Generation and reactions of alkyl radicals in solutions that contain S2O 8 2? , Ag(I), and Cu(II) ions

Abstract

1. The 1- and 3-heptyl radicals were generated by reacting the octanoic and 2-ethyl-hexanoic acids with the oxidation systems Na2S2O8-AgNO3 and Na2S2O8-AgNO3-CuSO4 in aqueous or aqueous acetonitrile solution. 2. In the absence of Cu(II) ions, these radicals in the mentioned solutions cleave H atoms from organic substrates and are converted to heptane, dimerize to the normal and branched tetradecanes, and are oxidized by Ag(II) to secondary heptanols. In addition, in aqueous solutions the 1-heptyl radicals are oxidized by the silver ions to 1-heptane. 3. In aqueous solutions that contain CuSO4, the 1- and 3-heptyl radicals are converted to heptenes and the corresponding heptanols. Heptane and n-heptyl octanoate are also formed from the 1-heptyl radicals in aqueous acetonitrile solutions. 4. The S2O 8 2− ions oxidize primary alkyl radicals to the corresponding primary alcohols. This reaction fails to occur in the presence of AgNO3.