Rearrangements in the Solvolysis of 2-Butyl-1-C^(14) p-Toluenesulfonate

Solvolysis of 2-butyl-1-C^(14)p-toluenesulfonate in acetic acid in the presence of acetate ion under conditions where the reaction rate is essentially independent of the acetate ion concentration leads to a mixture of 91 ± 1% of 2-butyl-1-C^(14) acetate and 9 ± 1% of the rearranged product, 2-butyl-4-C^(14) acetate. It has been shown that the rearrangement is not due to rearrangement of the starting material or to elimination to yield butenes followed by addition of acetic acid. Much less rearrangement occurs in the hydrolysis of 2-butyl-1-1-C^(14) p-toluenesulfonate in 75% acetone-25% water (by volume). It is concluded that a non-classical cation of the type CH_3CH-CHCH_2 is not an important intermediate in the unimolecular hydrolysis or acetolysis of 2-butyl p-toluenesulfonate