Question

Alkyl halides, when treated with alcoholic solution of silver nitrite, give nitroalkanes whereas with sodium nitrite they give alkyl nitrites. Explain.

Answer 1

Nitrite ion is an ambident nucleophile, which can attack through ‘O’ or ‘N’.

Both nitrogen and oxygen are capable of donating electron pair. C – N bond, being stronger than N – O bond, attack occurs through C atom from alkyl halide forming nitroalkane.

However, sodium nitrite (NaNO₂) is an ionic compound and oxygen is free to donate pair of electrons. Hence, attack occurs through oxygen resulting in the formation of alkyl nitrite.