Sulfonyl halides formation

Normally, reactive derivatives of sulfonic acids serve to transfer electrophilic sulfonyl groups259. The most frequently applied compounds of this type are sulfonyl halides, though they show an ambiguous reaction behavior (cf. Section III.B). This ambiguity is additionally enhanced by the structure of sulfonyl halides and by the reaction conditions in the course of electrophilic sulfonyl transfers. On the one hand, sulfonyl halides can displace halides by an addition-elimination mechanism on the other hand, as a consequence of the possibility of the formation of a carbanion a to the sulfonyl halide function, sulfenes can arise after halide elimination and show electrophilic as well as dipolarophilic properties. 

The key step in the radical chain decomposition of alkanesulfonyl halides as well as in the adduct formation of sulfonyl halides with alkenes (vide infra) is equation 8 in which the R radical abstracts an X atom from the sulfonyl halide to regenerate a sulfonyl radical. 

In the early solution phase syntheses of oligonucleotides, coupling of phosphate diesters was used. A mixed 3 -ester with one aryl substituent, usually o-chlorophenyl, was coupled with a deprotected 5 -OH nucleotide. The coupling reagents were sulfonyl halides, particularly 2,4,6-tri-i-propylbenzenesulfonyl chloride,53 and the reactions proceeded by formation of reactive sulfonate esters. Coupling conditions... 

A reaction which is related to hydroxy-de-diazoniations is the formation of aryl trifluoromethylsulfonic esters (aryl triflates, ArOSC CFs) which became widely used reagents because of their leaving-group properties. The classical method of synthesis by esterification of phenols with trifluoromethane-sulfonic anhydride or -sulfonyl halide is, however, not applicable for the preparation of aryl triflates bearing a (free)... 

The single-monomer route (eq. 5) is preferred as it proves to give more linear and para-linked repeat unit structures than the two-monomer route. Other sulfone-based polymers can be similarly produced from sulfonyl halides with aromatic hydrocarbons. The key step in these polymerizations is the formation of the carbon—sulfur bond. High polymers are achievable via this synthesis route although the resulting polymers are not always completely linear. 

B sulfonyl chloride is an amine-reactive reagent made by converting the 5-sulfonate group over to the reactive sulfonyl halide. Reaction with proteins and other amine-containing molecules results in the formation of sulfonamide bonds (Fig. 214). Lis-samine is a trademark erf Imperial Chemical Industries. 

The sulfonyl halides (ArSOjCl) convert the alcohol into a sulfonate (ArSOjOR), which is a better leaving group than the hydroxyl group. This allows a range of nucleophilic substitutions to be carried out, many of which parallel those found with alkyl halides. Alkyl halides such as iodides are formed by the nucleophilic substitution of the sulfonate by an iodide ion. The reaction in this case proceeds with inversion of configuration. Treatment of the sulfonate esters with bases such as sodium methoxide or collidine (2,4,6-trimethylpyridine), or even just heating them, can lead to the elimination of toluene-4-sulfonic acid and the formation of an alkene. 

Irreversible reactions of carbohydrates include the formation of glycosides and 1-deoxy-l-thioglycosides from acylglycosyl halides and thio-acetals, " respectively, esterifications by acyl and sulfonyl halides or anhydrides in pyridine, displacements of sulfonyloxy groups by various reagents, and most examples of formation and scission of anhydro rings, It is more difficult to define the influence of stereo effects on the course of these reactions and some of the results obtained await explanation. 

Attack by Halogen Formation of Sulfonyl Halides S-Halo-de-hydroxylation... 

General Discussion. Various kinetic and reactivity studies have been performed using TsBr alone or in comparison with other arene sulfonyl halides. Most of the literature describes the use of this reagent to initiate free radical ring formation, predominantly for five-membered ring systems. There are, however, reports of its use in vinyl sulfone and thiolsulfonate formation and in halogenation reactions. 

In another approach, poly(aryl ether sulfones) were synthesized by the electrophilic Friedel-Crafts reactions of sulfonyl halides with aromatic hydrocarbons. The critical step in these polymerizations is the formation of the carbon-sulfur bond. High polymers were obtained, though they were not always completely linear. Carbonyl aryl carbon-carbon bonds are created in Friedel Craft reactions leading to poly(aryl ketones). 

Studies of the thermodynamics of formation of complexes of zinc with 2,2 -bipyridine in the presence of halide and thiocyanate ions in DMF has been carried out.205 The zinc complexes of 2,2 -bipyridine with A-(benzenesulfonyl)glycine and A-(toluene- -sulfonyl)glycine were synthesized and infrared data implied a structural analogy with the cadmium complexes. This suggests that the zinc promotes sulfonamide nitrogen deprotonation in the amino acid ligands in the solid state.206... 

A commonly used and important reaction of sulfonic acids, or sulfonates, is their conversion to sulfonyl chlorides by treatment with phosphorus halides, or sometimes with thionyl chloride. Although it is easy to postulate mechanisms for this conversion, the exact path followed has never been determined. Similarly, although mechanisms can be suggested for other known reactions involving sulfonic acids, such as the cleavage of dialkyl ethers by anhydrous sulfonic acids (Klamann and Weyerstahl, 1965), or the formation of sulfones by treatment of an aromatic hydrocarbon with a mixture of sulfonic acid plus polyphosphoric acid (Graybill, 1967), nothing truly definitive is known about the details of the actual mechanisms of these reactions. 

N- Hydroxyindoles can be alkylated by primary halides to give 1-alkoxyindoles which, while not extensively studied, appear to show the chemical reactions characteristic of the indole ring (78JCS(Pl)1117). 1-Acyloxyindoles can be prepared from N-hydroxyindoles and acid anhydrides or acyl halides and are fairly stable thermally. Attachment of the more electronegative sulfonyl group, however, leads to facile rupture of the N—O bond and formation of 3-sulfonyloxyindoles (equation 194) (81CPB1920). 

Problem 13.16 How does sulfonate ester formation from sulfonyl chloride resemble nucleophilic displacements of alkyl halides ... 

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