Sulfenyl chloride

Tetrachloropyridine-4-thiol [10357-06-1] (41) reacts with chlorine in carbon tetrachloride to give a sulfenyl chloride (42), which is fairly stable. The sulfenyl chloride may be converted into a number of derivatives (39). 

With a few olefins, the addition can yield sulfenyl chlorides, eg, 2-dichloroethane sulfenyl chloride [2441 -27-2] ... 

Many other reactions of ethylene oxide are only of laboratory significance. These iaclude nucleophilic additions of amides, alkaU metal organic compounds, and pyridinyl alcohols (93), and electrophilic reactions with orthoformates, acetals, titanium tetrachloride, sulfenyl chlorides, halo-silanes, and dinitrogen tetroxide (94). 

Chlorination of thiiranes in hydroxylic solvents gives /3-chloroethylsulfonyl chlorides due to further oxidation of the intermediate sulfenyl chloride by chlorine or hypochlorous acid (Scheme 40). Polymer is usually obtained also unless the reaction is done in concentrated hydrochloric acid, which causes rapid ring cleavage to 2-chloroethylthiols which are subsequently oxidized to the sulfonyl chlorides. An 85% yield of (37) is obtained in concentrated hydrochloric acid-HCl(g) whereas only a 15% yield is obtained in CCI4-H2O. 

Fluoride ion attacks the sulfur atom in 2,3-diphenylthiirene 1,1-dioxide to give ck-1,2-diphenylethylenesulfonyl fluoride (23%) and diphenylacetylene (35%). Bromide or iodide ion does not react (80JOC2604). Treatment of S-alkylthiirenium salts with chloride ion gives products of carbon attack, but the possibility of sulfur attack followed by addition of the sulfenyl chloride so produced to the alkyne has not been excluded (79MI50600). In fact the methanesulfenyl chloride formed from l-methyl-2,3-di- -butylthiirenium tetrafluoroborate has been trapped by reaction with 2-butyne. A sulfurane intermediate may be indicated by NMR experiments in liquid sulfur dioxide. 

Thiirane is more bactericidal than oxirane, and derivatives of 2-mei captomethylthiirane inhibit tuberculosis. The following pharmacological uses have been reported for compounds derived from thiirane derivatives gold complexes of the adducts of diethylphosphine and thiirane (antiarthritic), adducts of thiiranes and malononitrile (antibacterial, blood vessel dilators, muscle relaxants, sedatives), thermolysis products of thiirane 1-oxides and adducts of thiirane 1-oxides with sulfenyl chlorides (antibacterial), adducts of 2,3-diarylthiirene 1,1-dioxides with ynamines (antibacterial, parasiticidal), adducts of 2,3-diarylthiirene 1,1-dioxides with enamines (antifertility), adducts of p-aminophenylacetic esters with thiirane (immunosuppressants), adducts of amines and thiiranes (radioprotective drugs). 

NO2C6H4SCI NaBH4- Treatment of the thioether with the sulfenyl chloride initially produces a disulfide which is then reduced to afford the free thiol. 

These sulfides are prepared from other sulfur protective groups by reaction with the sulfenyl chloride. The Npys group can also be introduced directly by treatment of the thiol with NpysCl. ... 

This sulfenamide, prepared from an amino acid, the sulfenyl chloride, and sodium bicarbonate, is cleaved by acid hydrolysis (HOAc/dioxane, 22°, 30 min, 95% yield). 

This group, which is more stable than the 2-hitrobenzenesulfenamide, has been developed to protect amino acids. It is readily introduced with the sulfenyl chloride (52-74% yield) and is cleaved with triphenylphosphine or 2-thiopyridine N-oxide. It is stable to CF3COOH but can be cleaved with 0.1 M HCl. ... 

The acetyl chloride obtained is yellow in color, probably because of the presence of the sulfenyl chlorides mentioned above. The addition of cyclohexene will discharge the color (although a darker color develops later) and redistillation then yields a stable water-clear product. The yield of acetyl chloride varies from 60% to 85%, depending on the care with which liquids are transferred and the vapors are trapped. O he amount... 

The utility of methanesulfinyl chloride lies in its great chemical reactivity. Through its ready hydrolysis, it serves as a convenient source of methanesulfinic acid. It reacts at low temperature with aromatic amines to form sulfinamides, and with alcohols to form sulfinate esters. When it is hydrolyzed in the presence of an equimolar quantity of sulfenyl chloride, a thiol-sulfonate ester is produced. 

The disulfides are useful intermediates in the preparation of sulfenyl chlorides. ... 

Preparation of fluorine-containing sulfides has been achieved mainly by the reacuon of sulfenyl chlorides (RSCl), which may react with a vanety of nucleophiles The method is based on the electrophilicity of sulfur and on the leaving-group ability of chlorine... 

The free-radical chemistry of fluoroalkanesulfenyl chlorides with hydrocarbons was also investigated [S, 9], Depending upon the structures of the sulfenyl chloride and the hydrocarbon, these reactions yield as major products up to three of the following four types of organic compounds thiols, disulfides, sulfides, and chlorohydrocarbons (equation 6), Perfluoroisobutanesulfenyl chloride is unique m that the only major products detected are the thiol and chlorohydrocarbon [ ] (equation 6) (Table 3). 

In the reaction of CF Cl3 SCl with triethylamine, the yield of the product (CF Cl3 S)2C=CHN(C2H5)2 decreases with decreasing n [fri] (equation 7) (Table 2). 2,3,4,5-Tetrakis(trifluoromethylthio)pyrrole salts react with sulfenyl chloride or SjjCl2 (x = 1,2) to give N-sulfenylaled pyrroles as well as dipyrrolylsulfane and -disulfene. Pentakis(trifluoroniethylthio)pyrrole is a mild sulfenylating... 

Hypochlorites [(59], chlorofluorosulfates [70], chloroamines [71], and sulfenyl chlorides [72] react with perfluorinated nitnles according to their polarity to form chloroiminoethers, chloroiminofluorosulfates, a-chlorohydrazones, and IV-sulfenyltnfluoro acetirmde chlorides, respectively. 

Elimination of hydrogen chloride from 2/f perfluoro-2-methylpropane-1 -sulfenyl chloride by the triethylamine-boron trifluoride complex results in cyclization to perfluoro-l,l-dimethylthiirane (perfluoroisobutylene sulfide) [, 9] (equation 9)... 

The cyclocondensation of trimethylsilyl azide with a bis(sulfenyl chloride) is an efficient synthesis of dithiazolium cations (Section 11.3.5) (Eq. 2.15). ... 

The primary route to 1,3,2-dithiazolium salts involves the cyclocondensation of l,2-bis(sulfenyl chlorides) with trimethylsilyl azide, which is illustrated for benzo-fused derivatives in Eq. 11.11. ° This method can be extended to the synthesis of bis( 1,3,2-dithiazolylium) salts. 

Benzotrithiadiazepine (12.14, R = H) is obtained as bright-yellow crystals by the reaction of benzo-l,2-bis(sulfenyl chloride) with McsSiNSNSiMcs (Eq. 12.4). The tetrafluoro derivative 12.14 (R = F) has been prepared by a similar procedure. The isomeric 1,2,4,3,5-benzotrithiadiazepine (12.15) is formed in the reaction of PhNSNSiMcs and S2CI2, followed by intramolecular cyclization (Eq. 12.5). " ... 

The enamino ketone 49 has also been found to react with o-nitrobenzene-sulfenyl chloride to give the derivative 156, having the o-nitrophenylthio group substituted in the 2 position (93), i.e., the same position at which normal acylation with acid chlorides takes place. 

XI. Reactions with Sulfonyl Chlorides, Sulflnyl Chlorides, and Sulfenyl Chlorides... 

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