Sommelet reaction

The Sommelet reaction is an organic reaction in which a benzyl halide is converted to an aldehyde by action of hexamine and water.^[1][2] It is named after the French chemist Marcel Sommelet, who first reported the reaction in 1913.^[3]

One example, thiophene-2-carboxaldehyde is prepared by the reaction of hexamine with 2-chloromethylthiophene.^[4] The reaction is formally an oxidation of the carbon.

Reaction mechanism and scope

The benzyl halide 1 reacts with hexamine to a quaternary ammonium salt 3, each time just alkylating one nitrogen atom. Then the benzylammonium undergoes an acid-catalyzed hydrolysis process.

Depending on the hydrolysis conditions, the hexamine unit might instead break apart, leaving a benzyl amine (the Delépine reaction).

The reaction can also be applied to the oxidation of benzylic amines. In this way, m-xylylenediamine can be converted to isophthalaldehyde.^[5]