[2] Trifluoromethanesulfonyl azide is prepared by treating trifluoromethanesulfonic anhydride with sodium azide, traditionally in dichloromethane.

[1] However, the use of dichloromethane is avoided since it can generate highly explosive azido-chloromethane and diazidomethane.

The reaction may also instead be conducted in toluene,[3] acetonitrile, or pyridine.

[4] An alternative route starts from imidazole-1-sulfonyl azide.

[5] Trifluoromethanesulfonyl azide generally converts amines to azides.