Sulfinyl fluorides reaction with

Nonmetal Halides. Vigorous or explosive reactions occur with phosphorus tribromide on addition of drops of water,20 phosphorus trichloride, phosphorus pentachloride,21 diselenium dichloride,22 sulfur dichloride, boron tribromide, sulfur dibromide,17 seleninyl bromide,23 phosphoryl chloride, sulfinyl fluoride, silicon tetrachloride, and silicon tetrafluoride.24... 

The Friedel-Crafts sulfonylation of aromatics with alkane- and arenesulfonyl halides and anhydrides has been studied (Eq. 9) [23]. In the reaction of pentafluorobenzenesul-fonyl fluoride with pentafluorobenzene, decafluorodiphenyl sulfone is formed with deca-fluorodiphenyl [23c]. Certain phenylacetylenes react with SO2 and benzene in the presence of SbFs to form benzothiophene 5-oxide [24]. (Eq. 10). Sulfinyl fluoride reacts similarly with arenes under SbFs catalysis to give sulfoxides (Eq. 11) [25]. 

Chlorodifluoroamine has been prepared by reaction of difluoro-amine with boron trichloride,1 phosgene (carbonyl chloride),2 or hydrogen chloride 2 treating a mixture of sodium azide and sodium chloride with fluorine 3 reaction of chlorine trifluoride with ammonium fluoride 4 reaction of chlorine with diflu oro-amine in the presence of potassium fluoride 5 and photolysis of tetrafluorohydrazine and sulfinyl chloride (thionyl chloride).6... 

The known thionyl hahdes include SOX2 (X = F, Cl, and Br Table 13) as well as the mixed compound SOFCl. They are pyramidal in geometry, with the S=0 bond being shorter in the fluoride than the chloride or bromide. Thionyl chloride is prepared industrially by reacting sulfin dioxide or trioxide with sulfin dichloride or sulfin monochloride, or by the reaction of phosphorus trichloride with sulfinyl chloride (equations 54 57). 

Ignition on contact with carbon + sulfinyl chloride (when ground), nitric acid (becomes violent), viton poly(l,l-difluorethylene-hexafluoropropylene), chlorine tri- and penta-fluorides (hypergolic reaction), diborane (forms a complex that is pyrophoric), hydrogen (above 300°C). 

Sulfur, Selenium and Tellurium Derivatives. TMSCF3 reacts with elemental sulfur, selenium or tellurium in the presence of a fluoride anion, leading to trifluoromethylthiolates, seleniates or tellurates, respectively.Aryltrifluoromethyl-sulfides, sulfoxides and sulfones were obtained from the corresponding arylsulfenyl, sulfinyl and sulfonyl halides, respectively, by treatment with TMSCF3 and TASF. The reaction of disulfides and diselenides with TMSCF3 and TBAF gave trifluoromethyl thioethers and selenoethers, respectively (eq 26). The same procedure can also be carried out from thiocyanates and selenocyanates. 

Preparation of 7V-Sulfonylimines. The title sulfonamide has been used to generate iV-sulfinyl-2-(trimethylsilyl)ethanesulfo-namide (SES-NSO), which reacts with aldehydes in the presence of BF3 Et20 to form, after loss of SO2, A-sulfonylimine derivatives. These can be trapped with 2,3-dimethylbuta-1,3-diene in Diels-Alder cycloaddition reactions (eq 2) The SES group can then be removed using a fluoride ion source. ... 

The N-SES group can be incorporated by treating an aldehyde with iV-sulfinyl-/3-trimethylsilylethanesulfonamide (SESNSO) (13), which can be made by treating the sulfonamide (12) with thionyl chloride and a catalytic amount of M,fV-dichloro-/7-toluenesulfonamide (eq 7) (see also fV-sulfinyl-/7-toluenesulfon-amide. The iV-sulfonyl imine can be used in situ in a number of reactions. For example, the fV-sulfonyl imine from aldehyde (14) reacts with 2,3-dimethylbutadiene (eq 8) to give the Diels-Alder adduct (15). Treatment of (15) with fluoride ion affords the bicycUc lactam (16). Also, the fV-sulfonyl imine derived from isobutyraldehyde and (13) reacts with vinylmagnesium bromide to provide the allylic SES-sutfonamide (17) in 65% yield (eq 9). ... 

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