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Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity
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Orientador(es)
Resumo(s)
The nitroso group transfer from N-nitrososulfonamides to thiolate ions was studied. Based on the results, the reaction rate is strongly dependent on the nature of the leaving group (αlg≈−1.30)(αlg≈−1.30), but virtually independent of the basicity of the thiol (βnuc≈0.10)(βnuc≈0.10). This dependence is ascribed to the presence of a nucleophile desolvation equilibrium (βd)(βd) that is followed by the attack of the thiolate ion on the nitroso group (βnuc′) via a concerted mechanism. The equilibrium constants for the loss of a nitroso group from a nitrosothiol and an N-nitrososulfonamide were used to obtain the equilibrium constants for the different reactions involved. By using rate–equilibrium correlations, the parameters αlgnorm, βdβd, and βnuc′norm were obtained.
Descrição
Palavras-chave
Kinetics Mechanism Nitrosation Thiol Sulfonamide
Contexto Educativo
Citação
Moreira, José A.; García-Río, Luís; Ramón Leis, José; Adam, Cláudia. Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity, Tetrahedron, 62, 37, 8822-8829, 2006.
Editora
Elsevier