Some Reactions of Partly‐Fluorinated Ethyl Radicals

A study has been made of the mercury‐photosensitized decomposition of CH3CH2F and CH3CHF2 in which the primary process in each case is the cleavage of a C‐H bond to produce a fluoro‐alkyl radical. In the case of CH3CH2F, the primary process leads exclusively to the formation of the CH3CHF· radical, and the hydrogen atoms formed in this process undergo further reactions to produce C2H5· radicals. Subsequent reactions of these radicals lead to the observed C2 and C4 products. In the case of CH3CHF2, the primary process leads predominantly to the formation of the CH3CF2 radical, although some CF2H · CH2· radicals are also formed. Further reactions of the hydrogen atoms formed in the primary processes lead to CH3CHF radicals and subsequent reactions of the three fluoro‐alkyl radicals lead to a large number of products.