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Nucleophilic reactions of 5‐(aryl)thianthrenium bromides with sodium aryl oxides
Author(s) -
Qian DingQuan,
Shine Henry J.,
Thurston John H.,
Whitmire Kenton H.
Publication year - 2003
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.585
Subject(s) - chemistry , aryl , halogen , medicinal chemistry , nucleophile , benzene , acetonitrile , toluene , sodium sulfide , sodium , sulfide , organic chemistry , alkyl , catalysis
Reactions between 5‐(aryl)thianthrenium bromides ( 1a – e ) with aryl (Ar) groups phenyl ( a ), p ‐tolyl ( b ), p ‐anisyl ( c ), p ‐chlorophenyl ( d ) and p ‐bromophenyl ( e ) and sodium aryl oxides ( 7a – c , Ar′ONa, Ar′ = phenyl, p ‐tolyl and p ‐chlorophenyl) were carried out in acetonitrile at 80 °C. Results are compared with those of earlier reactions of 1a – e with corresponding sodium aryl thiolates (Ar′SNa). In contrast with the thiolate reactions, those with 7a – c were too slow at room temperature to be useful. Reactions of 1a – c at 80 °C gave small amounts of benzene and toluene from 1a and b , small amounts of diaryl ethers ArOAr′ ( 9 ) and thianthrene (Th) and large amounts (90–97%) of 2‐(ArS)‐2′‐(Ar′O)diphenyl sulfide ( 10 ). Compared with reactions of 1a – c , those of 1d and e gave larger amounts (10–17%) of 9 , lesser amounts (25–30%) of 10 and substantial amounts (42–55%) of 2‐[4‐(Ar′O)‐ArS]‐2′‐(Ar′O)diphenyl sulfide ( 12 ). Small amounts of 1,4‐di(Ar′O)benzene ( 11 ) were also obtained from reactions of 1d and e . Formation of 11 and 12 is preceded by replacement of halogen by Ar′O − . Structures of products 10 and 12 were deduced by comparison with earlier products from thiolate reactions, elemental analyses, mass spectrometry molecular masses and, in the case of 10 , the crystal structure of 10d . It is proposed that products 9 – 12 are formed by nucleophilic reactions of Ar′O − at ipso positions in 1 . Copyright © 2003 John Wiley & Sons, Ltd.