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Zur Alkylierung von 1,3‐Dithietan‐1,1,3,3‐tetroxid (Disulfen) mit Nonafluorbutansulfonsäureestern
Author(s) -
Frasch Markus,
Sundermeyer Wolfgang,
Waldi Joachim
Publication year - 1991
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.19911240817
Subject(s) - chemistry , dimethyl sulfate , deprotonation , methyl iodide , potassium hydroxide , hydrolysis , medicinal chemistry , reagent , trimethylsilyl , alkylation , salt (chemistry) , yield (engineering) , potassium , silylation , polymer chemistry , organic chemistry , catalysis , ion , materials science , metallurgy
Alkylation of 1,3‐Dithietane 1,1,3,3‐Tetroxide (Disulfene) by Nonafluorobutanesulfonates Silyl and alkyl esters of nonafluorobutanesulfonic aicd are extremely powerful substitution reagents for disulfenes. Starting from trans ‐2,4‐trimethylsilyldisulfene ( 1 ) and methyl nonafluorobutanesulfonate ( 11 ), 2,4‐dimethyl‐2,4‐bis(trimethylsilyl)‐1,3‐dithietane 1,1,3,3‐tetroxide ( 2 ) is prepared. 2 is hydrolyzed to 2,4‐dimethyl‐1,3‐dithietane 1,1,3,3‐tetroxide ( 3 ). Rapid H/D exchange reaction of 3 with D 2 O leads to 4 . Compound 3 is deprotonated by aqueous potassium hydroxide and a potassium salt is obtained, the structure of which is most probably 5a . 2,2,4,4‐Tetramethyl‐1,3‐dithietane 1,1,3,3‐tetroxide ( 7 ) is obtained from 5 and methyl iodide, i.e. the ring system remains intact, whereas hydrolysis furnishes the ring‐opened product 6 . — Three new routes for the synthesis of methyl nonafluorobutanesulfonate ( 11 ) via the silver salt 9 or dimethyl sulfate (96% yield) or nonafluorobutanesulfonic anhydride ( 10 ) are described.