Fused 1,2,3-Dithiazoles: Convenient Synthesis, Structural Characterization, and Electrochemical Properties

Molecules. 2016 May 6;21(5):596. doi: 10.3390/molecules21050596.


A new general protocol for synthesis of fused 1,2,3-dithiazoles by the reaction of cyclic oximes with S₂Cl₂ and pyridine in acetonitrile has been developed. The target 1,2,3-dithiazoles fused with various carbocycles, such as indene, naphthalenone, cyclohexadienone, cyclopentadiene, and benzoannulene, were selectively obtained in low to high yields. In most cases, the hetero ring-closure was accompanied by chlorination of the carbocyclic moieties. With naphthalenone derivatives, a novel dithiazole rearrangement (15→13) featuring unexpected movement of the dithiazole ring from α- to β-position, with respect to keto group, was discovered. Molecular structure of 4-chloro-5H-naphtho[1,2-d][1,2,3]dithiazol-5-one 13 was confirmed by single-crystal X-ray diffraction. Electrochemical properties of 13 were studied by cyclic voltammetry and a complex behavior was observed, most likely including hydrodechlorination at a low potential.

Keywords: X-ray diffraction; cyclic voltammetry; fused 1,2,3-dithiazoles; sulfur monochloride; synthesis.

MeSH terms

  • Crystallography, X-Ray
  • Models, Molecular
  • Molecular Structure
  • Oximes / chemistry
  • Stereoisomerism
  • Thiazoles / chemical synthesis*
  • Thiazoles / chemistry
  • X-Ray Diffraction


  • Oximes
  • Thiazoles