Sulfonyl chlorides, reactions

Section 7.8). Other classes of derivatives are thus most conveniently prepared from the sulfonyl chloride. Reaction with an alcohol leads to formation of a sulfonate ester. Two common sulfonyl chloride reagents employed to make sulfonate esters from alcohols arep-toluenesulfonyl chloride, known as tosyl chloride, and methanesulfonyl chloride, known as mesyl chloride (see Section 6.1.4). Note the nomenclature tosyl and mesyl for these groups, which may be abbreviated to Ts and Ms respectively. 

It is often important to separate the three classes of amines, and this may be done by the application of the benzene sulfonyl chloride reaction. Cf. page 144. 

Similar halogenations have been done on 2-lithio-l-phenylsulfonylindole[2], 2-Lithio-l-phenylsulfonylindole is readily converted to the 2-(trimethylsilyl) derivative[2,3]. 2-Trialkylstannylindoles can also be prepared via 2-lithio-indoles[4,5], 2-Sulfonamido groups can be introduced by reaction of a 2-lithioindole with sulfur dioxide, followed by conversion of the sulfinic acid group to the sulfonyl chloride with A-chlorosuccinimide[6]. 

Fig. 11. Synthesis of DNQ photosensitizers found in commercial resists, (a) Condensation of l,2-diazonaphthoquinone-5-sulfonyl chloride with 1,2,3-trihydroxybenzophenone. Often the reaction is not carried to completion so the product is a mixture of monodi- and trisubstituted products, (b)...

Sulfonylation. Under Friedel-Crafts reaction conditions, sulfonyl haUdes and sulfonic acid anhydrides sulfonylate aromatics (139), a reaction that can be considered the analogue of the related acylation with acyl haUdes and anhydrides. The products are sulfones. Sulfonyl chlorides are the most frequently used reagents, although the bromides and fluorides also react ... 

Naphthalenesulfonic acid can be converted to l-naphthalenethiol/T25 -J6 - by reduction of the related sulfonyl chloride this product has some utihty as a dye intermediate, and is converted by reaction with alkyl isocyanates to 3 -naphthyl-A/-alkylthiocarbamates, which have pesticidal and herbicidal... 

On dehydration, nitro alcohols yield nitro-olefins. The ester of the nitro alcohol is treated with caustic or is refluxed with a reagent, eg, phthaUc anhydride or phosphoms pentoxide. A mil der method involves the use of methane sulfonyl chloride to transform the hydroxyl into a better leaving group. Yields up to 80% after a reaction time of 15 min at 0°C have been reported (5). In aqueous solution, nitro alcohols decompose at pH 7.0 with the formation of formaldehyde. One mole of formaldehyde is released per mole of monohydric nitro alcohol, and two moles of formaldehyde are released by the nitrodiols. However, 2-hydroxymethyl-2-nitro-l,3-propanediol gives only two moles of formaldehyde instead of the expected three moles. The rate of release of formaldehyde increases with the pH or the temperature or both. 

Phthalocyanine sulfonic acids, which can be used as direct cotton dyes (1), are obtained by heating the metal phthalocyanines in oleum. One to four sulfo groups can be introduced in the 4-position by varying concentration, temperature, and reaction time (103). Sulfonyl chlorides, which are important intermediates, can be prepared from chlorosulfonic acid and phthalocyanines (104). The positions of the sulfonyl chloride groups are the same as those of the sulfonic acids (103). Other derivatives, eg, chlormethylphthalocyanines (105—107), / /f-butyl (108—111), amino (112), ethers (109,110,113—116), thioethers (117,118), carboxyl acids (119—122), esters (123), cyanides (112,124—127), and nitrocompounds (126), can be synthesized. 

PoIysuIfonyIa.tlon, The polysulfonylation route to aromatic sulfone polymers was developed independendy by Minnesota Mining and Manufacturing (3M) and by Imperial Chemical Industries (ICI) at about the same time (81). In the polymerisation step, sulfone links are formed by reaction of an aromatic sulfonyl chloride with a second aromatic ring. The reaction is similar to the Friedel-Crafts acylation reaction. The key to development of sulfonylation as a polymerisation process was the discovery that, unlike the acylation reaction which requires equimolar amounts of aluminum chloride or other strong Lewis acids, sulfonylation can be accompHshed with only catalytic amounts of certain haUdes, eg, FeCl, SbCl, and InCl. The reaction is a typical electrophilic substitution by an arylsulfonium cation (eq. 13). 

Reaction of bis (sulfonyl chloride)s with diaryl ether produces polyethersulfones. For example, condensation of diphenyl ether with the disulfonylchloride of diphenyl ether yields polyethersulfone (5) ... 

N -Heterocyclic Sulfanilamides. The parent sulfanilamide is manufactured by the reaction of A/-acetylsulfanilyl chloride with excess concentrated aqueous ammonia, and hydrolysis of the product. Most heterocycHc amines are less reactive, and the condensation with the sulfonyl chloride is usually done in anhydrous media in the presence of an acid-binding agent. Use of anhydrous conditions avoids hydrolytic destmction of the sulfonyl chloride. The solvent and acid-binding functions are commonly filled by pyridine, or by mixtures of pyridine and acetone. Tertiary amines, such as triethylamine, may be substituted for pyridine. The majority of A/ -heterocycHc sulfanilamides are made by simple condensation with A/-acetylsulfanilyl chloride and hydrolysis. 

A variation of this procedure is used for sulfisomidine because of the different character of the amino group in the 4-position of a pyrimidine ring. Two moles of the sulfonyl chloride are condensed with one mole of 4-amino-2,6-dimethy1pyrimidine in the presence of triethylamine. The resulting bis(acetylsulfanilyl) derivative is readily hydrolyzed to the product. The formation of the bis(acetylsulfanilyl) derivative has also been employed for other heterocycHc amines, eg, for synthesis of sulfathiazole and sulfamoxole (44), but the 1 1 reaction is probably preferable. 

Pivalates. The selective pivaloylation of sucrose with pivaloyl (2,2-dimethylpropionyl) chloride has been thoroughly investigated (56). The reactivity of sucrose toward pivaloylation was shown to be significantly different from other sulfonic or carboxyflc acid chlorides. For example, reaction of sucrose with four molar equivalent of toluene-/)-sulfonyl chloride in pyridine revealed, based on product isolation, the reactivity order ofO-6 0-6 > 0-1 > 0-2 (57). In contrast, a reactivity order for the pivaloylation reaction, under similar reaction conditions, was observed to be 0-6 0-6 > 0-1 > 0-4. 

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, aHenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphoms oxychloride [10025-87-3] POCl (H)- Because sulfonic acids are generally not converted directiy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphoms pentachlotide [10026-13-8] and phosphoms pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl haUdes (12,13). The conversion may also be accompHshed by continuous electrolysis of thiols or disulfides in the presence of aqueous HCl [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfutic acid [7789-21-17, or by reaction of the sulfonic acid or sulfonate with fluorosulfutic acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl haUde, can be achieved under oxidative halogenation conditions (15). 

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). 

Methane Sulfonyl Chloride (MSC)—Properties, Reactions and Applications, Technical Bulletin S-104, Elf Atochem North America, Philadelphia, Pa. 

In the reaction between xanthates and sulfonyl chlorides, the xanthates convert to dixanthogens, and the sulfonyl chlorides reduce to sulfinic acids and other compounds (38) ... 

The sulfonyl chloride group is the cure site for CSM and determines the rate and state of cure along with the compound recipe. It is less stable than the Cl groups and therefore often determines the ceiling temperature for processing. The optimum level of sulfonyl chloride to provide a balance of cured properties and processibiUty is about 2 mol % or 1—1.5 wt % sulfur at 35% Cl. It also undergoes normal acid chloride reactions with amines, alcohols, etc, to make useful derivatives (17). 

Chlorination of thiiranes in hydroxylic solvents gives /3-chloroethylsulfonyl chlorides due to further oxidation of the intermediate sulfenyl chloride by chlorine or hypochlorous acid (Scheme 40). Polymer is usually obtained also unless the reaction is done in concentrated hydrochloric acid, which causes rapid ring cleavage to 2-chloroethylthiols which are subsequently oxidized to the sulfonyl chlorides. An 85% yield of (37) is obtained in concentrated hydrochloric acid-HCl(g) whereas only a 15% yield is obtained in CCI4-H2O. 

Pyrimidine-4-sulfonic acid, 2,6-dimethyl-reactions, 3, 97 Pyrimidinesulfonic acids acidic pif 3, 60 reactions, 3, 96 synthesis, 3, 138 Pyrimidine-2-sulfonic acids acidic pK, 3, 60 reactions, 3, 97 Pyrimidine-4-sulfonic acids hydrolysis, 3, 97 Pyrimidine-2-sulfonyl chloride synthesis, 3, 138... 

Pyrimidine-2-sulfonyl chloride, 4,6-dimethyl-reactions, 3, 97 Pyrimidinesulfonyl halides reactions, 3, 97 Pyrimidinethiols S-acylation, 3, 95 S-alkylation, 3, 94 oxidation, 3, 94 synthesis, 3, 135 Pyrimidine-5-thiols oxidation, 3, 94 synthesis, 3, 136... 

This sulfonate is prepared by reaction with the sulfonyl chloride. Cleavage occurs with 0.05 MNaOH (acetone, H2O, 25°, 5 min, 83-93% yield). Here also cleavage is facilitated by intramolecular participation through the hydrate of the aldehyde. ... 

An aiyl methane- or toluenesulfonate ester is stable to reduction with lithium aluminum hydride, to the acidic conditions used for nitration of an aromatic ring (HNO3/HOAC), and to the high temperatures (200-250°) of an Ullman reaction. Aiyl sulfonate esters, formed by reaction of a phenol with a sulfonyl chloride in pyridine or aqueous sodium hydroxide, are cleaved by warming in aqueous sodium hydroxide. ... 

The procedure given is applicable to many other aulfonyl chlorides as well (see Table I). Solid sulfonyl chlorides are added as such. When heavy frothing occurs in the reduction (e.g., with p-nitrobenzenesulfonyl chloride), addition of 50 ml. of chloroform to the reaction mixture will eliminate the foam without reducing the final yield. When the sulfonyl chlorides were prepared according to Meerwein and co-workers, it was found advantageous to use the crude, damp sulfonyl chlorides, since these are more easily reduced than the dried or recrystallized materials. 

When crude aulfonyl chlorides were used as starting materials, the reaction mixture was washed with a suitable solvent to remove organic impurities. In the case of higher-melting crystalline sulfonyl chlorides, heating to 50 may be necessary to complete their reduction. The solution of the sulfinate salt may be kept overnight, if desired, with no decrease in the yield of sulfonyl cyanide. 

---