Ab initio study of the S(N)2 and E2 mechanisms in the reaction between the cyanide ion and ethyl chloride in dimethyl sulfoxide solution.
[reaction: see text] Reliable theoretical calculations predict a free energy barrier for nitrile formation from the reaction between the cyanide ion and ethyl chloride in DMSO solvent of 24.1 kcal/mol, close to the experimental value of 22.6 kcal/mol. We have also predicted that the isonitrile formation is less favorable by 4.7 kcal/mol, while the elimination mechanism is less favorable by more than 10 kcal/mol. These results indicate that isonitrile formation and bimolecular elimination are not significant side reactions for primary alkyl chloride reactions.
Almerindo
Gizelle I
GI
Departamento de Química, Universidade Federal de Santa Catarina, CEP 88040-900, Florianópolis, SC, Brazil.
Pliego
Josefredo R
JR