Chlorides, from thiols

Alkanesulfonic acids and alkanesulfonyl chlorides from thiols and disulfides... 

Vinyl chloride reacts with sulfides, thiols, alcohols, and oximes in basic media. Reaction with hydrated sodium sulfide [1313-82-2] in a mixture of dimethyl sulfoxide [67-68-5] (DMSO) and potassium hydroxide [1310-58-3], KOH, yields divinyl sulfide [627-51-0] and sulfur-containing heterocycles (27). Various vinyl sulfides can be obtained by reacting vinyl chloride with thiols in the presence of base (28). Vinyl ethers are produced in similar fashion, from the reaction of vinyl chloride with alcohols in the presence of a strong base (29,30). A variety of pyrroles and indoles have also been prepared by reacting vinyl chloride with different ketoximes or oximes in a mixture of DMSO and KOH (31). 

Complete reduction of sulfonyl chlorides to thiols can be achieved by lithium aluminum hydride [680,693], with zinc [696] and with hydriodic acid generated in situ from iodine and red phosphorus [230]. m-Nitrobenzenesulfonyl chloride, however, was reduced not to the thiol but to bis(m-nitrophenyl)disulfide by hydriodic acid in 86-91% yield [697]. 

Tributyltin hydride, 316 Zinc iodide, 280 From alkyl halides Lithium aluminum hydride-Ceri-um(III) chloride, 159 Palladium catalysts, 230 Sodium cyanoborohydride-Tin(II) chloride, 280 From alkyl sulfonates Lithium triethylborohydride, 153 From thiols... 

The crystal and molecular structures of disulfane 1-oxides (R = 4-tolyl) and of trisulfane 2-oxides have been determined by X-ray diffraction. The latter compounds are usually obtained from thionyl chloride and thiols (RSH) in ether or in the presence of pyridine (equations 154 and... 

RSOO are generated by the hydrogen abstraction from thiols by OH radicals, alcohol radicals, etc., producing thiyl radicals (RS ) which on reaction with oxygen produce RSOO [Eqs. (34) and (35)]. Alternatively, reaction of alkylsulfonyl chloride with e q produces alkyl sulfonyl peroxyl radicals [Eq. (36)]. 

AgSD differs from other silver salts in its physical properties it does not react rapidly with chloride or thiol groups or with protein and thus its antibacterial activity is not reduced. It does not become dark on standing or in contact with body tissues and unlike other sulphonamides its activity is not eliminated in the presence of p-aminobenzoic acid (PABA) (2) [40]. 

Several optically active S-(2-methylbutyl) alkanethioates (25) ° and the naturally occurring thiocar-boxylic esters (26) and (27) were synAesized from the corresponding acid chlorides and thiols, as well as S-phenyl arenecarbothioates and thiocinnamates, which are applicable for the preparation of radio-labeled CoA derivatives (14 equation 17), and the acyl sulfenates (28) occurring in the cultural media of Pseudomonas species (equation 18). ... 

In contrast to the free acids, sulfenate esters, amides and halides are more stable. Disulfides (52) can be obtained from thiols by mild oxidation (see p. 57), and sulfenyl chlorides () can in turn be prepared from disulfides (52) by treatment with chlorine (Scheme 30). Sulfenyl chlorides (51) react with alcohols to give esters, e.g. the methyl sulfenate (53) which on alkaline hydrolysis yields the sulfenic acid (45) (Scheme 30). 

Initial derivatizations were performed using trifluoroacetic anhydride and 4-fluorobenzoyl chloride. Trifiuoroacetylated thiols were found to coelute with sulfides from the same sample. In addition, during EI/MS spectral fragmentation, patterns of trifluoroacylarylthiols were less intense... 

Thioesters have the general formula RCSR. They resemble their oxygen counterparts RCOR (oxoesters) in structure and reactivity more than other carboxylic acid derivatives such as acyl chlorides, acid anhydrides, and amides. Thioesters can be prepared from thiols by reaction with acyl chlorides or acid anhydrides in much the same way as oxoesters are prepared from alcohols. 

The direct conversion of thiols into chlorides has been effected by a soft base-induced fragmentation (56) of the acyl chloride (4). The formation of (4) from thiols also involves a specific soft-soft interaction. 

The free-radical addition of TFE to pentafluoroethyl iodide yields a mixture of perfluoroalkyl iodides with even-numbered fluorinated carbon chains. This is the process used to commercially manufacture the initial raw material for the fluorotelomer -based family of fluorinated substances (Fig. 3) [2, 17]. Telomeri-zation may also be used to make terminal iso- or methyl branched and/or odd number fluorinated carbon perfluoroalkyl iodides as well [2]. The process of TFE telomerization can be manipulated by controlling the process variables, reactant ratios, catalysts, etc. to obtain the desired mixture of perfluoroalkyl iodides, which can be further purified by distillation. While perfluoroalkyl iodides can be directly hydrolyzed to perfluoroalkyl carboxylate salts [29, 30], the addition of ethylene gives a more versatile synthesis intermediate, fluorotelomer iodides. These primary alkyl iodides can be transformed to alcohols, sulfonyl chlorides, olefins, thiols, (meth)acrylates, and from these into many types of fluorinated surfactants [3] (Fig. 3). The fluorotelomer-based fluorinated surfactants range includes noiuonics, anionics, cationics, amphoterics, and polymeric amphophiles. 

Introduction. Methoxycarbonylsulfenyl chloride (Scm-Cl), easily prepared from equimolar amounts of methanol and chlorocarbonylsulfenyl chloride (eq 1), finds many applications, based on the reactivity of alkoxycarbonylsulfenyl chlorides against thiols. Brois and co-workers realized the value of methoxycarbonylsulfenyl chloride in the synthesis of asymmetric disulfides, which led to important applications in the chemistry of cysteine and its derivatives, particularly cysteinyl peptides. Other applications include preparation of aromatic thiols, symmetric trisulfides, etc. The applicability of Scm-Cl surpasses its drawbacks which include relatively short storage life (1-2 months at —20°C in sealed ampules) and relatively rapid hydrolysis in the protic media that some of its most important uses require. 

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