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Folgereaktionen von Sulfenen aus Sulfonylchloriden und tertiären Aminen, 1 Über die konkurrierende Bildung von Sulfen–Trialkylamin‐S,N‐ und ‐C,N‐Addukten
Author(s) -
Opitz Günter,
Rieth Karlheinz,
Ehlis Thomas
Publication year - 1990
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19901230717
Subject(s) - chemistry , triethylamine , adduct , trimethylamine , medicinal chemistry , dimethylamine , quinuclidine , diethylamine , tertiary amine , polymer chemistry , organic chemistry
Secondary Reactions of Sulfenes from Sulfonyl Chlorides and Tertiary Amines, 1. ‐ On the Competing Formation of Sulfene ‐ Trialkylamine S,N‐ and C,N‐Adducts Phenylmethanesulfonyl chloride ( 1a ) reacts with an excess of triethylamine in acetonitrile solution at ‐40°C to give stilbene episulfone ( 9a , 95%) via the phenylsulfene–triethylamine S,N‐adduct 1ah . With trimethylamine and quinuclidine the yield of stilbene is reduced by the additional formation of (benzylsulfonyl)phenylsulfene–amines S,N‐adducts 11ag and 11ae and C,N‐adducts 15ag and 15ae which was proven by reaction with dimethylamine to 16 and by hydrolysis to 17 – 19 , respectively. 1d reacts with triethylamine yielding 94% of α‐chloro sulfones 4s and 6d via pentamethylenesulfene–triethylamine S,N‐adduct 5dh , with trimethylamine, however, C,N‐adduct 12dg is obtained which is easily oxidized to 20dg (47%). The air‐sensitive dimethylsulfene–trimethylamine C,N‐adduct 12cg was isolated and characterized.