Synthesis of Fluorinated Dialkyl Carbonates from Carbon Dioxide as a Carbonyl Source

Abstract Fluorinated dialkyl carbonates (DACs), which serve as environmentally benign phosgene substitutes, were produced successfully from carbon dioxide either directly or indirectly. Nucleophilic addition of 2,2,2‐trifluoroethanol to carbon dioxide and subsequent reaction with 2,2,2‐trifluoroethyltriflate ( 3 a ) afforded bis(2,2,2‐trifluoroethyl) carbonate ( 1 ) in up to 79 % yield. Additionally, carbonate 1 was obtained through the stoichiometric reaction of 3 a and cesium carbonate. Although bis(1,1,1,3,3,3‐hexafluoro‐2‐propyl) carbonate ( 4 ) was difficult to obtain by either of the above two methods, it could be synthesized through the transesterification of carbonate 1 .