Triazenes are prepared from the N-coupling reaction between diazonium salts and primary or secondary amines. The coupling reactions are typically mild, using a base such as sodium acetate, sodium carbonate, or sodium bicarbonate.
The diazonium reagents are themselves available starting from amines. For symmetrical triazenes derived from primary amines, partial diazotization gives a mixture of the original amine and its diazo derivative that then couple with each other. For example, 1,3-diphenyltriazene (PhN=N−NHPh) can be made from aniline in a one-pot reaction. For asymmetrical triazenes, for example (phenyldiazenyl)pyrrolidine (PhN=N−NCH), the diazonium salt must be pre-made.
Analogues of Tröger's base containing a symmetric pair of asymmetric triazene side-chains have been obtained similarly.