Alkanesulfonyl chlorides

Poly(vinyl nitrate) has been prepared and studied for use in explosives and rocket fuel (104,105). Poly(vinyl alcohol) and sulfur trioxide react to produce poly(vinyl sulfate) (106—111). Poly(vinyl alkane sulfonate)s have been prepared from poly(vinyl alcohol) and alkanesulfonyl chlorides (112—114). In the presence of urea, poly(vinyl alcohol) and phosphoms pentoxide (115) or phosphoric acid (116,117) yield poly(vinyl phosphate)s. 

The injected sulfonyl chlorides decompose instantaneously to give peaks of monochloroalkanes and 1-alkenes from alkanesulfonyl chlorides and dichloro-alkanes, and monochloro- 1-alkenes from monochloroalkane sulfonyl chlorides ... 

Alkanesulfonyl chlorides, when treated with diazomethane in the presence of a base (usually a tertiary amine), give episulfones (67). The base removes HCl from the sulfonyl halide to produce the highly reactive sulfene (66) (17-13), which then adds CH2. The episulfone can then be heated to give off SO2 (17-20), making the... 

The first evidence that an elimination-addition mechanism could be important in nucleophilic substitution reactions of alkanesulfonyl derivatives was provided by the observation (Truce et al., 1964 Truce and Campbell, 1966 King and Durst, 1964, 1965) that when alkanesulfonyl chlorides RCH2S02C1 were treated in the presence of an alcohol R OD with a tertiary amine (usually Et3N) the product was a sulfonate ester RCHDS020R with exactly one atom of deuterium on the carbon alpha to the sulfonyl group. Had the ester been formed by a base-catalysed direct substitution reaction of R OD with the sulfonyl chloride there would have been no deuterium at the er-position. Had the deuterium been incorporated by a separate exchange reaction, either of the sulfonyl chloride before its reaction to form the ester, or of the ester subsequent to its formation, then the amount of deuterium incorporated would not have been uniformly one atom of D per molecule. The observed results are only consistent with the elimination-addition mechanism involving a sulfene intermediate shown in (201). Subsequent kinetic studies... 

Not every substitution of alkanesulfonyl chlorides, by any means, involves an elimination—addition mechanism. Thus, while the reactions of cr-toluene-sulfonyl chloride, PhCH2S02Cl, with either hydroxide ion, or primary and... 

Alkanesulfonyl chlorides, when treated with diazomethane in the presence of a base (usually a tertiary amine), give episulfones (79).774 The base removes HC1 from the sulfonyl... 

Alkanesulfonyl chlorides are prepared in good yields by the photoreaction of sulfur dioxide and chlorine with saturated hydrocarbons.89 157 158 This sulfochlorination, known as the Reed reaction,159 presumably proceeds by a free-radical mechanism 158 160... 

Related compounds such as alkanesulfonyl chlorides by treatment with base afford sulfene intermediates, which undergo attack by nucleophiles (H2O, alcohols, amines,. ..) present in the reaction mixture. Although sulfenes have been the subject of intense studies345,346 it has been impossible so far to succeed in the isolation of even one of them. 

A solution of 0.1 mol of alkanesulfonyl chloride in 50-100 mL of Et20 is added dropwise under stirring over a 30-120min period to a cold (0°C to — 40 C) solution of 0.11-0. 3mol of diazoalkane and 0.11 mol of Et,N in 300-500 mL of Et,0. After addition of the alkanesulfonyl chloride, the mixture is stirred for a further 15 -60 min and filtered to remove F,t,N HC1. Evaporation of the filtrate and washing the residue under reduced pressure affords the crude product which is purified by recrystallization from an appropriate solvent at —20CC to — 70°C. 

To an ethereal solution of one equiv of enamine and one equiv of Et3N is added dropwise at r.l. over a period of 10-30 mill a solution of one equiv of alkanesulfonyl chloride in F.t20. When the addition is complete, the mixture is stirred for an additional 30 min. Then. Et3N HC1 is filtered off and washed with small portions of F.t.O. The combined filtrates and washings are evaporated lo afford a crude residue which after drying over P.O, under reduced pressure is recrystallized from a suitable solvent. 

Alkanesulfonyl chlorides are known to be a good source of alkanesulfonyl radicals or alkyl radicals with the aid of redox catalysts [3]. A series of studies using RuCl2(PPh3)3 as the redox catalyst have been carried out by Kamigata and coworkers (Scheme 13.6) [33-39]. Arenesulfonyl chlorides add to styrene derivatives to form the corresponding adducts, which undergo dehydrochlorination of EtsN to form the unsaturated sulfones [33]. When styrylsulfonyl chlorides are used as the precursor. 

The postulated mechanism resembles that proposed for the thermal decomposition of alkanesulfonyl chlorides. 

Alkanesulfonyl chlorides are decomposed thermally and lose sulfur dioxide according to... 

Methanesulfonyl chloride is the largest-volume alkanesulfonyl chloride. Benzenesulfonyl chloride is the only aromatic sulfonyl halide with significant commercial production, primarily as a feedstock for the manufacture of A-butyl benzenesulfonamide. All sulfonyl chlorides are poorly water soluble, which limits their hydrolysis except at elevated temperatures or in the presence of a homogenizing agent such as a cosolvent, surfactant or phase-transfer agent. 

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

Methanesulfonic acid and methanesulfonyl chloride (MSC) are the alkanesulfonic acids and alkanesulfonyl chlorides produced in the largest volumes. 

Methanesulfonic acid is primarily manufactured by the batch or continuous oxidation of the methyl mercaptan or dimethyl disulfide with chlorine in saturated aqueous hydrochloric acidJ This chemistry is also the basis for much of the worldwide production of MSC, with photochlorination of methane (vide infra) being the most significant commercial alternative. Other alkanesulfonyl chlorides and sulfonic acids have also been produced in lesser quantities by the CI2/H2O oxidation. Reaction yields are typically 92-100%. The HCl by-product separates as vapor from the saturated reaction mixture. It is absorbed into water to afford a... 

When the desired product is the alkanesulfonyl chloride RSO2CI, reaction, temperatures are maintained at 10-35°C to inhibit hydrolysis of the poorly soluble sulfonyl chlorides. Extraction with clean... 

The alkanesulfonic acids are produced at elevated temperatures to ensure complete hydrolysis of the intermediate RSO2CI, with residual HCl being stripped from the reaction product. Methanesulfonic acid and other alkanesulfonic acids are typically obtained as 60-70% aqueous solutions. Similarly, isolated alkanesulfonyl chlorides can be hydrolyzed to afford the aqueous or anhydrous sulfonic acids. ° Anhydrous nonfluorinated alkanesulfonic acids can also be prepared by evaporative removal of water from the aqueous acids. ... 

Other oxidants for the conversion of alkanethiols and disulfide alkanesulfonic acids have been described. H2O2, in combination with catalysts, e.g., peroxycar-bonates, alkanesulfonic acids, molybdates, tungstates, or HCl, was effective in producing alkanesulfonic acids.At lower temperatures (25-35°C) the combination of H2O2 catalytic HCl afforded the alkanesulfonyl chlorides. Kinetic studies of the photooxidation with O2 in acetonitrile and other solvents have been reported and the relative stabilities of the various... 

Photochemical sulfochlorination of saturated hydrocarbons has been used in the production of long-chain alkanesulfonyl chlorides, again as precursors to the salts as surfactants. These processes involve free radical intermediates. Analogous to the sulfoxidation of long-chain alkanes, these processes also provide mixtures of alkanesulfonyl chloride and chloroalkane products. Nonetheless, pure products can be obtained for short C1-C3 alkyl chain lengths. A high-pressure gas phase process for the reaction of CH4 with CI2 and excess SO2 is used in one commercial manufacturing route to... 

Alkanesulfonyl chlorides can also react by an initial elimination in water, mesyl chloride hydrolyses below pH 6.7 by an S 2 reaction of water at sulfur, between pH 6.7 an 11.8 by capture of the sulfene by water and above pH 11.8 by capture of the sulfene with hydroxide ion. An extended study of mesylations of phenols catalysed by various pyridines revealed a competition between the sulfene pathway and a general base-catalysed attack of the phenol, which was dependent on the pAa of both phenol and pyridine, with no mention of an A-mesylpyridinium ion. However, formation of an A-triflylpyr-idinium ion occurs immediately pyridine and triffic anhydride are mixed and this is probably the triflating species. Reaction via an A-sulfonyl quaternary ammonium ion therefore becomes important with more basic amines and more electrophilic sulfonylating reagents. 

This chapter describes subsequent experiments to clarify the mechanism of reactions of alkanesulfonyl chlorides and related compounds with water, alcohols, and aromatic amines. In the course of these studies, we also noted a third-order term in the rate law and further work on this led to the observation of hydrogen-deuterium multiexchange with small tertiary amines. These results prompted further study, which has proceeded gradually over a number of years. The current state of this work is described. 

The most elegant method of converting alkanesulfonyl chlorides into the sulfonic acids is alcoholysis 683 no ester is formed in the absence of acidbinding agents ... 

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