Sulfones, alkylation from sulfonic acid salts

Aromatic sulfonic acids can be converted to their respective salts by neutralization with an appropriate base. For example, reaction of potassium hydroxide (KOH) with a sulfonic acid produces a potassium sulfonate sodium hydroxide (NaOH) and the sulfonic add produce a sodium sulfonate and ammonium hydroxide (NH4OH) and the aromatic sulfonic acid produce anunonium sulfonate. A wide range of aromatic sulfonic acid salts can be produced from various aliphatic and aromatic amines and metal cations. The neutralization is conveniently done in water, since the sulfonates, and even more so the short alkyl chain hydrotropes, are generally water soluble to the extent of 30-50%. 

Alkyl halides are often used as substrates instead of alcohols. In such cases the salt of the inorganic acid is usually used and the mechanism is nucleophilic substitution at the carbon atom. An important example is the treatment of alkyl halides with silver nitrate to form alkyl nitrates. This is used as a test for alkyl halides. In some cases there is competition from the central atom. Thus nitrite ion is an ambident nucleophile that can give nitrites or nitro compounds (see 0-60).731 Dialkyl or aryl alkyl ethers can be cleaved with anhydrous sulfonic acids.732... 

An anionic mlcroemulslon system was based on blends of monoethanolamlne salts of bilinear dodecyl benzene sulfonic acid and branched pentadecyl o-xylene sulfonic acid. The bilinear structure results from the alkylation of benzene with a linear a-olefin. The former acts as a surfactant hydrophile (H) while the latter acts as a surfactant lipophile (L) at room temperature for the oil and water phases used in this study. The hydrophile tends to form water-continuous emulsions while the lipophile forms oil-continuous emulsions. The hydrophile-lipophile characteristics were varied by changing the weight ratio of H/L from 0.5 to 0.8. Decane was used as the oil phase and 2.0 wt. X NaCl In water as the aqueovis phase. The water-oil ratio was fixed at 95/5 and the total surfactant content was fixed at 2 g/dl. 

Certain nitriles add amines to form N-substituted amidines. This reaction has been modified and extended through the use of ammonia and alkyl- or aryl-ammonium salts of sulfonic acids. Many amidines have been prepared in yields ranging from 13% to 86%. Some amidines are obtained in better yields by heating a cyanide with ammonium thiocyanate or an alkylammonium thiocyanate."... 

Incidentally, 34 contributes more to the hybrid than 35, as shown by bond-distance measurements. In benzenediazonium chloride, the C—N distance is 1.42 A, and the N—N distance 1.08 A, which values fit more closely to a single and a triple bond than to two double bonds (see Table 1.5). Even aromatic diazonium salts are stable only at low temperatures, usually only < 5°C, although more stable ones, such as the diazonium salt obtained from sulfanilic acid, are stable up to 10 or 15°C. Diazonium salts are usually prepared in aqueous solution and used without iso-lation, although it is possible to prepare solid diazonium salts if desired (see 13-23). The stability of aryl diazonium salts can be increased by crown ether complexion. For aromatic amines, the reaction is very general. Halogen, nitro, alkyl, aldehyde, sulfonic acid, and so on, groups do not interfere. Since aliphatic amines do not react with... 

Electrophilic N-aminations have been performed with hydroxylamine-O-sulfonic acid (HOSA)," O-(2,4-dinitrophenyl)hydroxylamine and C>-mesitylenesulfonylhydroxylamine. The use of HOSA is mainly restricted to aqueous reaction media. Imide sodium salts of some heterocycles such as theobromine (88) can be converted to hydrazine derivatives by treatment with 0-(diphenylphosphinyl)hydroxylamine (equation 35)." This reaction has been extended to synthesis of N-arylhyd ines, where R and R are hydrogen, alkyl or aryl (equation 36)." Similarly, trisubstituted hydrazines can be prepared by the use of N-aryl-O-acetylhy oxylamines and secondary amines." A recent publication" concerning the synthesis of l-acyl-2-dkylhydrazines from hydroxamic acids and amines in the presence of activating agents has been found to be erroneous no N—N bond formation occurs under these conditions." ... 

Chlorobenzene is employed in the synthesis of certain amino-containing vat dye intermediates. When reacted with phthalic anhydride, the product is 2-chloroanthraquinone, which, with ammonia, is converted readily into 2-aminoanthraquinone (61). Other routes include replacement of halogen by amino groups, with ammonia or ammonium salts of urea, and alkyl- and aryl amines to afford secondary amines. Modification of the amino group by alkylation, with dimethyl sulfate, alkyl halides or esters of toluenesul-fonic acids, is of synthetic value. Arylation of the amino groups is of importance only in the reaction between aminoanthraquinones and nitro- or chloroanthraquinones to yield dianthraquinonylamines, or anthrimides48. For example, the reaction between 62 and 63 yields 64, which can then be converted into carbazole 65, Cl Vat Brown R (Scheme 14). Amination of haloanthraquinones such as l-amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) (66), prepared from 1-aminoanthraquinone, is of industrial use. 

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