Friedel-Crafts chemistry. 10. Observation of the methyl fluoride-antimony pentafluoride complex in sulfuryl fluoride solution, an exceedingly low nucleophilicity solvent. Reinvestigation of the complex in sulfur dioxide and sulfuryl chloride fluoride solution showing O-methylation

1976 ◽  
Vol 98 (9) ◽  
pp. 2661-2663 ◽  
Author(s):  
George A. Olah ◽  
Daniel J. Donovan ◽  
Henry C. Lin
Keyword(s):  
Sulfur Dioxide ◽  
Sulfuryl Chloride ◽  
Antimony Pentafluoride ◽  
Methyl Fluoride ◽  
Fluoride Solution ◽  
Sulfuryl Fluoride

O-Methylation of a sulfone with methyl fluoride – antimony pentafluoride – sulfur dioxide. Preparation and properties of tetrahydro-1-methoxythiophenium 1-oxide hexafluoroantimonate

1984 ◽  
Vol 62 (1) ◽  
pp. 69-73 ◽  
Author(s):  
Magdy Malak Abdel-Malik ◽  
Philip Arthur Woodworth Dean ◽  
James Frederick King
Keyword(s):  
Sulfur Dioxide ◽  
Antimony Pentafluoride ◽  
Liquid Sulfur ◽  
Methyl Fluoride ◽  
Methyl Group ◽  
Spectroscopic Evidence ◽  
Group A

Reaction of sulfolane (tetrahydrothiophene 1,1-dioxide) (1) with methyl fluoride – antimony pentafluoride in liquid sulfur dioxide gives crystalline tetrahydro-1-methoxythiophenium 1-oxide hexafluoroantimonate (2), thereby providing the first characterized example of an alkoxysulfoxonium salt. This salt (2) is also formed, but more slowly, by reaction of methyl fluoride with the crystalline 1:1 complex of sulfolane and antimony pentafluoride. Reaction of 2 with nucleophiles leads to transfer of the methyl group, a facile process even with such weak nucleophiles as nitrobenzene and phenyl N,N-dimethylsulfamate. Spectroscopic evidence has been obtained for O-methylation of other sulfones, either by reaction with MeF•SbF5•SO2, or via the sulfone•SbF5 complex and methyl fluoride, or by transmethylation with 2.

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