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

Abstract

Abstract:A new general protocol for synthesis of fused 1,2,3-dithiazoles by the reaction of cyclic oximes with S 2 Cl 2 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 (15Ñ13) 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.

Antimicrobial and Antifungal Activity of Rare Substituted 1,2,3-Thiaselenazoles and Corresponding Matched Pair 1,2,3-Dithiazoles

“…We utilize a sulfur extrusion method with a selenium insertion strategy starting from the corresponding 1,2,3-dithiazoles ( Scheme 1 ). These 1,2,3-dithiazoles were created using functionalized oxime intermediates [ 25 , 26 , 50 ]. The 1,2,3-dithiazoles were then reacted with 10 equivalents of selenium dioxide in dimethylformamide (DMF) at temperatures between 80−110 °C.…”

Fused 1,2,3‐Thiaselenazoles Synthesized from 1,2,3‐Dithiazoles through Selective Chalcogen Exchange

“…Melting points were determined with a Boetius hot‐stage apparatus and are uncorrected. 1,2,3‐Dithiazoles 1 , 3 , and 5 – 9 were prepared according to published procedures …”

Synthesis and Applications of 5‐Membered Chalcogen‐Nitrogen π‐Heterocycles with Three Heteroatoms

“…According to DFT, both RAs possessed π*‐SOMOs ,. For other variously fused 1,2,3‐dithia‐ and thiaselenazoles electrochemical reduction was irreversible and RAs were not observed ,. DFT calculations suggested that their RAs unprecedentedly belonged to two types featuring normal and abnormal elongation of the S1–E2 (E=S, Se) bond as compared with neutral precursors and possessing π*‐ and σ*‐SOMOs, respectively…”

“…However, no general procedure was established and products needed additional purification. Re‐investigation gave simplified general synthetic protocol based on the treatment of cyclic oximes with an excess of S 2 Cl 2 and pyridine in MeCN (Scheme ) …”