Uses
Azidomethyl Phenyl Sulfide is a reagent for amination of organomagnesium compounds; allows amination and oxidation of α,α-
disubstituted ester enolates via 1,2,3-triazol-5-ones; a synthetic equivalent of methyl azide for the synthesis
of methylaziridines; substituted α-azido sulfides undergo Beckmann-type rearrangements to provide
lactams and imino thioethers.
Preparation
Preparative Method of Azidomethyl Phenyl Sulfide: chlorination of Thioanisole with Sulfuryl Chloride followed by treatment of the
resultant α-chloro sulfide with Sodium Azide in acetonitrile
[1].
reaction suitability
reaction type: click chemistry
storage
Azidomethyl Phenyl Sulfide is the same as with all azides of low or moderate molecular weight, heat or shock
can cause vigorous, possibly explosive, nitrogen evolution. Distillation should be performed behind a blast
shield at reduced pressure and temperatures less than 110 °C. Similar compounds have been shown to
decompose with nitrogen evolution at ~120 °C. Striking neat azidomethyl phenyl sulfide with a hammer
fails to cause detonation. Storage under nitrogen in an amber bottle in a refrigerator is recommended. It is
incompatible with strong acids, bases, and oxidizing agents. When the reagent is used for the amination of
organomagnesium reagents, an intermediate triazene is formed. Certain triazenes are known to be
carcinogenic, thus caution in handling these intermediates should be exercised. Rinsing glassware with
bleach will dispel the disagreeable odor associated with azidomethyl phenyl sulfide,
phenylthiomethyltriazenes, and other sulfur-containing byproducts encountered in the use of this reagent.
Handle in a fumehood.
References
1. Trost, B. M.; Pearson, W. H. JACS 1981, 103, 2483.
