Solvolyis of 1-Adamantyl Nitrate. Y(ONO2) Scale and Product Partitioning in Aqueous Ethanol

Article abstract of DOI:10.1021/jo00306a018

The specific rate of solvolysis of 1-adamantyl nitrate has been measured for four solvents over a range of temperature, including 50.0 deg C, and for 30 additional solvents at 50.0 deg C.Autocatalysis is observed only in 100percent 2,2,2-trifluoroethanol, and this can be removed by addition of pyridine.A scale of solvent ionizing power values (Y_ONO2) is developed in terms of Grunwald-Winstein equation.The Y_ONO2 values correlate well with previously determined Y_OTs values, with a slope of close to unity.In aqueous ethanol, attack by water is favored.A selectivity value of 1.96 +/- 0.04 is observed in the 90-60percent ethanol range, falling slightly in value in more aqueous mixtures; possible explanations for this fall are discussed.