Sulfenyl chlorides reactions

This synthesis could not be extended directly to the monocyclic compound because of the instability of Z-ethene-1,2-dithiol and the associated difficulties of its chlorination to the bis(sulfenyl chloride). However, ethane-1,2-dithiol was readily and quantitatively converted into ethane-1,2-bis(sulfenyl chloride). Reaction of this compound with sulfurdiimide in dichloromethane, as above, gave the orange dihydro derivative (20) (20%) (Equation (19)) <85CC396,87JCS(Pi)211>. 

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. 

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. ... 

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... 

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). " ... 

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

Tlie bifunctional sulfenyl chloride 213 was obtained by chlorination of 144 in good yield, although excessive chlorination led to the saturated compound 214 (94CB533). A series of compounds 215-220 were obtained from 213 by reactions with secondary amines ferf-butyl methyl ketone hexane-2,4-dione 2,6-dimethylcyclohexanone diethyl malonate and acetylacetone, respectively. 

A heterocyclic ring may be used in place of one of the benzene rings without loss of biologic activity. The first step in the synthesis of such an agent starts by Friedel-Crafts-like acylation rather than displacement. Thus, reaction of sulfenyl chloride, 222, with 2-aminothiazole (223) in the presence of acetic anhydride affords the sulfide, 224. The amine is then protected as the amide (225). Oxidation with hydrogen peroxide leads to the corresponding sulfone (226) hydrolysis followed by reduction of the nitro group then affords thiazosulfone (227). ... 

It is therefore not unexpected to find a similar effect in a heterocycle fused to a benzene ring. Reaction of the substituted benzothiazole, 71, with sodium hypochlorite in a mixture of sodium hydroxide and ammonia affords the sulfenamide, 72, probably by the intermediacy of the sulfenyl chloride. 

The reaction of organic sulfenyl chlorides RSCl or chlorodisulfanes RSSCl with sulfanes provides organic polysulfanes in preparative quantities [2] ... 

Alkenes and alkynes react with sulfur dichloride (SC12), giving 2-chloroethyl(or vinyl)sulfenyl chlorides. The reaction is an electrophilic addition to the multiple bond, and consequently the possible intermediacy of thiiranes, or thiiranium ions analogous to bromonium ions, has been... 

Sulfur dichloride is difficult to handle it disproportionates readily, has an unpleasant odor, and tends to introduce extra, unwanted chlorine atoms. Several reagents have been developed, especially by Harpp and co-workers, in which these undesirable features have been modified or eliminated. Succinimide-N-sulfenyl chloride (28) and phthalimide-N-sulfenyl chloride (29) are both stable crystalline compounds which undergo many of the reactions of the sulfur dichloride itself. They can, for example, be used in a facile, high yield synthesis of thiiranes from alkenes.33... 

In the reaction of ketones with thionyl chloride the intermediate sulfinyl (or sulfenyl) chloride can cyclize on to an aromatic ring located two carbon atoms away giving benzo[b]thiophenes (48) (Scheme 7).54 Additional... 

Amidines and cyclic amidines are also converted into 1,2,4-thiadiazoles by reaction with isothiocyanates, imino-sulfenyl chlorides, di- and trichloromethyl sulfenyl chlorides, and carbon disulfide in the presence of sulfur. Ureas, thioureas, guanidines, carbodiimides, and cyanimides react with chlorocarbonylsulfenyl chloride to produce 1,2,4-thiadiazol-5-one derivatives in another example of a type B synthesis <1996CHEC-II(4)307>. 

A useful method for the synthesis of 5-chloro-l,2,4-thiadiazoles 125 is the reaction of amidines with trichloromethyl-sulfenyl chloride (Equation 34). 

B. 2,4-Dinitrobenzenesulfenyl chloride. Dry 2,4-dinitrophenyl benzyl sulfide (232 g., 0.80 mole) and 400 ml. of dry ethylene chloride are placed in a 2-1., one-necked, round-bottomed flask equipped with a stirrer (Note 3). Sulfuryl chloride (119 g., 0.88 mole) (Note 4) is added to the resulting suspension at room temperature. A mildly exothermic reaction causes the solid to dissolve quickly, usually within 1 to 2 minutes, with a temperature rise of 10-15° (Note 5). The resulting clear yellow solution is concentrated to an oil by heating under aspirator vacuum on a steam bath (Note 6). Caution Do not heat with gas or electricity because the product, like many nitro compounds, can explode if overheated.) The residual oil is cooled to 50-60°, and 3-4 volumes of dry petroleum ether (b.p. 30-60°) are added with vigorous handswirling. The oil quickly crystallizes. The mixture is cooled to room temperature and filtered to separate 2,4-dinitrobenzene-sulfenyl chloride as a yellow crystalline solid. The sulfenyl chloride is washed well with dry petroleum ether and dried at 60-80° (Note 7) weight 150-170 g. (80-90%) m.p. 95-96° (Notes 8, 9). 

When the thiole derivatives are converted into the corresponding sulfenyl chloride such as 56, an addition reaction to styrene or /3-methylstyrene in nitromethane gives regioisomeric mixtures of adducts 57 and 58 (Scheme 11) <2001CHE702> as well as the cyclization products 59 which are generated in 47% (R = H) and 52% (R = OI I () yield, respectively. 

Nevertheless, new examples have also been reported of allenyl sulfoxides [101] and especially allenyl trichloromethyl sulfoxides [39, Y+-X = S(0)CC13] [102]. There have been many trials to use these sigmatropic rearrangements for the synthesis of diallenes (compare 40 — 42), e.g. the reaction of the diols 43 with trichloromethane-sulfenyl chloride 44 to the diallenes 45 (Scheme 7.7) [103]. 

N-Allenylazetidinone 181 rearranges to cephalosporin 182 in the presence of lithium chloride (Eq. 13.62) [70], This is a very unusual reaction that is presumed to be initiated by chloride ion-induced cleavage of the disulfide to give sulfenyl chloride 183. Thiolate attack at the allene sp carbon atom of 183 generates ester enolate 184, which cyclizes to 182. The reactivity of the allene function in 181 ensures the success of the reaction. 

Trichloromethanesulfenyl chloride is a sulfenyl chloride that does not form a thiolsulfinate upon hydrolysis, however. Instead it gives the sulfine C12C=S=0 (Silhanek and Zbirovsky, 1969) because trichloromethanesulfenic acid loses HC1 (13) faster than it undergoes any other reaction. 

Thiolsulfonates have the structure shown in [58]. That they may be considered the mixed anhydride of a sulfenic and a sulfinic acid is indicated by one of the principal synthetic methods for their preparation, namely reaction (166) of a sulfinic acid with a sulfenyl chloride (Stirling, 1957). Once again, as we have... 

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