Intramolecular Geminal and Vicinal Element Effects in Substitution of Simple Bromo(chloro)alkenes by Methoxide and Thiolate Ions. An Example of a Single Step Substitution?

Abstract

Intramolecular element effects k(Br)/k(Cl) for substitution of geminal bromochloroalkenes BrC(Cl)=C(Br)Cl (1), BrC(Cl)=CCl(2) (2), Me(2)C=C(Br)Cl (3), and XCH=C(Br)Cl (X = Cl, 4; X = Br, 5), with MeO(-) and RS(-) nucleophiles were investigated. 3 did not give substitution, and 4 and 5 gave substitution with MeO(-) via an initial elimination (to acetylene)-addition route, followed by further reactions. In reactions of 4 with thiolates, geminal element effects of 2-10 were obtained. Formation of RSC(Cl)=C(Cl)Y, Y = SR, Br, is ascribed to an initial halophilic reaction, followed by addition of RSCl to the formed acetylene. Reaction of 2 with MeO(-) gave a high vicinal element effect, and RS(-) gave a high geminal element effect. Reaction of 1 with both MeO(-) and RS(-) ions gave high (2 orders of magnitude) geminal element effects, which were interpreted as indicating a rate-determining C-X bond cleavage. This is supported by the high k(Br)/k(Cl) intermolecular element effects (k(1)/k(Cl(2)C=CCl(2)) with MeO(-) and PhCH(2)S(-) ions. Mechanistic alternatives based on these observations are discussed.