ISSN:
0009-2940
Keywords:
1,3-Dithietane 1,1,3,3-tetroxides, substituted
;
Nonafluorobutanesulfonates
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Alkylation of 1,3-Dithietane 1,1,3,3-Tetroxide (Disulfene) by NonafluorobutanesulfonatesSilyl 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 D2O 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.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240817
