Reactions of Arylthiazylamides with Internal and External Fluoro Electrophiles − Formation of Products with Unusual Structures

Abstract

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 de-

2,1,3‐Benzothiadiazole and Derivatives: Synthesis, Properties, Reactions, and Applications in Light Technology of Small Molecules

“…An elegant reaction pathway was used to perform the synthesis of new, naphthalene‐containing, polyfluorinated derivative 78 , as shown in Scheme 72. It was show that intramolecular nucleophilic cyclization of arylthiazylamides bearing at least one ortho ‐fluorine offers a novel synthetic approach to BTD derivatives.…”

Recent Developments in the Synthesis and Applications of 1,2,5-Thia- and Selenadiazoles. A Review

“…73 N-Polyfluoroarylsulfur diimides 72 were proposed as intermediates in the synthesis of fused perfluoronaphthothiadiazole 73 (Scheme 34). 75,77 The cesium fluoride deprotects the sulfur diimide to afford a sulfur diimide anion, which can be regarded as a thiazylamide due to the short terminal SN bond. 78 This reacted with the fluorinated arene 74 to give an intermediate sulfur diimide, which subsequently undergoes intramolecular cyclisation to afford the fused thiadiazole 37.…”

Molecular complexes of octafluoronaphthalene with catenated chalcogen–nitrogen compounds C6H5–X–NSN–SiMe3 (X=S, Se)

“…Recently, 1:1 molecular complexes between octafluoronaphthalene and acyclic (Ar-N S N-Ar, Ar-N S NSiMe 3 ) and heterocyclic (7-methyl-2,1-benzothiazole) sulfur-nitrogen compounds featuring p-stacking interactions of the arene-polyfluoroarene type were synthesized [5,6]. Also, 2:1 inclusion complexes of the bicyclic sulfur-nitrogen compounds Ar-CN 5 S 3 (including polyfluorinated derivatives) and fluorocarbon and hydrocarbon aromatics were prepared, the inclusion is driven by arene-polyfluoroarene p-stacking interactions [4].…”

“…Also, 2:1 inclusion complexes of the bicyclic sulfur-nitrogen compounds Ar-CN 5 S 3 (including polyfluorinated derivatives) and fluorocarbon and hydrocarbon aromatics were prepared, the inclusion is driven by arene-polyfluoroarene p-stacking interactions [4]. These investigations [4][5][6] showed that the molecular geometries of the sulfur-nitrogen derivatives were practically not affected by these interactions. In some cases, the co-crystals were much better suited for X-ray crystallography than the crystals of the individual compounds.…”

“…In some cases, the co-crystals were much better suited for X-ray crystallography than the crystals of the individual compounds. Based on these findings, a methodology was suggested [4] which uses arene-polyfluoroarene co-crystals for the structural characterization of aromatic compounds (including liquids [5,6]) for which good quality homocrystals are not available. With the present work we continue our investigations [4][5][6] on the ability of aryl-substituted chalcogen-nitrogen compounds to produce co-crystals with polyfluoroaromatic derivatives.…”