Substituted 1,3,2,4-benzodithiadiazines and related compounds

Substituted 1,3,2,4-benzodithiadiazines and related compounds Full article

Journal

Heteroatom Chemistry
ISSN: 1042-7163

Output data

Year: 1999, Volume: 10, Number: 2, Pages: 113-124 Pages count : 12 DOI: 10.1002/(SICI)1098-1071(1999)10:2<113::AID-HC4>3.0.CO;2-R

Authors

Bagryanskaya Irina Yu. ¹ , Gatilov Yuri V. ¹ , Makarov Alexander Yu. ¹ , Maksimov Alexander M. ¹ , Miller Alexey O. ² , Shakirov Makhmut M. ¹ , Zibarev Andrey V. ¹

Affiliations

1	Institute of Organic Chemistry, Russian Academy of Sciences, Novosibirsk, 630090, Russia
2	Chemistry Department, Rostock University, D–18051 Rostock, Germany

Despite some limitations, the 1:1 condensation of n-RC6H4-N=S=N-SiMe3 (n = 2, 3 ,4; R = CH3 OCH3 F, Cl, CF3) with SCl2 followed by intramolecular electrophilic ortho-cyclization, was found to be a general synthetic approach to the corresponding 5-R, 6-R, and 7-R-substituted 1,3,2,4-benzodithiadiazines, formally antiaromatic 12 pi-electron compounds. For precursors with n = 3, the high regioselectivity of the cyclization resulted in exclusive (R = OCH3, F) or predominant (R = CH3 Cl) formation of 6-R isomers; the ratio of the major 6-R isomer to the minor 8-R one was found to be 72:28 (R = CH3) or 78:22 (R = Cl). The preferred direction of cyclization is consistent with thermodynamics of the corresponding intermediate sigma-complexes as well as factors of kinetic control for an orbital-controlled El-Nu reaction. According to the X-ray diffraction data, the molecules of 5-CF3 (15) and 6-F (12) derivatives are nearly planar, while the molecules of 5-OCH3 (7) and 6-CH3 (4) derivatives are bent along the S-1... N-4 line by similar to 11 degrees (7) or 7 degrees (4). An attempt to adopt CsF-induced intramolecular nucleophilic ortho-cyclization of Ar-F-S-N=S=N-SiMe3, into polyfluorinated 1,3,2,4-benzodithiadiazines for polyfluroropyridine derivatives resulted in formation of polyfluorinated aminopyridines. Data obtained ave consistent with a previously suggested scheme of sulfur-nitrogen chain shortening during cyclization. Mild acid hydrolysis of the title compounds was shown to be a convenient synthetic route to substituted 2,2'-diaminodiphenyl disulfides (including polyfluorinated ones) via the corresponding 2-aminobenzenethiols. (C) 1999 John Wiley & Sons, Inc.

Bagryanskaya I.Y. , Gatilov Y.V. , Makarov A.Y. , Maksimov A.M. , Miller A.O. , Shakirov M.M. , Zibarev A.V.
Substituted 1,3,2,4-benzodithiadiazines and related compounds
Heteroatom Chemistry. 1999. V.10. N2. P.113-124. DOI: 10.1002/(SICI)1098-1071(1999)10:2<113::AID-HC4>3.0.CO;2-R WOS Scopus OpenAlex

Web of science:	WOS:000079429600004
Scopus:	2-s2.0-0001196326
OpenAlex:	W2065705967

DB	Citing
Web of science	25
Scopus	25
OpenAlex	25