Inorganic Salts and Dehydrating Agents Cooperatively Promoted Ru-Catalyzed Ethylene Methoxycarbonylation Using CO₂ as a CO Surrogate

Abstract

The use of CO2 as a CO surrogate for the carbonylation of olefin has attracted considerable attention due to its abundance, readily availability, nontoxicity, and recyclability. In this work, we describe the synthesis of methyl propionate (MPA), a key intermediate for methyl methacrylate in the commercial Lucite Alpha process, by the ruthenium-catalyzed methoxycarbonylation of ethylene with CO2 as a carbonyl source. An efficient approach to producing MPA has been developed by adding metal halide promoters and dehydrating agents. Control experiments suggest that the NHC-Ru-hydride may be the real active species formed in situ by the reaction of Ru3(CO)12 with ionic liquid (IL). NMR data demonstrate that inorganic salts favor the formation of active species, which is an important issue for their promotion effect. In terms of the strategy to overcome chemical equilibrium by the addition of dehydrating agents and IL participation in the formation of NHC-Ru-hydride active species, a tasked IL containing a siloxyl group was employed to Ru-catalyze the methoxycarbonylation of ethylene, which showed higher catalytic efficiency in comparison to IL without a siloxyl group.

Keywords

• carbon dioxide
• hydroesterification
• inorganic salts
• methyl propionate
• Ru-hydride species
• the siloxyl-containing ionic liquid