Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners with Ph3P and Some Properties of the Iminophosphorane Products

Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners with Ph3P and Some Properties of the Iminophosphorane Products Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669

Output data

Year: 2011, Volume: 50, Number: 7, Pages: 3017-3027 Pages count : DOI: 10.1021/ic102565x

Authors

Makarov Alexander Yu ¹ , Zhivonitko Vladimir V. ^2,4 , Makarov Arkady G. ¹ , Zikirin Samat B. ^2,3,4 , Bagryanskaya Irina Yu ¹ , Bagryansky Victor A. ³ , Gatilov Yuri V. ¹ , Irtegova Irina G. ¹ , Shakirov Makhmut M. ¹ , Zibarev Andrey V. ^1,2,4

Affiliations

1	(Данные Web of science) Russian Acad Sci, Inst Organ Chem, Siberian Branch, Novosibirsk 630090, Russia
2	(Данные Web of science) Russian Acad Sci, Int Tomog Ctr, Siberian Branch, Novosibirsk 630090, Russia
3	(Данные Web of science) Russian Acad Sci, Inst Chem Kinet & Combust, Siberian Branch, Novosibirsk 630090, Russia
4	(Данные Web of science) Novosibirsk State Univ, Natl Res Univ, Dept Phys, Novosibirsk 630090, Russia

Interaction between Ph3P and 1,3,2,4-benzodithiadiazine (I); its 6,7-difluoro (2), 5,6,8-trifluoro (3) and 5,6,7,8-tetrafluoro (4) derivatives; and 5,6,8-trifluoro-3,1,2,4-benzothiaselenadiazine (5) proceeded via a 1:1 condensation to give Ph3P=N-R iminophosphoranes (1a-5a, R = corresponding 1,2,3-benzodichalcogenazol-2-yls), which are inaccessible by general approaches based on the Staudinger and Kirsanov reactions. In contrast, neither Ph3As nor Ph3Sb reacted with 1 and 4. Molecular structures of 1a-5a and 5 were confirmed by X-ray diffraction (XRD). The crystals formed by chiral molecules of 2a-5a were racemic, whereas the crystal of la was formed by a single enantiomer. In all Of the Ph3P=N-R derivatives, one of the Ph rings is oriented face-to-face to the hetero ring, R. Upon heating to similar to 120 degrees C in squalane (1a, 3a, 4a) or dissolving in chloroform at ambient temperatures (1a, 2a, 4a) the Ph3P=N-R derivatives generated the 1,2,3-benzodithiazolyls (1b-4b, respectively) whose identity was confirmed by electron paramagnetic resonance (EPR). 2,1,3-Benzothiaselenazolyls 5b and 6b were detected by EPR as the main paramagnetic products of solution thermolysis of 5 and its 5,6,7,8-tetrafluoro congener (6), respectively. Passing a chloroform solution of 4a through silica column unexpectedly gave 5-6-6-6 tetracyclic (9) and 6-10-6 tricyclic (10) sulfur-nitrogen compounds, which were 'characterized by XRD.

Makarov A.Y. , Zhivonitko V.V. , Makarov A.G. , Zikirin S.B. , Bagryanskaya I.Y. , Bagryansky V.A. , Gatilov Y.V. , Irtegova I.G. , Shakirov M.M. , Zibarev A.V.
Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners with Ph3P and Some Properties of the Iminophosphorane Products
Inorganic Chemistry. 2011. V.50. N7. P.3017-3027. DOI: 10.1021/ic102565x WOS Scopus РИНЦ

Published print:

Apr 4, 2011

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