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

Abstract

The recent progress in the synthesis of the title heterocycles exemplified by closed-and open-shell 1,2,5chalcogenadiazoles, 1,2,3-dichalcogenazoles and their hybrids (chalcogens: S, Se, and Te), and in actual or potential applications of these compounds in materials science and biomedicine, is discussed. The synthetic importance of the chalcogen exchange, both direct and indirect, is emphasized, as well as the significance of the heavier chalcogen derivatives in the design and synthesis of smart molecular materials.[a] Prof. Scheme 1.Representative examples of 1,2,5-chalcogenadiazoles and 1,2,3dichalcogenazoles including Appel and Herz cations and Herz radicals.

Synthesis of 2-((2-(Benzo[d]oxazol-2-yl)-2H-imidazol-4-yl)amino)-phenols from 2-((5H-1,2,3-Dithiazol-5-ylidene)amino)phenols through Unprecedented Formation of Imidazole Ring from Two Methanimino Groups

“…1,2,3-Dithiazoles are one of the most investigated groups of five membered sulfur–nitrogen heterocycles [ 1 , 2 , 3 ]. In addition to the utility of these heterocyclic compounds as potent biologically active compounds [ 4 , 5 , 6 , 7 , 8 ], they are efficient precursors for functional materials applied in electronics and spintronics [ 9 , 10 , 11 , 12 , 13 , 14 ].…”

“…In addition to the utility of these heterocyclic compounds as potent biologically active compounds [ 4 , 5 , 6 , 7 , 8 ], they are efficient precursors for functional materials applied in electronics and spintronics [ 9 , 10 , 11 , 12 , 13 , 14 ]. The chemistry of monocyclic 1,2,3-dithiazoles has attracted considerable attention through recent decades [ 1 , 2 , 3 ] due to the easy availability of 4,5-dichloro-1,2,3-dithiazolium chloride (Appel’s salt, 1 ) [ 15 , 16 ]. 4-Chlorosubtituted monocyclic 1,2,3-dithiazoles [ 1 , 2 , 3 , 17 , 18 , 19 , 20 ] were thoroughly investigated.…”

“…The chemistry of monocyclic 1,2,3-dithiazoles has attracted considerable attention through recent decades [ 1 , 2 , 3 ] due to the easy availability of 4,5-dichloro-1,2,3-dithiazolium chloride (Appel’s salt, 1 ) [ 15 , 16 ]. 4-Chlorosubtituted monocyclic 1,2,3-dithiazoles [ 1 , 2 , 3 , 17 , 18 , 19 , 20 ] were thoroughly investigated. The most interesting and valuable parts of this reactivity are various rearrangements of 4-chloro-1,2,3-dithiazoles, especially 5-arylimino derivatives (i.e., 2 ), which showed a great potential for the synthesis of multiple heterocycles, such as 1,2,4-thiadiazoles [ 21 ], isothiazoles [ 22 ], benzoxazines and benzothiazines [ 23 ], benzimidazoles [ 24 ], quinazolones [ 25 ], benzothiazoles [ 26 ] and benzoxazoles ( 3 , see Scheme 1 ) [ 26 , 27 , 28 ], and many others [ 1 , 2 , 29 , 30 ].…”

Revising the common understanding of metamagnetism in the molecule-based bisdithiazolyl BDTMe compound

“…[2][3][4] Neutral heterocyclic radicals containing sulfur/seleniumnitrogen rings, i.e., heterocyclic thiazyl/selenazyl radicals, play important roles in the development of molecule-based functional materials. [5][6][7][8][9][10][11][12][13] In fact, there is a long-lasting interest in the charge transport [14][15][16][17] and magnetic 8,[18][19][20] properties of heterocyclic thiazyl and selenazyl radicals, as the presence of heavy heteroatoms in these systems enhances both intermolecular electronic and magnetic exchange interactions. 10,21,22 In such compounds, the crucial component is the conjugated p-electron system.…”

3,6-Dibromopyridazine-4,5-diamine

“…1,2,5-Chalcogenadiazoles fused with benzene or heterocyclic rings are intensively used in the construction of various photovoltaic materials such as organic solar cells (OSCs) and organic light emitting diodes (OLEDs) [1][2][3][4][5][6][7]. 4,7-Dibromo-2,1,3-benzothia/selenadiazoles, [1,2,5]thia/selena [3,4-c]pyridines are the most convenient precursors for the synthesis of photoactive materials [8]. 1,2,5-Thia(selena, tellura)diazole cycle can be easily formed from the ortho-diamine moiety of 3,6-dibromobenzene-1,2-diamine and 2,5-dibromopyridine-3,4-diamine [9].…”