1,2,3-Dithiazolyle, eine neue Klasse persistenter Radikale

Abstract

Die persistenten 1,2,3-Dithiazolyle bilden sich aus den verschiedenartigsten Ausgangsverbindungen, zum Teil in sehr einfacher Weise. Es wurde eine größere Anzahl unterschiedlich substitüierter 1,2,3-Dithiazolyle hergestellt und ESR- bzw. UV-spektroskopisch characteristiert. Die Struktur der Radikale konnte durch Rückoxidation in die u. a. als Ausgangsstoffe dienenden 1,2,3-Dithiazoliumsalze, durch 33S-ESR-Spektren und durch Vergleich der Hyperfeinaufspaltungskonstanten aN bzw. der Spindichten mit quantenchemisch berechneten Werten gesichert werden.

Photochemistry of 1,3,2,4-benzodithiadiazines: formation and oxidation of 1,2,3-benzodithiazolyl radicals

“…1). The experimental hfc constants of the ESR spectrum of 2c are very close to those reported previously 3,15, 16 and agree fairly well with the values calculated at the UB3LYP/6-311G** level of theory (Fig. 1).…”

Benzo[1,2,3]dithiazole Compounds: A History of Synthesis and Their Renewed Applicability in Materials and Synthetic Chemistry, Originating from the Herz Reaction

“…This hydrolysis (Scheme 21) also appears in several later publications, and while the conditions may not have been optimised or fully investigated, the process was favoured at the time as a means to rapidly synthesise 2-aminothiophenols on moderate scales for other projects [19]. The procedure works best when applied towards ortho aminonaphthalenethiols, as the selectivity and isolated yields are seemingly higher [13,16,58,59]. Yields as high as 84% for the benzodithiazole formation and 90% for the final hydrolysis have been reported at a moderate (70 g) scale of 2-aminonaphthalene-1-thiol [60].…”

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

“…1,2,3‐Dithiazolyls were obtained by reduction of 1,2,3‐dithiazoliums,, and by thermolysis or photolysis of various sulfur‐nitrogen rings and cages . The former approach has preparative significance, whereas the latter is suitable for spectral ( e. g .…”

“…Variously fused 1,2,3‐dithiazolyls obtained by reduction of Herz cations and related 1,2,3‐dithiazoliums are more stable. Some of them were only observed by EPR, whereas some were isolated and structurally characterized by XRD ,,–,,. Especially interesting and important are bis(1,2,3‐dithiazolyls) (Scheme )–,, which revealed molecular conductor and magnetic properties in the solid state (see below).…”