Methyl Formate: How It Can Be Used as Formyl Group Source for Synthesis of Aldehydes via Hydroformylation?

摘要

For the first time the mixture of methyl formate and water is used as an alternative syngas source for hydroformylation of unsaturated compounds in the presence of rhodium catalysts modified with phosphine ligands to obtain aldehydes.Under reaction conditions,methyl formate decomposes producing methanol and carbon monoxide.The water-gas shift reaction(WGSR)takes place under the same conditions resulting in carbon dioxide and hydrogen generation.Influence of different parameters(temperature,ratios of reagents,type of the ligand)on the process is observed and the possibility of different olefins to transform to aldehydes with sufficient yields by this procedure is demonstrated.In this system methanol,hydrogen,and CO2 are accumulated.These components can be isolated and used as starting materials for the synthesis of methyl formate,an initial source for gas production.Thus,methyl formate acts as a"workhorse"in the system.In addition,to gain cyclic acetals tandem hydroformylation-acetalization was performed in the methyl formate/water system for the first time.