Solvolysis of 2-Propyl 4-Nitrobenzenesulfonate in 1,1,1,3,3,3-Hexafluoro-2-propanol

Article abstract of DOI:10.1021/jo00275a014

The reaction of the halide nucleophiles and of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) with methyl 4-nitrobenzenesulfonate (methyl nosylate) and 2-propyl nosylate was examined in the solvent 1,1,1,3,3,3-hexafluoro-2-propanol.A plot of the logarithm of the second-order rate constant, k(nuc), for reaction of the halides and solvent with 2-propyl nosylate against log k(nuc) for reaction with methyl nosylate is linear and has a slope of 0.34.The point corresponding to the reaction with HFIP falls on the same line as the halide nucleophiles.On the basis of these results, it is suggested that the solvolysis in HFIP of the simple secondary compound 2-propyl nosylate may be occuring by a concerted S(N)2 mechanism and may not involve an ion-pair intermediate