A thermodynamic resolution of dimethyl carbonate decarboxylation and the first example of its reversibility: Dimethyl ether carboxylation

• DMC decarboxylation to DME and CO2 was found to be reversible.
• Reaction performed in a continuous fixed bed reactor.
• Catalyst was a zinc-exchanged faujasite.
• Apparent activation energy from DMC to DME = 66.7 kJ mol−1.

Dimethyl carbonate (DMC) decarboxylation and dimethyl ether (DME) carboxylation was found to be a system under equilibrium in which CO2 is the cornerstone. DMC decarboxylation to DME and CO2 was thermodynamically and kinetically resolved, which allowed obtaining conditions in which DME carboxylation is thermodynamically favourable. Subsequent demonstration of DME carboxylation represents the first example of CO2 insertion in an aliphatic ether function. This study was carried out using a continuous fixed bed reactor loaded with zinc-exchanged faujasite catalyst, design to mimic the equilibrium mechanism of CO2 hydration by the enzyme carbonic anhydrase.

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