Sulfinyl chlorides

Benzisothiazoles are formed by the action of ammonia or amines on benzenesulfenyl halides bearing an o-carbonyl function (72AHC 14)43, 80MI41700). Analogous diphenyl disulfides behave similarly (77SST(4)339). Sulfinyl chlorides or phenylsulfoxides produce... 

Section 5.10.3.2). Treatment of methyl 6-phthalimido penicillinate (jR)-sulfoxide (40) with JV-chlorosuccinimide in refluxing carbon tetrachloride gives an epimeric mixture of sulfinyl chlorides (41) which are ring closed to epimeric 3-methylenecepham sulfoxides (42a) using tin(IV) chloride. Reduction with phosphorus tribromide gives the desired methyl 7-phthalimido-3-methylenecepham 4-carboxylate (42b). 

Alkanesulfinyl chlorides have been prepared by the action of thionyl chloride on alkanesulfinic acids and by the solvolysis of alkylsulfur trichlorides with water, alcohols, and organic acids. The present procedure, which appears to be general for the preparation of sulfinyl chlorides in either the aliphatic or the aromatic series, is based on an improvement in the solvolysis method whereby the use of inert solvent is eliminated and the reaction is carried out in a one-phase system. ... 

Sulfinyl azides have higher thermal stability than their divalent counterparts. For example, benzenesulfmyl azides ArS(0)N3 (Ar = Ph, 4-MeCelFt, 4-NO2C6H4), which are obtained by the metathetical reaction of the sulfinyl chloride and sodium azide in acetonitrile, can be stored in the solid state at low temperatures. ... 

Reactions with Sulfonyl Chlorides, Sulfinyl Chlorides,... 

Hydrogen chloride has also been eliminated from sulfinyl chlorides by addition of triethylamine. The thioketone oxide obtained from 9-fluorene-sullinyl chloride reacted with morpholinocyclohexene to give a zwitterionic adduct (475). 

Sulfinyl chlorides may be prepared from the corresponding thiols or disulfides by oxidative reactions rather than by reductions of sulfonyl compounds. A recent example, which improves the earlier procedure of Douglass, is given by equation (3)50. The chemistry of sulfinic acids and their derivatives has been reviewed51 52,53. 

Solladie and coworkers avoided the use of a sulfinyl chloride when they prepared (— )-menthyl 1-naphthalenesulfinate in an overall yield of 45% by the reaction of thionyl diimidazole, obtained from imidazole and thionyl chloride, with 0.7 equivalent of ( — )-menthol followed by 1 equivalent of 1-naphthylmagnesium bromide (equation 4). 

Sharpless and Klunder22 are developing a new procedure for conversion of sulfonyl chlorides directly into menthyl sulflnate esters using trimethyl phosphite as a reducing agent (equation 2). This method, starting with sulfonyl chlorides rather than with the much less available sulfinyl chlorides, should allow access to an even wider range of sulfinate esters and, ultimately, to various chiral, non-racemic sulfoxides. 

Also, sulfinyl chlorides (precursors to sulfinate esters) have recently been prepared directly from disulfides (equation 3)23. 

Methyl disulfide, oxidation to methane-sulfinyl chloride by chlorine, 40, 62... 

Mikolajczyk and coworkers have summarized other methods which lead to the desired sulfmate esters These are asymmetric oxidation of sulfenamides, kinetic resolution of racemic sulfmates in transesterification with chiral alcohols, kinetic resolution of racemic sulfinates upon treatment with chiral Grignard reagents, optical resolution via cyclodextrin complexes, and esterification of sulfinyl chlorides with chiral alcohols in the presence of optically active amines. None of these methods is very satisfactory since the esters produced are of low enantiomeric purity. However, the reaction of dialkyl sulfites (33) with t-butylmagnesium chloride in the presence of quinine gave the corresponding methyl, ethyl, n-propyl, isopropyl and n-butyl 2,2-dimethylpropane-l-yl sulfinates (34) of 43 to 73% enantiomeric purity in 50 to 84% yield. This made available sulfinate esters for the synthesis of t-butyl sulfoxides (35). 

Lithium, Lithium tetrachloroaluminate, Sulfinyl chloride See Lithium Carbon, etc. 

Tetraphosphorus decaoxide Organic liquids Sodium hydride Dimethylformamide Sodium tetrahydroborate Dimethylformamide Sodium Dimethylformamide Sulfinyl chloride Dimethylformamide Triethylaluminium Dimethylformamide... 

Diethylaminosullinyl chloride [34876-30-7] Et2NS( 0)Cl Preparative hazard See Sulfinyl chloride Bis(dimethylamino) sulfoxide See other N-S compounds c4h10cinos... 

Linseed oil, Thionyl chloride See Sulfinyl chloride Linseed oil, etc. 

Sulfinyl chloride Bailar, 1973, Vol. 2, 1442 The anhydrous acid ignites the chloride. 

Addition of a solution of 4-nitrobenzoyl chloride (1 g) in a large excess (10 ml) of sulfinyl chloride to ice-cold cone, ammonia solution caused a violent explosion. This may certainly be attributed to the instantaneous hydrolysis of the excess sulfinyl chloride by the aqueous ammonia with production of several 1 of unneutralised acid gases in a test tube. 

A previous method of making 4-oximino-4,5,6,7-tetrahydrobenzofurazan by cyclising the oxime with sulfinyl chloride in liquid sulfur dioxide sometimes led to explosive reactions [1]. A new procedure involving aqueous calcium carbonate is quite safe [2],... 

Unstirred mixtures of sulfinyl chloride and tetrahydrofuran may react extremely exothermally and with gas evolution when heated to 60°C, the products of ring-scission being bis(4-chlorobutyl) ether, 1,4-dichlorobutane and sulfur dioxide. Some ratios of the two reactants enhance the tendency, and relatively confined mixtures may explode. Sufficient heat to initiate the reaction may arise from selfmixing of the layered liquids, the chloride being twice as dense as THF. 

Anon., Univ. Safety Assoc., Safety Newsletter, 1982-1984 A solution of the chloride (120 ml) in toluene (750 ml) was treated (apparently without effective stirring) with excess sodium bicarbonate solution to destroy it. When reaction had ceased, the organic layer was poured into a waste solvent drum. Vigorous evolution of sulfur dioxide and hydrogen chloride then ensued from reaction with ethanol (toluene-soluble) in the waste drum. For destruction of solutions of sulfinyl chloride in water-insoluble solvents, extremely good agitation is necessary to ensure proper contact with a basic reagent. Ammonia is more soluble in toluene than is water, so ammonia solution should be used after bicarbonate treatment to ensure complete destruction. 

As with sulfinyl chloride, the exothermic reaction with limited amounts of water may be dangerously violent under confinement because of rapid gas evolution. See other gas evolution incidents, non-metal halides... 

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