Precursors and derivatives of bis(perfluoroalkyl) sulfoxides

Abstract

The concept that reactivity is vested in functional groups, and that the attached aryl or alkyl groups have only a moderating effect, is inherent in much of the systematization of organic chemistry. Thus ketones, carboxylic acids, esters, and the like are recognized as functional classes with characteristic physi-

Sulfuranes. XII. Relative reactivities of acyclic, cyclic and spirobicyclic sulfuranes and sulfurane oxides

“…The reaction of an equimolar mixture of the potassium salt of 11 and potassium hexafluoro-2-phenyl-2propoxide (KORr) with bromine in tetrahydrofuranether as solvent gives cyclic hexafluorocumyloxysulfurane 14 in 75% yield (by 19F nmr, 46% isolated), Scheme II, and bromosulfurane 15 (15% by 19F nmr) Scheme II 15(15%) 16 (ca. 5%) in addition to small amounts of hydrolysis products RfOH and sulfoxide alcohol 16 (ca.…”

“…Found: C,54.76;H,4.36;S,4.57. From the 19F nmr spectrum of the crude reaction mixture, the yields of cyclic sulfurane 14 and bromosulfurane 15 obtained are 75.5 and 14.6%, respectively. Also found was about 5% each of hydroxy sulfoxide 16 and RfOH, attributed to hydrolysis. In another run larger amounts of the latter two products were formed.…”

“…Hexafluoroacetone (21.0 ml, 33.6 g, 0.202 mol) was bubbled into the magnetically stirred mixture at 65 °. After 4.75 hr reflux became slow but an nmr spectrum indicated the presence of starting material, suggesting that volatile ketone had escaped through the condenser; so more hexafluoroacetone (10.0 ml, 16.0 g, 0.0964 mol) and aluminum chloride (4.25 g, 0.0318 mol) were added at this point. After the mixture had been heated for 2 hr, water (20 ml) was added and the reaction mixture was filtered.…”

“…2-(l,l,l,3,3,3-Hexafluoro-2-hydroxy-2-propyl)-4,4'-di-tort-butyldiphenyl Sulfoxide (16). Crude hydroxy sulfide 11 (23.7 g, 0.0504 mol) prepared as above was dissolved in ca.…”

“…Fluorination of perfluoroalkyl sulfoxides has also been reported to lead to analogs of 8. 16 Treatment of spirosulfurane 3 with ruthenium tetroxide gave4 spirosulfurane oxide 9. F F. I ./i S=0 8a, X = N(CH3)2 b, X = N(C2H5)2 c, X = OPh Sulfurane oxide intermediates have often been proposed in nucleophilic displacement on sulfur involving a temporary expansion of the valence octet.…”