INFIQC   05475
INSTITUTO DE INVESTIGACIONES EN FISICO- QUIMICA DE CORDOBA
Unidad Ejecutora - UE
artículos
Título:
Substitution reactions between arenethiolate anions and 1,3-dihalo-2,2-dimethylpropanes. Synthetic scope and mechanistic aspects.
Autor/es:
CECILIA A. BARRIONUEVO, JUAN E. ARGÜELLO AND ALICIA B. PEÑÉÑORY
Revista:
ARKIVOC - ONLINE JOURNAL OF ORGANIC CHEMISTRY
Editorial:
ARKAT USA INC
Referencias:
Año: 2011 vol. vii p. 145 - 259
ISSN:
1551-7004
Resumen:
The synthetic scope of the reactions between benzenethiolate, 4-methoxybenzenethiolate, 2‑naphthalenethiolate, and 2-pyridinethiolate anions with 1,3-dihalo-2,2-dimethylpropane was studied. These reactions render mono and disubstituted products from good to excellent yields. For all the substrates studied the monosubstituted halogenated product is the intermediate or the main product depending on the nature of the second leaving group. Aryl cyclopropyl sulfides were found as side products and their yields strongly depend on the base concentration (tert-BuOK). Finally, using neopentyl iodide as a model, the mechanism of these reactions was evaluated based on non-kinetic evidence, demonstrating that the reactions switch from SRN1 to polar SN2 according to the solvent employed.