The tertiary aliphatic amine oxides (tertiary
N
‐oxides) undergo to thermal transformation into substituted
N
‐alkoxylamines or
N
‐hydroxylamines, and generally referred to as the Meisenheimer rearrangement. The study finds that this reaction takes place through a radical mechanism involving a homolytic cleavage of a nitrogen‐carbon bond and the migration of an alkyl group to form the
N
‐alkoxylamine. This rearrangement does not apply to aromatic
N
‐oxides. The reaction mechanism for such rearrangement has been discussed for aryl allyl
N
‐oxides,
N
‐propargylmorpholine
N
‐oxide and
N
‐propargylmorpholine
N
‐oxide. This reaction has been found to be useful for organic synthesis.