Synthesis of Halogenated Esters of Fluorinated Carboxylic Acids by the Regio- and Stereospecific Addition of Acyl Hypochlorites to Olefins

Article abstract of DOI:10.1021/jo01295a009

Addition reactions of the fluorinated acyl hypochlorites CF3CO2Cl, C2F5CO2Cl, n-C3F7CO2Cl, ClCF2CO2Cl, and HCF2CO2Cl with CF2=CF2 and CF2=CH2 form the respective esters in varying yields.The reactions are regiospecific with CF2=CH2.Additional reactions of CF3CO2Cl with CF2=CFCl, CF2=CCl2, CH2=CH2, and cis- and trans-CFH=CFH further illustrate the potential of the acyl hypochlorites for the synthesis of a variety of esters.In addition, the latter reactions provide further examples of the regiospecificity of these additions and two examples of their stereospecificity.A concerted cis addition is proposed.The new esters exhibit excellent thermal stability, but are unstable in the presence of KF.