Sulfenylation amines

For the s3Githesis of other triply sulfenylated amines, it is best to start with the primary ones ... 

General Procedure for Organocatalytic Sulfenylation-Amination Reaction Sequence [102] (p. 114)... 

General Discussion. (V-Phenylthiophthalimide has been shown to be a mUd sulfenylating reagent that is useful for a range of synthetic appUcations. This reagent reacts with amines and thiols to give the corresponding sulfenyl amines and disulfides respectively (eq 1). 

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). 

Sulfenamides, R2NSR, prepared from an amine and a sulfenyl halide, " are readily cleaved by acid hydrolysis and have been used in syntheses of peptides, penicillins, and nucleosides. They are also cleaved by nucleophiles, and by Raney nickel desulfurization. ... 

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. 

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). ... 

When thionyl chloride is used, diaryl sulfoxides are usually the main products. Unsymmetrical diaryl sulfides can be obtained by treatment of an aromatic compound with an aryl sulfenyl chloride (ArSCl) in the presence of a trace amount of iron powder.Aromatic amines and phenols can be alkylthiolated (giving mostly ortho product) by treatment with an alkyl disulfide and a Lewis acid catalyst. With certain substrates (primary amines with a chloro group, or a group not replaceable by chloro, in the para position), treatment with S2CI2 and NaOH gives thiophenolate salts ... 

Sigmatropic rearrangements of anions of (V-allyl amines have also been observed and are known as aza-Wittig rearrangements.291 The reaction requires anion stabilizing substituents and is favored by (V-benzyl and by silyl or sulfenyl substituents... 

A new stable sulfenylating reagent 3-phenylsulfenyl-2-GV-cyano-imino)thiazolidine 57 has been described. It reacts with amines or thiols to give sulfenamides or disulfides in excellent yields. a-Sulfenylation of carbonyl compounds also proceeds smoothly and if an optically active 4-diphenylmethyl substituent is attached to the thiazolidine ring (58), the cyclic (3-ketoester 59 can be sulfenylated in high yield with an ee of 96% to give the sulfide 60 <00SL32>. 

The mixed amines, CF Cls SNH2 (n=l, 2), are synthesized from the corresponding sulfenyl chlorides and ammonia at —60°C with the use of a perhalogenated solvent (58) ... 

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) ... 

All derivatives, sulfenylated at the nitrogen atom, are stable for a prolonged period of time only at low temperature. 5-Trifluoromethyl-mercaptouracil is an extraordinarily stable compound. In contrast to 5-bromouracil (129), the substituent cannot be exchanged by amines. Nevertheless, a complete fluorine-chlorine exchange can be brought about with the aid of boron trichloride, just as with other aromatic CF3S compounds (170) ... 

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-... 

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