Abstract: Although an interaction between hydrocarbon and fluorocarbon 1,3,2,4-benzodithiadiazines (1) and P(C6H5)(3) continuously produces chiral 1,2,3-benzodithiadiazol-2-yl iminophosporanes (2; in this work, 5,7-difluoro derivative 2a) via 1:1 condensation, an interaction between 1 and other PR3 reagents gives different products. With R OC6H5 and both hydrocarbon and fluorocarbon 1, only X=P(OC6H5)(3) (X = S, O) were identified in the complex reaction mixtures by C-13 and (31)? NMR and GC-MS. With R = C6F5, no interaction with the archetypal 1 was observed but catalytic addition of atmospheric water to the heterocycle afforded 2-amino-N-sulfinylbenzenesulfenamide (4). With electrophilic B(C6F5)(3) instead of nucleophilic P(C6F5)(3), only adduct H3NB(C6F5)(3) and a new polymorph of C6F5B(OH)(2) were isolated and identified by X-ray diffraction (XRD). A molecular structure of 2a was confirmed by XRD, and the -stacked orientation of one of phenyl groups and heterocyclic moiety was observed. This structure is in general agreement with that calculated at the RI-MP2 level of theory, as well as at three different levels of DFT theory with the PBE and B3LYP functionals. Mild thermolysis of 2a in a dilute decane solution gave persistent 5,7-difluoro-1,2,3-benzodithiazolyl (3a) identified by EPR in combination with DFT calculations.

Cite: Grayfer T.D. , Makarov A.Y. , Bagryanskaya I.Y. , Irtegova I.G. , Gatilov Y.V. , Zibarev A.V.
Interaction of 1,3,2,4-Benzodithiadiazines with Aromatic Phosphines and Phosphites
Heteroatom Chemistry. 2015. V.26. N1. P.42-50. DOI: 10.1002/hc.21209 WOS Scopus OpenAlex

Dates:

Published online:	Aug 11, 2014
Published print:	Jan 1, 2015

Identifiers:

Web of science:	WOS:000347543500006
Scopus:	2-s2.0-84920527759
OpenAlex:	W1539796006

Citing:

DB	Citing
Web of science	8
Scopus	9
OpenAlex	9

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