Sulfuryl bromide

Diorgano tellurium compounds can be easily converted to diorgano tellurium dihalides in reactions with sulfuryl chloride, bromide, and iodide. Carbon tetrachloride, dichlorometh-ane, diethyl ether, petroleum ether, or benzene have been used as reaction media. Chlorinations with sulfuryl chloride, a liquid reagent, avoid the use of gaseous chlorine. Required amounts of sulfuryl chloride can be more easily measured than those of chlorine. Sulfur dioxide formed during the reaction escapes the reaction mixture as a gas, thus facilitating the isolation of the product. For these reasons, sulfuryl chloride has been frequently used, whereas sulfuryl bromide and iodide5-6 have been only infrequently employed. 

Sulfuryl bromide fluoride is stored by melt-sealing in quartz ampoules. 

The decomposition of sulfuryl chloride is accelerated by light and catalyzed by aluminum chloride and charcoal. Many of the reactions of sulfuryl chloride are explainable on the basis of its dissociation products. Sulfuryl chloride reacts with sulfur at 200°C or at ambient temperature in the presence of aluminum chloride producing sulfur monochloride. It hberates bromine or iodine from bromides or iodides. Sulfuryl chloride does not mix readily with water and hydrolyzes rather slowly. 

Oxidation of sulfur dioxide in aqueous solution, as in clouds, can be catalyzed synergistically by iron and manganese (225). Ammonia can be used to scmb sulfur dioxide from gas streams in the presence of air. The product is largely ammonium sulfate formed by oxidation in the absence of any catalyst (226). The oxidation of SO2 catalyzed by nitrogen oxides was important in the eady processes for manufacture of sulfuric acid (qv). Sulfur dioxide reacts with chlorine or bromine forming sulfuryl chloride or bromide [507-16 ]. 

Diphenyl diselenide has been prepared by disproportionation of phenyl selenocyanate in the presence of potassium hydroxide" or ammonia/ and by air oxidation of benzeneselenol. The preparation of benzeneselenol is described in an earlier volume in this series/ In the present procedure phenylselenomagnesium bromide formed from phenylmagnesium bromide and selenium is oxidized directly to diphenyl diselenide with bromine/ Thus the liberation of the malodorous and toxic hydrogen selenide and benzeneselenol is avoided. Benzeneselenenyl chloride has been prepared by thermal elimination of ethyl chloride from ethyl phenyl selenide di-chloride/ by thermal elimination of chlorine from phenylselenium trichloride," and by chlorinolysis of diphenyl diselenide with either sulfuryl chloride " or chlorine. " ... 

Anger WK, Moody L, Burg J, et al. 1986. Neurobehavioral evaluation of soil and structural fumigators using methyl bromide and sulfuryl fluoride. Neurotoxicology 7 137-156. 

Reactions with chlorine or bromine yield sulfuryl chloride, SO2CI2, or sul-furyl bromide, S02Br2 ... 

Alkylsulfenyl chlorides.2 Sulfenyl chlorides are usually prepared by reaction of thiols with chlorine or sulfuryl chloride. NCS can also be used. NBS can be used to obtain sulfenyl bromides, but these substances are extremely sensitive to heat. 

Pyridinium bromide perbromide efficiently brominates pyrroles already substituted by electron-withdrawing substituents and also gives a high yield of 3-bromoindole in its reaction with indole. In conjunction with sulfuryl chloride, it has been used in the synthesis of 3-bromo-2-chloro-, 2-bromo-3-chloro- and 2,3-dibromo-indole (81SC253). 3-Methylindole reacts with A-bromosuccinimide in acetic acid to give the 2-bromo derivative which reacts further with an excess of A-bromosuccinimide to yield 2,6-dibromo-3-methylindole (B-70MI30500, 72HC(25-2)127) whilst in aqueous or alcoholic media, 3-bromo-3-methylox-indole is produced (cf. Scheme 15). All of these reactions proceed via the 3-bromo-3A-indolium cation, but the course of the reaction depends not only upon the orientation or... 

The reaction of methyl glycopyranosides with sulfuryl chloride has also provided a route to 6-chloro (and other monochloro, dichloro, and trichloro) derivatives. 44 Schlubach and Wagenitz 44 observed that reaction of /3-d-galactopyranose pentaacetate with hydrogen bromide affords a 1,6-dibromo derivative which they converted into crystalline D-fucose in two steps. 

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