Alkyl sulfonates with sodium

The reactions of alkyl sulfonates with sodium, potassium or tetraalkylammonium carboxylates generally proceed with inversion of configuration. In the case of f-alkyl sulfonates, however, a varied amount of elimination products is invariably formed. Of all metal carboxylates, cesium salts (Scheme 43) have proved vastly superior with respect to reactivity and the suppression of undesirable side reactions. ... 

Nitdles may be prepared by several methods (1). The first nitrile to be prepared was propionitdle, which was obtained in 1834 by distilling barium ethyl sulfate with potassium cyanide. This is a general preparation of nitriles from sulfonate salts and is referred to as the Pelou2e reaction (2). Although not commonly practiced today, dehydration of amides has been widely used to produce nitriles and was the first commercial synthesis of a nitrile. The reaction of alkyl hahdes with sodium cyanide to produce nitriles (eq. 1) also is a general reaction with wide appHcabiUty ... 

A.lkyl Sulfosuccinate Half Asters. These detergents are prepared by reaction of maleic anhydride and a primary fatty alcohol, followed by sulfonation with sodium bisulfite. A typical member of this group is disodium lauryl sulfosucciaate [26838-05-1]. Although not known as effective foamers, these surfactants can boost foams and act as stabilizers when used ia combination with other anionic surfactants. In combination with alkyl sulfates, they are said to reduce the irritation effects of the latter (6). 

The cyclopropane cyclizations by elimination of triflinic acid (CF3S02H) are readily effected by basic treatment of triflones (trifluoromethyl alkyl sulfones) with activated /-protons (equations 46 and 47)39. The cyclopropane diesters 45 are formed on treatment of 44 with potassium hydride in DMSO or sodium methoxide in methanol (equation 48). In contrast, the monoester 46 failed to give the desired cyclopropane40. Addition of carbanions derived from /f, y-unsaturated phenyl sulfones to a, /i-unsaturated carboxylic esters and subsequent elimination of benzenesulfinate ion give cyclopropanes possessing the unsaturated side chain and the ester function in trans positions (equation 49)41. 

The antifoam compounds were tested in 0.375% Mersolat H30, a sodium alkyl sulfonate with pH 6.5. The Persistence Value was calculated according to the formula Persistence Value = [mL KD/(seconds to 125 mL - seconds to KD)] x 150. The results at 23 °C and 70 °C are given in Tables 2 and 3, respectively. 

The alkyl phenyl sulfone precursors for the olefination may be prepared by the reaction of alkyl halides with sodium benzenethiolate, followed by oxidation of the alkyl phenyl sulfides formed with mCPBA. Alternatively, displacement of an alkyl bromide or iodide with the less nucleophilic sodium benzenesulfmate PhS02Na leads directly to the alkyl phenyl sulfone. 

The majority of aliphatic compounds tend to be resistant to direct sulfonation and under forcing conditions often form a complex mixture of products. Consequently, aliphatic sulfonic acids are generally prepared by other methods, such as treatment of an alkyl halide with sodium sulfite (see p. 101). However, in certain cases direct sulfonation works well, namely with terminal alkynes (36) and tertiary alkanes (37) (Scheme 19). 

Description. Sulfosuccinates are the sodium salts of alkyl esters of sulfosucctuic acid they generally result from the condensation of maleic anhydride with a fatty alcohol, followed by sulfonation with sodium bisulfite (NaHSOa). Maleic or fumaric acids are also appropriate bifunctional reactives. 

The direct sulfonation of alkanes is not generally of much practical significance as a synthetic route to alkanesulfonic acids as these are usually more conveniently obtained indirectly by reaction of the appropriate alkyl halide with sodium sulfite or hydrosulfite. ... 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

Detergent All late. In the 1940s, sodium dodecylben2ene sulfonate [25155-30-0] (DDES) produced by the alkylation of ben2ene with propylene tetramer followed by sulfonation with oleum [8014-95-7] (H2SO4 mixture with sulfur trioxide) or sulfur trioxide and then neutrali2ation... 

Naphthalene, xylenes and alkyl benzenes can be purified by sulfonation with concentrated sulfuric acid and crystallisation of the sodium sulfonates. The hydrocarbon is distilled out of the mixture with superheated steam. 

In a further development on this theme, the thiol, 153, is first alkylated to the corresponding benzyl ether (158). Treatment with sodium methoxide removes the proton on the amide nitrogen to afford the ambient anion (159). This undergoes alkylation with methyl bromide on the ring nitrogen thus it locks amide into the imine form (160). Chlorolysis serves both to oxidize the sulfur to the sulfone stage and to cleave the benzyl ether linkage there is thus obtained the sulfonyl chloride, 161. 

Allylic sulfones and a, /5-unsaturated sulfones are known to be in equilibrium314-319. Allylic sulfones, such as 242, isomerize to a, /5-unsaturated sulfones 243 upon treatment with a catalytic amount of potassium t-butoxide in dry THF. The a, /5-unsaturated sulfones can be converted to the corresponding olefins upon desulfonation with sodium amalgam320 or aluminium amalgam294,321. Since treatment of allylic sulfones with potassium-graphite gives 2-alkenes, alkylation of allylic sulfones and subsequent desulfonation is a useful process for the synthesis of olefins, as shown in Scheme 6. 

Compared with sodium w-alkyl sulfates the ester sulfonates with the same number of carbon atoms in the hydrophobic chain have lower CMC values because the methyl group also contributes to the micellization. 

Alkyl halides or sulfuric or sulfonic esters can be heated with sodium or potassium thiocyanate to give alkyl thiocyanates, though the attack by the analogous cyanate ion (10-66) gives exclusive N-alkylation. Primary amines can be converted to thiocyanates by the Katritzky pyrylium-pyridinium method (pp. 447, 489). "... 

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