Sulfuryl halides

Sulfone molecular structures, including sulfuryl halides, have been repeatedly reviewed through the late seventies28 and early eighties5. Scheme 1 contains a list of the compounds discussed in these references. While the structures of these compounds will be discussed, recent structural information that was not included in the above compilations will be described initially. The relevant substances are listed in Table 3 along with the S=0 bond lengths and OSO bond angles. 

Fluorination of sulfuryl halides by halogen exchange is apparently a very difficult process to force to completion even at temperatures as high as 300° the usually effective Swarts reagent takes sulfuryl chloride only to the chloride... 

Higher-valent metal halides oxidize diaryl tellurium compounds to diaryl tellurium dihalides. Copper(II) halides can be generated in the reaction mixture from easily accessible copper(II) acetate and hydrohalic acids4. These halogenation reactions are convenient alternatives to the methods using corrosive elemental halogens or sulfuryl halides. 

Occasionally, displacements occur in the process of reacting oxoazines with phosphorous oxychloride or pentasulfide or with an arylsulfonyl halide, thionyl chloride, or sulfuryl halide. The phos-phoryloxy or sulfonyloxy intermediates (201) are now activated by virtue of the protonated ring-nitrogen plus the electron-attracting acyloxy substituent. 

Apart from sulfur hexafluoride (and sulfuryl halides), the oxidation state is maintained for species SF5R and SF4R2. All of these compounds are octahedral and the latter species may adopt cis or trans configurations. 

The sulfuryl halides are usually prepared by reaction of X2 with SO2. SO2F2 and SO2CI2 are both tetrahedral in geometry S02Br2 is not well characterized and is probably unstable at room temperature. The S X and S=0 bonds are shorter than in the simple halides (SFe and S2CI2) and the S=0 is also shorter in SO2F2 than in SO3 or SO2CI2. 

Dimethyl-lO-ethylphenotellurazine reacted with sulfuryl halides or bromine in diethyl ether solution to quantitatively precipitate re,7e-dihalides. The dihalides were recrystallized from chlorobenzene. The dihalides can be reduced to the parent heterocycle with hydrazine or sodium sulfide. ... 

Only S and Se are known to form well-defined oxo halides. These are of the three main types (a) the thionyl and selenyl halides, SOX2 and SeOX2 (b) the sulfuryl halides, SOzX2, and their one selenium analog, Se02F2 and (c) a number of more complex sulfur oxo chlorides and oxo fluorides. 

The sulfuryl halides may be considered, formally, as derivatives of sulfuric acid in which both OH groups have been replaced by halogen atoms. If only one OH group be replaced, the acids, FS03H (page 181), C1S03H and BrS03H, are obtained. 

Sulfuryl amide (LXXIX), the diamide of sulfuric acid, has been known for a very long time. It was discovered by Traube (111, 112) and isolated as a colorless solid mp, 92-93°. It is formed in a quite normal way both in the ammonolysis of sulfuryl halides (see, for example, refs. 22,26,29, 77,103, 119) and also in the ammonolysis of sulfur trioxide (6). It is common to both modes of preparation that other reactions occur besides the formation... 

S + CI2 S2CI2 S2CI2 + CI2 2SCI2 In addition to these binary halides, sulfur forms two groups of oxyhalides the sulfur dihalide oxides (thionyl halides), SOX2 (F, Cl, and Br, but not I), and the sulfur dihahde dioxides (sulfuryl halides), SO2X2 (F and Cl, but not Br and I). 

Halothienylaminopyridines (IX-172) (Table IX-26) are prepared by treating thienylaminopyridines with sulfuryl halides. ... 

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