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Sulfone‐Linked Paracyclophanes via Macrocyclic Aromatic Thioethers: Synthetic and Structural Investigations
Author(s) -
Baxter Ian,
BenHaida Abderrazak,
Colquhoun Howard M.,
Hodge Philip,
Kohnke Franz H.,
Williams David J.
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/1521-3765(20001201)6:23<4285::aid-chem4285>3.0.co;2-d
Subject(s) - thioether , sulfone , random hexamer , chemistry , crystal structure , crystallography , stereochemistry , organic chemistry
Abstract Reaction of 4,4′‐sulfonylbis(benzenethiol) with 4,4′‐dichlorodiphenylsulfone under pseudo‐high‐dilution conditions leads to macrocyclic thioethersulfones [‐S‐Ar‐SO 2 ‐Ar‐] n (Ar=1,4‐phenylene). These include a highly strained [1+1] cyclodimer ( n =2), a cyclotrimer resulting from thioether‐exchange reactions, and a [2+2] cyclotetramer which can adopt two entirely different conformations in the crystalline state, one having molecular D 2d (“tennis‐ball‐seam”) symmetry. The same type of reaction is successful using 4,4′‐thiobis(benzenethiol) instead of 4,4′‐sulfonylbis(benzenethiol) and affords macrocycles with a higher ratio of thioether to sulfone linkages. Exhaustive oxidation of macrocyclic thioethersulfones with hydrogen peroxide affords a series of sulfone‐linked paracyclophanes, [‐Ar‐SO 2 ‐] 4 , [‐Ar‐SO 2 ‐] 6 , [‐Ar‐SO 2 ‐] 8 and [‐Ar‐SO 2 ‐] 12 . Single crystal X‐ray analysis reveals [Ar‐SO 2 ‐] 4 to be a near‐perfect square box, whilst the cyclic hexamer [‐Ar‐SO 2 ‐] 6 adopts a much more irregular conformation, and [‐Ar‐SO 2 ‐] 8 displays a “double‐box” structure clearly related to that of [Ar‐SO 2 ‐] 4 .