Nitroso group transfer from N-nitrososulfonamides to thiolate ions. Intrinsic reactivity

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 (alfa -13.0), but virtually independent of the basicity of the thiol (beta aprox. 0.1). This dependence is ascribed to...

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Detalles Bibliográficos
Autores: Adam, Claudia Guadalupe, García-Río, L., Leis, J.R., Moreira, J.A.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2006
País:Argentina
Institución:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/106827
Acceso en línea:http://hdl.handle.net/11336/106827
Access Level:acceso abierto
Palabra clave:https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
Descripción
Sumario: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 (alfa -13.0), but virtually independent of the basicity of the thiol (beta aprox. 0.1). This dependence is ascribed to the presence of a nucleophile sesolvation equilibrium that is followed by the arrack of the thiolate ion on the niroso group via a concerted mechanism. The equilibrium constants for the loss of a nitroso group form a nitrosothiol and correlations, the parameters alfa, beta and beta nuclef were obtanided.