Premium
Reactions of Arylthiazylamides with Internal and External Fluoro Electrophiles − Formation of Products with Unusual Structures
Author(s) -
Lork Enno,
Mews Rüdiger,
Shakirov Makhmut M.,
Watson Paul G.,
Zibarev Andrey V.
Publication year - 2001
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 - 10.1002/1099-0682(200108)2001:8<2123::aid-ejic2123>3.0.co;2-g
Subject(s) - chemistry , intramolecular force , electrophile , reactivity (psychology) , pyridine , aryl , nucleophile , intermolecular force , stacking , stereochemistry , crystallography , dihedral angle , medicinal chemistry , hydrogen bond , molecule , organic chemistry , medicine , alkyl , alternative medicine , pathology , catalysis
The heteroatom reactivity of the title anions [as (Me 2 N) 3 S + and Cs + salts] toward both internal and external fluoro electrophiles has been investigated. The intramolecular nucleophilic cyclization of [ArNSN] − (as the cesium salts) bearing at least one ortho fluorine afforded 2,1,3‐benzothiadiazoles (e.g. 2a , b ), whereas intermolecular condensation with polyfluorinated pyridine and naphthalene afforded Ar−N=S=N−R with R = 4‐Py F ( 4 ) and R = 2‐Np F ( 8 ). Further interaction of [ArNSN] − with 4 or 8 proceeded with the transfer of NSN units resulting in (ArN=) 2 S ( 5 ) and [RNSN] − , followed by decomposition (R = 4‐Py F ) to 4‐Py F NH 2 ( 6 ) or intramolecular cyclization (R = 2‐Np F ) to the polyfluorinated thiadiazole 9 . The compounds of types 4 , 5 , 8 , and 9 have been characterized by single‐crystal X‐ray diffraction as having both Z,E and Z,Z configurations [ 8 and 9 as molecular complexes with C 10 F 8 and (Ph−N=) 2 S ( 5e ), respectively, featuring π‐stacking interactions of the arene−polyfluoroarene type]. Besides normal aryl−polyfluoroaryl interactions, the 8· C 10 F 8 complex also displays unusual polyfluoroaryl−polyfluoroaryl π‐stacking.