Synthesis of an alpha-Amino Nitrile and a bis alpha-Amino Nitrile Derivative of Thiadiazole. Reaction mechanism.

MARÍA VIRGINIA MIRÍFICO; JOSÉ ALBERTO CARAM; OSCAR ENRIQUE PIRO; ENRIQUE JULIO VASINI.

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY

John Wiley & Sons, Ltd.

Año: 2007 vol. 20 p. 1081 - 1087

0894-3230

Abstract: The first nucleophilic addition of an inorganic nucleophile (cyanide) to the activated, rigid, a-diazomethine groups of a 1,2,5-thiadiazole 1,1-dioxide is reported here. An a--amino nitrile and a bis a--amino nitrile derivatives were obtained in good yields (62 and 98% respectively) and characterized by spectroscopic, analytical and single crystal X-ray diffraction techniques. The course of the reaction, followed by cyclic voltammetry, showed that cyanide adds to only one of the two C=N double bonds of the thiadiazole, forming an anion from which an N-methyl derivative was obtained. Adequate concentrations of cyanide and methyl iodide produced directly the bis á-amino nitrile derivative.