From sulfonyl halides

TABLE 4. Absolute kinetic data for halogen abstraction by some radicals from sulfonyl halides... 

The rapid desulfonylation of PhCHjSOj has been used successfully as a probe for laser flash photolytic investigations of various reactions generating sulfonyl radicals from sulfonyl halides . 

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. 

Whereas sulfonyl halides have been known for a long time and, especially the chlorides, have become of great synthetic value, sulfonyl cyanides were unknown until 1968. They were first prepared by van Leusen and co-workers from the reaction of sulfonylmethylenephos-phoranes with nitrosyl chloride. The same group also investigated part of their chemistry. Since then, two more, completely different, methods of synthesis were published from sulfinates with cyanogen chloride,and by the oxidation of thiocyanates. ... 

Sulfonate esters are especially useful substrates in nucleophilic substitution reactions used in synthesis. They have a high level of reactivity, and, unlike alkyl halides, they can be prepared from alcohols by reactions that do not directly involve bonds to the carbon atom imdeigoing substitution. The latter aspect is particularly important in cases in which the stereochemical and structural integrity of the reactant must be maintained. Sulfonate esters are usually prepared by reaction of an alcohol with a sulfonyl halide in the presence of pyridine ... 

Recently, Co(III)-allyl complexes have been described to be sulfonylated regiospecifi-cally by sulfonyl halides under irradiation232 (equation 42). Similarly, allyl methyl sulfone has been obtained from allyltrimethylsilane under copper(I) catalysis213. 

TABLE 6. Sulfones from unsaturated systems and sulfonyl halides R S02X by radical routes... 

TABLE 9. Sulfones R S02X from different C-nucleophiles and sulfonyl halides... 

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. 

This reaction, parallel with 10-77, is the standard method for the preparation of sulfonyl halides. Also used are PCI3 and SOCI2, and sulfonic acid salts can also serve as substrates. Sulfonyl bromides and iodides have been prepared from sulfonyl hydrazides (ArS02NHNH2, themselves prepared by 10-126) by treatment with bromine or iodine.Sulfonyl fluorides are generally prepared from the chlorides, by halogen exchange. 

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... 

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, allenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphorus oxychloride [10025-87-3], POCl3 (11). Because sulfonic acids are generally not converted direcdy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphorus pentachloride [10026-13-8] and phosphorus pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl halides (12,13). The conversion may also be accomplished by continuous electrolysis of thiols or disulfides in the presence of aqueous HQ [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfuric acid [7789-21-1], or by reaction of the sulfonic acid or sulfonate with fluorosulfuric acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl halide, can be achieved under oxidative halogenation conditions (15). 

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