising approach: the use of homogenous organometallic and/or inorganic complexes in liquid solutions to mediate the oxidative conversion of methane. Heterogeneous (gas/solid) systems are not covered. Considering the ultimate goal of replacing petroleum with NG, we have organized this article with respect to both fundamental chemistry as well as the important practical considerations of whether or not systems can utilize dixoygen as the ultimate co‐reactant. Two fundamentally different mechanistic strategies have emerged: (i) the use of coordination catalysts that coordinate and cleave the CH bond of methane (defined as CH activation) or that coordinate and activate the co‐reactant (defined as oxidant activation), and (ii) the use of chain reactions based on reactive species such as free radicals or other chain carrying species. Systems that fall into these two categories are further categorized with respect to whether or not oxygen is or can be utilized as the ultimate co‐reactant. The goal is to provide the reader with an efficient way of quickly finding or classifying the rapidly growing body of literature by reaction mechanism and co‐reactant utilized.

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Facile and Selective Carbonylation of Methane in Superacids

Abstract: The carbonylation of CH4 with carbon monoxide in superacids HF/SbF5 or HSO3F/SbF5 leads to the exclusive and quantitative formation of the acylium ion ([CH3CO]+[SbF6]−) with the concomitant stoichiometric formation of SbF3.

Cited by 22 publications

References 18 publications

Solvents from nature

Solvents from nature

Homogeneous, catalytic, oxidative coupling of methane to acetic acid in one step

Methane–to–Methanol Conversion

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