From sulfonyl chlorides

The corresponding AfA -sulfonyldiimidazole, prepared from sulfonyl chloride and imidazole, is of surprisingly low reactivity in every respect. It forms stable crystals of m.p. 141 °C which can be sublimed in vacuum and recrystallized from ethanol without alcoholysis. Even in dilute aqueous hydrochloric acid hydrolysis occurs only very slowly. 

Cycloaddition of ynamines with sulfenes (generated from sulfonyl chlorides) to give thiete sulfones 132 and 133 has been reported by Truce et (Eq. 21). Acid hydrolysis yields the corresponding enols (134). Other compounds that have been prepared in this manner are 135 and 136. Sulfene... 

Similarly, sulfamidce (XXXVI) ace formed by the reaotkm of rutin -dines with dialkytsul myl halides,2,8 and sulfonamides (XXXVI I)1 from sulfonyl chlorides,... 

Preparation of Sulfonamides and Sulfinamides 249 Table 8.8. Miscellaneous preparations of sulfonamides from sulfonyl chlorides and from sulfinamides. 

Arylsulfonyl chlorides are pivotal precursors for the preparation of many diverse functional types including sulfonate esters,8 amides,4 sulfones,9 sulfinic acids,10 and others.11 Furthermore, sulfonyl fluorides are best prepared from sulfonyl chlorides.12 The sulfonyl fluorides have many uses, among which is their utilization as active site probes of chymotrypsin and other esterases.13 The trifluoromethyl group also plays valuable roles in medicinal chemistry.14... 

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

An alternative procedure involves in situ generation of sulfenes from sulfonyl chlorides and subsequent reaction with diazoalkanes affording a mixture of cis- and tram-thiirane 1,1-dioxides 2 and 3116. 

The reaction of thialdehyde and thioketone 5,5-dioxides, generated in situ from sulfonyl chlorides, with enamines leads to a mixture of cis- and /rum-substituted 3-aminothietane 1,1-dioxides 111. The pure frans-isomers are obtained by stirring the isomeric mixtures obtained with a catalytic amount of potassium fe/7-butoxide in tert-butyl alcohol for one day to two weeks. 

The synthesis of these thiols is relatively straightforward from commercially available phenols via the Newman-Karnes rearrangement (6) (Eq. (1)) or from sulfonyl chlorides (also obtainable commercially) by Li[AlH4] reduction (7) (Eq. (2)). 

Sulfenes generated from sulfonyl chlorides and tertiary amines do not react with simple alkenes or dienes however, the sulfene generated from (trimethylsilyl) methanesulfonyl chloride (112) and caesium fluoride affords the [4+2] cycloadduct (113) with cyclopentadiene (114) (Scheme 73). 

Sulfenes (see Chapter 7, p. 114) generated from sulfonyl chlorides by treatment with a tertiary amine may be used to prepare p-sultams. Thus, the sulfonyl chloride (184) may be converted to the sultam (185) via the sulfene (186) by reaction with an activated alkene (Scheme 77)... 

Sulfonate ester, formation from sulfonyl chloride and alcohol, 67, 78, 84, 145 Sulfonation, benzoic acid, 269 phenol, 104 o-xylene, 47... 

PREPARATION OF SYMMETRICAL THIOSULFONATES FROM SULFONYL CHLORIDES... 

Sulfonyl fluorides are readily obtained from sulfonyl chlorides and KF or KHF2j even in an aqueous medium.801"804 Carboxylic acid fluorides are formed when the acid chlorides are heated with dry KF and can be removed continuously from the reaction mixture by distillation through a column formyl and acetyl fluorides are thus obtained when the acid is heated with benzoyl chloride and KF.805,806 Xylene or acetamide may be used as diluent. Further, a>chloro and at-bromo fatty esters, nitriles, and amides react with KF at temperatures around 100-150°. 

Several groups202-204 reported almost simultaneously that sulfenes, generated from sulfonyl chlorides and triethylamine, also react with the acetylenic analogue of enamines (i.e. ynamines or alkynylamines) to give a mixture of the dialkylaminothiete 1,1-dioxides (equation 92). Block and Aslam98 reported that sulfene generated from... 

Hanefeld and coworkers179 have recently noted that the reaction of sulfenes generated in situ from sulfonyl chlorides and tertiary amines, with vicinal tricarbonyl compounds such as indan-l,2,3-trione, alloxane, diethyl mesoxalate and 1-methyl-1,2,3,4-tetrahydroquinoline-2,3,4-trione, afford products derived mainly from ring opening of /i-sultones (equation 139). 

Sulfonyl cyanides. The compounds can be prepared from sulfonyl chlorides by reduction to sodium sulfinates followed by reaction with cyanogen chloride. Example ... 

The second concealed ElcB elimination is disguised in the mechanism of formation of methanesulfonates (mesylates). When we introduced sulfonate esters in Chapter IS, and revisited them on p. 391 of this chapter, we avoided (uncharacteristically, you may say) explaining the mechanism by which they are formed from sulfonyl chlorides. This was deliberate because, while TsCl reacts with alcohols by the mechanism you might predict, the reaction with MsCl involves an elimination step. 

The use of molybdenum compounds in organic synthesis has attracted greater attention. Thus, molybdenum hexacarbonyl has been used in various reactions, such as the preparation of disulfides from sulfonyl chlorides, the alkylation of aryl derivatives, and the synthesis of 4-quinazolones from amines Oxygen has been replaced by fluorine with molybdenum hexafluoride. Molybdenum pentachloride in combination with hydroperoxides has served as oxidant Chelates of MoOg " have been investigated as catalysts for oxidations with molecular oxygen 2,2-Dichloro-7-butyrolactones have been prepared from olefins and methyl trichloracetate with cyclopentadienylmolyb-denum tricarbonyl dimer as catalyst ... 

Oxidation of Ben Iic Methylene Compounds. The peroxy intermediate (1) generated from sulfonyl chloride (3) oxidized compounds containing benzylic methylene groups to ketones under mild conditions (—35 °C) (eq 3). ... 

Epoxidation of Arenes. Certain arenes (acenaphthylene, phenanthrene, and pyrene) are readily oxidized to the corresponding arene oxides by the peroxy intermediate (1) generated from sulfonyl chloride (3) in polar aprotic solvents such as MeCN and DME. Superoxide (4) is a strong base and reactions with (1) take place under mild and basic conditions. Acenaphthylene oxide (10) is unstable under acidic conditions but is more stable under basic conditions. Oxide (10) was obtained in 95% yield. ... 

A number of photochemical approaches are possible to generate sulfonyl radicals in fluid solutions. A traditional method for production of high concentrations of sulfonyl radicals is based on chlorine atom abstraction from sulfonyl chlorides by trialkyIsilyl radicals [61, 62]. The rate constants for chlorine atom abstraction by triethylsilyl radical from methane and benzene sulfonyl chlorides were reported to be 3.2 x 10 M s and 4.6x 10 M s", respectively [63] ... 

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