New 3,1,2,4-benzothiaselenadiazines, related π-heterocycles including Herz cations, radicals and molecular complexes, and Bunte salts

New 3,1,2,4-benzothiaselenadiazines, related π-heterocycles including Herz cations, radicals and molecular complexes, and Bunte salts Full article

Journal

New Journal of Chemistry
ISSN: 1144-0546

Output data

Year: 2022, Volume: 46, Number: 7, Pages: 3687-3696 Pages count : 10 DOI: 10.1039/D1NJ05979C

Authors

Makarov Alexander Yu. ¹ , Volkova Yulia M. ¹ , Zikirin Samat B. ² , Irtegova Irina G. ¹ , Bagryanskaya Irina Yu. ¹ , Gatilov Yuri V. ¹ , Nefedov Andrey A. ¹ , Zibarev Andrey V. ¹

Affiliations

1	N. N. Vorozhtsov Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences
2	V. V. Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch, Russian Academy of Sciences

New chalcogen–nitrogen π-heterocycles covering 3,1,2,4-benzothiaselenadiazines, 1,3,2,4-benzodithiadiazines and 1,2,4,3,5-benzotrithiadiazepines were synthesized via the electrophilic cyclization of compounds Ar–N[double bond, length as m-dash]S[double bond, length as m-dash]N–SiMe3 under the action of SeCl2, SeCl4/FeCp2, SCl2 and S2Cl2. Heterocycles obtained were thermolyzed into persistent 2,1,3-benzothiaselenazolyls and 1,2,3-benzodithiazolyls (Herz radicals), which were characterized using EPR spectroscopy and DFT calculations. Reaction of the archetypal 3,1,2,4-benzothiaselenadiazine with SCl2 afforded 2,1,3-benzothiaselenazolium chloride (Herz salt), whereas that of sterically hindered 1,3,2,4-benzodithiadiazine resulted in a complex of the corresponding Herz salt with unexpected carbocycle-chlorinated and non-chlorinated 3,3-dioxides of the starting material, which is a rare example of a molecular complex involving a Herz cation. Formation of the dioxides can be explained through intermediate participation of the benzodithiadiazine radical cation. Hydrolysis of 3,1,2,4-benzothiaselenadiazine or 1,3,2,4-benzodithiadiazine led to Se-(2-aminophenyl)selenosulfate (Se-Bunte salt) or S-(2-aminophenyl)thiosulfate (Bunte salt), respectively.

Makarov A.Y. , Volkova Y.M. , Zikirin S.B. , Irtegova I.G. , Bagryanskaya I.Y. , Gatilov Y.V. , Nefedov A.A. , Zibarev A.V.
New 3,1,2,4-benzothiaselenadiazines, related π-heterocycles including Herz cations, radicals and molecular complexes, and Bunte salts
New Journal of Chemistry. 2022. V.46. N7. P.3687-3696. DOI: 10.1039/D1NJ05979C WOS Scopus РИНЦ

Submitted:	Dec 16, 2021
Accepted:	Jan 19, 2022
Published print:	Jan 20, 2022

Web of science	WOS:000750491600001
Scopus	2-s2.0-85125491808
Elibrary	48187129
OpenAlex	W4206051707