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New Polysulfur‐Nitrogen Heterocycles by Thermolysis of 1,3λ 4 δ 2 ,2,4‐Benzodithiadiazines in the Hydrocarbon and Fluorocarbon Series
Author(s) -
Zhivonitko Vladimir V.,
Makarov Alexander Yu.,
Bagryanskaya Irina Yu.,
Gatilov Yuri V.,
Shakirov Makhmut M.,
Zibarev Andrey V.
Publication year - 2005
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200500383
Subject(s) - chemistry , thermal decomposition , bicyclic molecule , fluorocarbon , hydrocarbon , decomposition , stacking , derivative (finance) , nitrogen , organic chemistry , medicinal chemistry , economics , financial economics
In contrast to thermolysis of 1,3λ 4 δ 2 ,2,4‐benzodithiadiazine ( 1 ) and its 5,6,7,8‐tetrafluoro derivative 2 in dilute (10 –3 M ) hydrocarbon solutions, which leads to persistent 1,2,3‐benzodithiazolyls in nearly quantitative yields, the thermolysis of 1 and 2 (the 6‐6 bicyclic system) in concentrated (0.5 M ) solutions at 150–170 °C results in complex mixtures of various polysulfur‐nitrogen heterocycles, in particular differently fused 5‐5‐6, 5‐6‐7 and 5‐6‐6‐6 polycyclic systems that were previously unknown. The products were isolated by column chromatography, and the structures of the 5‐5‐6 ( 11 , 12 ), 5‐6‐7 ( 5 , 13 ), and 5‐6‐6‐6 ( 6 , 14 , 15 ) polycyclic systems, as well as the 6‐7 ( 4 ) and 5‐6 ( 16 ) bicyclic derivatives, confirmed by X‐ray diffraction. The crystal packing of 6 and 11 – 16 is discussed with special emphasis on π‐stacking interactions. The fluorescent properties of the 5‐6‐6‐6 systems synthesized are reported. An alternative approach to the linear 5‐6‐6‐6 system 15 based on self‐condensation of an R–N=PPh 3 precursor (R = 4,5,6,7‐tetrafluoro‐1,2,3‐benzodithiazol‐2‐yl) is described, and the free‐radical character of this new reaction is proved. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)