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Kinetical studies and products analyses of the thermal decomposition of t-butyl heptafluoroperoxybutyrate (TBH) in benzene, octane, nitrobenzene, pyridine, and methoxybenzene have been carried out. In benzene and octane, the decomposition appears to be entirely a radical process. In nitrobenzene and pyridine, the reactions are found to give ionic decomposition products exclusively. On the other hand, the decomposition of TBH in methoxybenzene is characteristic of mixed ionic and radical cleavages.

Bis(heptafluorobutyryl) peroxide (1) smoothly reacted with furans and thiophenes under mild conditions to regioselectively give 2-perfluoropropylfurans and thiophenes in high yields. Mechanistically, reactions with furans or thiophenes are considered to be initiated by one-electron transfers from substrates to 1. On the other hand, the perfluoropropylation of pyridine was proceeded by the usual free-radical substitution to a pyridinium salt by a heptafluoropropyl radical produced by the homolytic decomposition of 1.

The decomposition of t-butyl heptafluoroperoxybutyrate (TBH) was studied in both toluene and methanol. Kinetic and product studies from the thermolysis showed that this peroxy ester decomposes heterolytically in nonpolar solvents like toluene with homolysis, whereas in methanol this peroxy ester undergoes principally transesterification.