Addition of free radicals to unsaturated systems. Part XXII. Photochemical addition of trifluoroiodomethane and iodine to perfluoro-(3-methylbut-1-ene) and photochemical dimerisation of the olefin

Abstract
Photochemical reaction of trifluoroiodomethane with the title olefin gives the 1:1 adduct (CF3)2CF·CFI·CF2·CF3 in low yield (22%), the perfluoroalkane (CF3)2CF·CF(CF3)·C2F5, the iodo-compounds (CF3)2C:CF·CF2I (VII), (CF3)2CF·Cl:CF2(VIII), and (CF3)2CF·CFI·CF3(IX), formed via the iodine adduct (CF3)2CF·CFI·CF2I, and the unsaturated compounds (CF3)2C:CF·CF2·CF2·CF:C(CF3)2(IV), (CF3)2C:CF·CF2·CF(CF3)·CF(CF3)2(V), and (CF3)2C:CF·CF2·CF(C2F5)·CF(CF3)2(VI), which are considered to arise by combination reactions involving the allyl radical (CF3)2C:CF·CF2. Under comparable conditions the reaction of iodine with the olefin yields the iodo-compounds (VII), (VIII), and (IX), the alkene (V), and the diene (IV). Irradiation of the olefin alone affords mainly the dimers (V) and (CF3)2CF·CF(CF3)·C[CF(CF3)2]:CF2, together with small amounts of the dimer (CF3)2CF·CF2·CF2·C[CF(CF3)2]:CF2 and the diene (IV); dimer formation probably involves rearrangement of intermediate dimer diradicals.
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