Alkane sulfonyl chlorides

The reaction of sulfur dioxide and chlorine with paraffin hydrocarbons to yield alkane sulfonyl chlorides (RH + S02 + Cl2 - RS02C1 + HC1) (the Reed reaction) was patented in 1939.221 This reaction has usually been run in the liquid phase under strong illumination with short wavelength visible or ultraviolet light.107,218 267... 

Of the large number of possible ways of synthesizing alkanesulfonates, only sulfochlorination of alkanes (conversion with sulfur dioxide and chlorine to form alkane sulfonyl chlorides and their saponification with sodium hydroxide Table 1, entry 10) and sulfoxidation (reaction with sulfur dioxide and oxygen and neutralization of the sulfonic acids Table 1, entry 11) are of industrial importance [18]. 

The sulfoxidation and chlorosulfoxidation of hydrocarbons yields sulfonic acids and alkane sulfonyl chlorides, respectively. 

The reaction of alkyl mercaptans and dialkyl disulfides with chlorine in an aqueous system yields alkane sulfonyl chlorides in good yield. 

Formation of alkane sulfonyl chlorides by hydrogenation and reaction with thionyl chloride... 

Simultaneous treatment of an alkane with sulfur dioxide and chlorine affords a sulfonyl chloride, eg, hexylsulfonyl chloride [14532-24-2] and is referred to as chlorosulfonation or the Reed reaction (247,248). 

Although reaction 6 is essentially a diffusion-controlled process for all kinds of substituents, the small differences observed in the rate constants through the series alkane-, amino- and alkoxy-sulfonyl chlorides have been attributed to the increased importance of polar effects to the transition state11. 

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 ... 

Ruthenium complexes are capable of catalyzing halogen atom transfer reactions to olefins. This has been illustrated in the enantioselective atom transfer reactions of alkane and arene-sulfonyl chlorides and bro-motrichloromethanes to olefins using chiral ruthenium complexes. Moderate ee s up to 40% can be achieved for these transformations [74-77]. These specific reactions are believed to follow a radical redox transfer chain process. 

Photolysis of CsFsSCl in cyclohexane leads to formation of both arylthio- and chloro-cyclohexane by a radical pathway.Sulfiiryl chloride in pyridine can chlorosulfonate alkanes by a radi( route under photolytic conditions, the chloride being a minor product (equation 68).SO2 and Ch also gives the sulfonyl chloride by the route shown in equations (69) to (72). ... 

Photolysis of alkane/S02 mixtures leads to the formation of alkylsulfonic acids,the Hostapon process utilizing SOdOilhvP It is curious that this reaction seems to be so efficient, given the low e for alkane and SO2 at the wavelengths used, and an efficient chain reaction is presumably involved. The Reed reaction uses SO2/CI2/I11 to convert alkanes to the corresponding sulfonyl chlorides. Alkanes also react with SO3 to give alkyl sulfonates, sulfones and sulfates. ... 

Chen, J Preparation of Alkane Sulfonic Acids and Sulfonyl Chlorides by Oxidation of Alkanethiols and Dialkyl Disulfides. U.S. Patent 6,124,497,, Sep 26, 2000. 

The present volume is a revised and enlarged third edition of the book formerly titled Tables for Identification of Organic Compounds, Four new classes of compounds, i.e., sulfonyl chlorides, sulfonamides, thiols and thioethers were added, bringing the number of classes included in the book to twenty-six. The tables of alkanes, alkenes, alkynes, aromatic hydrocarbons, phenols, nitriles and sulfonic acids were all thoroughly revised and considerably enlarged. In all, the addition of 2400 compounds to the third edition, raised the total number of parent compounds in the book to over 8150. 

Sulfonic acid esters are prepared by the reaction of an alkane- or arenesulfonyl chloride with an alcohol or phenol. Two of the most common sulfonyl chlorides are p-toluenesulfonyl chloride, abbreviated TsCl, and methanesulfonyl chloride, abbreviated MsCl (Section 18.1A). 

The cyclization of diphenyl ether 206 to the cyclic sulfone derivatives 208 and 209 achieved by prolonged heating with a large excess of the reagent is analogous to similar reactions observed with biphenyl and the diphenyl alkanes (see Section 2, pp 42 and 40). 4-Bromodiphenyl ether by treatment with excess chlorosulfonic acid (two equivalents) at 25-30 °C afforded the 4-sulfonyl chloride (45%). In this molecule, the other reactive 4-position is blocked by the bromine atom. In contrast, with diphenyl ether 206 all attempts to obtain the monosulfonyl chloride by reaction with chlorosulfonic acid failed, and the only isolated product was the 4,4 -disulfonyl chloride. In the case of 4,4 -dibromodiphenyl ether, in which... 

In the case of sulfonylation (Scheme 10) [56] and sulfinylation reactions [34], Bi salts proved again to be efficient catalysts. In contrast to the arylsulfonylation, which is under partial control of triflic acid, depending on the substrates, a complete synergistic effect between triflic acid and Bi chloride has been found in the alkanesulfonylation of arenes. In this case, the formation of mixed triflic/alkane-sulfonic anhydrides leads to the active electrophilic species. The formation of the latter exclusively requires the transient formation of a Bi chlorobistriflate species that acts as an intermediate shuttle for triflic acid, leading to the formation of the mixed anhydride precited (Scheme 11). Our experiments have shown that triflic... 

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