Benzo[5,6][1,4]dithiino[2,3-c][1,2,5]chalcogenadiazoles: synthesis and structural pecularities

Benzo[5,6][1,4]dithiino[2,3-c][1,2,5]chalcogenadiazoles: synthesis and structural pecularities Full article

Journal

Tetrahedron
ISSN: 0040-4020 , E-ISSN: 1464-5416

Output data

Year: 2026, Volume: 201, Article number : 135447, Pages count : DOI: 10.1016/j.tet.2026.135447

Tags

Fused 1.4-dithiines 1.2.5-chalcogenadiazoles Synthesis X-ray diffraction DFT calculations

Authors

Konstantinova Lidia S. ¹ , Chechulina Alexandra S. ¹ , Knyazeva Ekaterina A. ¹ , Kan Bin ² , Chen Yongsheng ³ , Aysin Rinat R. ⁴ , Rakitin Oleg A. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation
2	School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin, China
3	The Centre of Nanoscale Science and Technology and Key Laboratory of Functional Polymer Materials, Institute of Polymer Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Renewable Energy Conversion and Storage Center (RECAST), Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin, China
4	A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, ul. Vavilova 28, str.1, 119334, Moscow, Russia

A series of previously unknown molecular framework - benzodithiinochalcogenadiazoles, benzo[5,6][1,4] dithiino[2,3-c][1,2,5]thia- and oxadiazoles, and its N-oxide, have been synthesized starting from readily available dichloroglyoxime via a key intermediate, benzo[b][1,4]dithiine-2,3-dione dioxime. Benzo[5,6][1,4]dithiino [2,3-c][1,2,5]thiadiazole was successfully prepared using disulfur dichloride in DMF, while the corresponding [1,2,5]oxadiazole was unexpectedly obtained by dehydration of starting dioxime with selenium dioxide. Oxidation of benzo[b][1,4]dithiine-2,3-dione dioxime with concentrated nitric acid gave the 1,2,5-oxadiazole Noxide derivative. The molecular structures of all three compounds were unambiguously confirmed by singlecrystal X-ray diffraction, which revealed a strong dependence of the molecular planarity on the nature of the chalcogenadiazole ring and the presence of the exocyclic N→O bond. DFT calculations using the EDDB method demonstrated that the compounds do not form a unified aromatic system. The thiadiazole ring shows the highest aromaticity, whereas the oxadiazole ring is only weakly aromatic. Electron affinity (EA) values, calculated at the DLPNO-CCSD(T) level, are moderate for thia- and oxadiazoles, but increase substantially for 1,2,5-oxadiazole Noxide, correlating with spin density localization in the corresponding anion radicals. These findings provide a basis for fine-tuning the electronic and structural properties of benzodithiinochalcogenadiazoles by chalcogen variation, which may be of interest for the design of functional materials in optoelectronics and related fields.

Konstantinova L.S. , Chechulina A.S. , Knyazeva E.A. , Kan B. , Chen Y. , Aysin R.R. , Rakitin O.A.
Benzo[5,6][1,4]dithiino[2,3-c][1,2,5]chalcogenadiazoles: synthesis and structural pecularities
Tetrahedron. 2026. V.201. 135447 . DOI: 10.1016/j.tet.2026.135447 WOS Scopus OpenAlex

Submitted:	Jul 15, 2026
Accepted:	Sep 1, 2026
Published online:	Sep 10, 2026

≡ Web of science:	WOS:001874803200001
≡ Scopus:	2-s2.0-105049848712
≡ OpenAlex:	W7169842470