Preparation sulfenyl chloride

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). 

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... 

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

Another -activation of amino acids for peptide synthesis is achieved by preparing sulfenamides from sulfenylimidazoles. A sulfenylimidazole is formed in situ from the sulfenyl chloride (prepared from the disulfide and chlorine) and imidazole, which reacts further with an amino acid ester to give a sulfenamide in high yield. Conversion of such sulfenamides with IV-acyl amino acids by means of triphenylphosphine affords dipeptides with racemization of less than 0.5%.[481... 

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... 

Chlorine monofluoride combines smoothly with thiocarbonyl compounds. For instance, the sulfenyl chlorides of the series CFnClg-n-SCl (w= 1, 2, 3), which were already prepared by other methods, are obtained in good yield ... 

Chlorolysis of the corresponding disulfanes is a favorable procedure for the preparation of aliphatic, aromatic, and heterocyclic sulfenyl chlorides under not too demanding conditions [low temperature mild chlorinating agents, such as SO2CI2 14) or CH3SCI3 (15)]. Perfluorinated sulfenyl chlorides can also be prepared by this procedure in special cases a mixture of CF3SSCF3 and chlorine reacts in a Pyrex Carius tube imder UV irradiation to form sulfenyl chloride in an equilibrium reaction 84) ... 

On heating the sulfane mixture [C4F9CF(CF3)2]2Sn (average sulfur chain length n = 2.5) with chlorine fca 125 hr at 106°C, the perfluorohexane-2-sulfenyl chloride is formed in appreciable yield 86, 127). The patent literature (5, 19, 87-89,127) abounds with long-chain sulfenyl chlorides prepared according to this latter procedure, but physical data are lacking. 

Relatively few perfluorohalogenoalkanesulfenyl bromides are presently known. These are orange-to-red colored substances which are prepared with difficulty and are too unstable to arouse interest. Apart from a few specific syntheses they may be obtained by the methods used for the preparation of sulfenyl chlorides. 

In an attempt to prepare tris(mercapto)amines of the type (CF3S)2-NSCF Cl3 n (w = 0, 1,2) from (CF3S)2NH and the appropriate sulfenyl chloride, it was observed that, besides the expected bis(trifluoromethyl-mercapto)derivatives, other products were also formed (57) ... 

In order to obtain heterodimers a cysteine residue of one peptide has to be specifically activated for subsequent reaction with the cysteine residue of the second peptide. Thiols are activated by introducing an electron-withdrawing substituent that increases the responsiveness of the sulfur to nucleophilic substitution. This topic has been reviewed 41311 Of the various older methods known in sulfur chemistry for the preparation of unsymmetrical disulfides, i.e. thiosulfates,11321 S-alkylthiosulfonates,11331 5-alkylthiosulfinates,11341 sulfanyl-amines,11351 sulfanylimides,11361 sulfanyl thiocyanates and sulfenyl chlorides,1137,1381 sulfan-... 

Chlorodifluorothioacetyl fluoride prepared by this reaction has a boiling point of 23° C. NMR characterization of this compound gave a low-field triplet and high-field doublet in a ratio of 1 2, as would be expected. However, a material boiling at 36° C had been reported earlier as chlorodifluorothioacetyl fluoride (54). This material was obtained by dehalogenation erf 2-chlorotetrafluoroethane-sulfenyl chloride with tin. In view of... 

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. 

Trithianes are rare but routes established for the 3-methyl derivative (226) could provide the basis of more general methods. These include the chlorination of diethyl disulfide and the reaction of the sulfenyl chloride (227) with 1,2-ethanedithiol (74MI22601). 1,2,4,5-Tetrathiane (228) has been prepared by the cyclization of two equivalents of the bis sulfenyl chloride CH2Y2 (229 Y = SCI) or the bis Bunte salt CH2Y2 (230 Y = SSQ3Na) using sodium... 

N-Arylamidines act as 1,5-dinucleophiles towards sulfur dichloride, N-sulfinyltosylamide and bis(N-tosyl)sulfur diimide. The products are 1,2,4-benzothiadiazines (Scheme 14) (73ZOR2038, 68LA(715)223), and in the case of sulfur dichloride, chlorination of the aromatic ring also occurs. 1,2,4-Benzothiadiazines can also be prepared from N-arylamidines by reaction with sulfenyl chlorides or disulfides in the presence of NCS. Thus N-phenylben-zamidine and benzenesulfenyl chloride give the 1,2,4-benzothiadiazine (182) (78CC1049). 

A -Sulfenylarnines are prepared from sulfenyl chlorides ArSCl, and can be cleaved by acids, phosphines, or various nucleophiles [230,321], The 2-nitrobenzenesulfenyl protective group (2-(02N)C6H4-S-NH-R), developed as amino group protection for cx-amino acids [321,322], has been completely superseded by the Fmoc group. 

Addition of a sulfenyl chloride to an alkene in the presence of silver fluoride affords (3-fluoro sulfides, as shown in equation (2).18 The same trans adducts can also be prepared from the sulfenyl chloride adducts and silver fluoride. An alternative procedure for the formal addition of methanesulfenyl fluoride to alkenes involves the use of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine tris(hy-drofluoride) as in equation (3).19... 

Refluxing of monothioxamides 140 with sulfenyl chloride 131 in toluene results in 5-arylcarbamoyl-l,2,4-dithia-zole-3-ones 141 (Equation 21) <2003PS1283>. A series of 5-(A-alkyl-A-arylamino)-l,2,4-dithiazolc-3-thiones 143 were prepared by the condensation of A-alkyl-A-arylthioureas 142 with CS2 in the presence of NaH followed by oxidation of the formed intermediate with I2 (Scheme 40) <2000EPP992506>. 

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