960-37-2Relevant academic research and scientific papers
α-,β-, and γ-Deuterium Isotope Effects in the Solvolysis of Octan-2-yl p-Bromobenzenesulphonate in 88percent Aqueous Trifluoroethanol and 83percent Aqueous Hexafluoroisopropyl Alcohol
Gregoriou, George A.,Varveri, Fannie S.
, p. 985 - 990 (2007/10/02)
Solvolysis of octan-2-yl p-bromobenzenesulphonate (1) and its α-2H1, β-2H3, β2H2 2)-(1)>, and γ-2H2 deuteriated derivatives in 88percent w/w aqueous trifluoroethanol and 83percent w/w aqueous hexafluoroisopropyl alcohol at 66 deg C gave isotope effects kH/kD of 1.154, 1.250, 1.503, and 0.997 and 1.174, 1.270, 1.553, and 1.000, respectively.These results when supplemented with those earlier reported in 65percent w/w aqueous ethanol represent a complete α- to γ-deuterium isotope effect spectrum in the solvolysis of a model secondary straight-chain alkyl system in aqueous hexafluoroisopropyl alcohol and a group of solvents covering a wide spectrum of nucleophilic ability and proposed as a model for the study of solvolytic reactions.The isotope effects increase in the order 65percent w/w ethanol 88percent w/w trifluoroethanol 83percent w/w hexafluoroisopropyl alcohol, corresponding to the decrease in the nucleophilic properties of these media.These trends are discussed in terms of Winstein's mechanistic scheme on one hand, and some features of our unified mechanism on the other.
