Formation of alkyl sulfonates

Formation of alkyl sulfonates by reaction of alkyl halides with alkali or ammonium sulfites in aqueous solution in the presence of iodide ... 

In laboratory preparations, sulfuric acid and hydrochloric acid have classically been used as esterification catalysts. However, formation of alkyl chlorides or dehydration, isomerization, or polymerization side reactions may result. Sulfonic acids, such as benzenesulfonic acid, toluenesulfonic acid, or methanesulfonic acid, are widely used in plant operations because of their less corrosive nature. Phosphoric acid is sometimes employed, but it leads to rather slow reactions. Soluble or supported metal salts minimize side reactions but usually require higher temperatures than strong acids. 

Formation of Alkyl Halides from Esters of Sulfuric and Sulfonic Acids... 

A series of bromoalkyl sulfonates was therefore needed to form the N-alkyl sulfonated 2-pyridones. Formation of bromoalkyl sulfonates has not been described extensively in the literature (19). 

Breuer, E., Karaman, R., Goldblum, A., and Leader, H., Sulfonic acid-induced fragmentation of dialkyl acylphosphonates. Formation of alkyl carboxylates and alkyl sulfonates, 7. Chem. Soc.. Perkin Trans. 2, 2029, 1988. 

Sulfides react faster with hydrogen peroxide and alkyl hydroperoxides than do alkenes. For this reason, transition metal catalysts are rarely necessary, but these reactions are acid catalyzed and first order in both sulfide and peroxide. The acid (HX) can be as weak as alcohol or water but the "effectiveness (of the oxidation) is determined by the pXa of the acid. Sulfides also react faster with peroxides than do ketones (see the Baeyer-Villiger reaction, sec. 3.6). Formation of the sulfone in these reactions is straightforward, but requires more vigorous reaction conditions. It is usually easy to isolate the sulfoxide from oxidation of a sulfide. Direct conversion of a sulfide to a sulfone requires excess peroxide and vigorous reaction conditions (heating, long reaction times, more concentrated peroxide). 

A Cr(VI) sulfoxide complex has been postulated after interaction of [CrOjtClj] with MejSO (385), but the complex was uncharacterized as it was excessively unstable. It was observed that hydrolysis of the product led to the formation of dimethyl sulfone. The action of hydrogen peroxide on mesityl ferrocencyl sulfide in basic media yields both mesityl ferrocenyl sulfoxide (21%) and the corresponding sulfone (62%) via a reaction similar to the Smiles rearrangement (165). Catalytic air oxidation of sulfoxides by rhodium and iridium complexes has been observed. Rhodium(III) and iridium(III) chlorides are catalyst percursors for this reaction, but ruthenium(III), osmium(III), and palladium(II) chlorides are not (273). The metal complex and sulfoxide are dissolved in hot propan-2-ol/water (9 1) and the solution purged with air to achieve oxidation. The metal is recovered as a noncrystalline, but still catalytically active, material after reaction (272). The most active precursor was [IrHClj(S-Me2SO)3], and it was observed that alkyl sulfoxides oxidize more readily than aryl sulfoxides, while thioethers are not oxidized as complex formation occurs. 

In analogy to hydroformylation, alkenes react with SO2 and H2 to give a so-called hydrosulftnation product, sulfinic acids [116]. Cationic Pd(II) and Pt(II) complexes bearing bidentate phosphine ligands are effective catalyst precursors. A plausible mechanism for the hydrosulfination involves formation of alkyl intermediates by olefin insertion into metal hydrides, subsequent insertion of SO2, and reformation of the hydrides with the release of sulfinic acids (Scheme 7.19). However, ahphatic sulfinic acids readily undergo disproportionation to give thiosulfinic acid esters, sulfonic acids, and water at the reaction temperature. The unstable sulfinic acids can be conveniently converted into y-oxo sulfones by addition of a,-unsaturated carbonyl compounds as Michael acceptors to the reaction mixtine (Eq. 7.23) [117]. 

Over 50% of the consumption of traditional blooming antistatic agents consists of ethoxylated amines and glyceryl monostearate (GMS), and much of the rest consists of alkyl sulfonates, fatty alkanolamides and amide ethoxylates. Films containing amide antistats usually pass the American Mil-B-81705C (commonly known as Mil spec) test for electrostatic dissipation when the film is a few days old, but not after three or four weeks. This has been attributed to the formation of crystallites of the antistatic agent. 

The rate of formation of sulfonic acids may be expressed as a function of the concentration of dissolved oxygen, [02] the light intensity absorbed by SOj, I the rate of formation of alkyl free radicals, R and the rate constants of two of the preceding reactions. 

Perfluorooctanesulfonamidoethanol derivatives, which are important intermediates for the synthesis of surfactants, cannot be synthesized by the reaction of ethanolamine derivatives with perfluoroalkanesulfonyl fluorides because of the formation of several products that cannot be separated. An important side reaction is the intermediate formation of sulfonyl esters by reaction of the fluoride with the OH group. The sulfonyl esters are excellent alkylating agents that participate in various side reactions, for example, the alkylation of ethanolamine derivative under formation of a sulfonate anion. ... 

Flotation reagent can react with dye to form colored complex. Absorbance of colored complex is in proportion to the concentration of reagent. Therefore, dye-reagent complex formation had been widely used for the testing process of alkyl sulfonate, sulfate, fatty acid, and fatty amine. The common color dyes consist of methylene blue, pinacyanol, bromophenol blue, methyl green, and eosin. In general, anionic collector is colored with cationic dye (such as methylene blue and pinacyanol). And anionic collector is colored with cationic dye (such as eosin). 

The ability of ruthenium to act as a DG in electrophilic substitutions has been highlighted. Although substitution usually takes place at the metallated ring position, it has been shown that reactions of cyclometallated intermediates such as (51) with arylsul-fonyl chlorides results in attack, by an gAr pathway, at the position para to ruthenium. The result is the formation of meta-sulfonated products, such as (52). Meto-alkylated products may be formed by reaction with alkyl bromides. It has been shown that the... 

The potential of alkyl-sulfonated diphosphane ligands associated with methylated a- and P-cyclodextrins during the reaction of rhodium-catalyzed hydroformylation of 1-decene was studied. In all cases, the presence of cydodextrins increased the conversion and the diemoselectivity, whereas the hnear-to-branched ratio of the aldehyde product decreased. The decrease in regiosdectivity was attributed to the formation of low-coordinated phosphane spedes [112]. 

Alkali metal (K, Na) [ CJcyanides have been extensively employed in the formation of alkyl [ CJnitriles via nucleophilic displacement of leaving groups such as primary halides, sulfonates and trialkylammonium salts in examples too numerous to mention. In special cases (e.g., 1) other leaving groups have been used, such as benzotriazol-l-yl. The most important considerations in the choice of leaving group are often the ease of substrate preparation and the compatibility of the displacement reaction with substrate ancillary functional groups. 

Ci()-Ci4 LAS trace analysis alkyl chain length and isomer separation Formation of methyl sulfonates with PCI5 and MeOH 1.5%OV-l dimethylsilicone on Chromosorb W AW-DMCS, 3 mm X 2 m FID 118... 

C12-C1S -alkane sulfonates separation by alkyl chain length isomer separation Formation of methyl sulfonates with diazomethane 10% SE-30 dimethylsilicone on Diatopoit P, 4 mm x 1.5 m l30to25(FCatl X /min FID 126... 

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). 

ButylatedPhenols and Cresols. Butylated phenols and cresols, used primarily as oxidation inhibitors and chain terrninators, are manufactured by direct alkylation of the phenol using a wide variety of conditions and acid catalysts, including sulfuric acid, -toluenesulfonic acid, and sulfonic acid ion-exchange resins (110,111). By use of a small amount of catalyst and short residence times, the first-formed, ortho-alkylated products can be made to predominate. Eor the preparation of the 2,6-substituted products, aluminum phenoxides generated in situ from the phenol being alkylated are used as catalyst. Reaction conditions are controlled to minimise formation of the thermodynamically favored 4-substituted products (see Alkylphenols). The most commonly used is -/ fZ-butylphenol [98-54-4] for manufacture of phenoHc resins. The tert-huty group leaves only two rather than three active sites for condensation with formaldehyde and thus modifies the characteristics of the resin. 

The kinetics of formation and hydrolysis of /-C H OCl have been investigated (262). The chemistry of alkyl hypochlorites, /-C H OCl in particular, has been extensively explored (247). /-Butyl hypochlorite reacts with a variety of olefins via a photoinduced radical chain process to give good yields of aUyflc chlorides (263). Steroid alcohols can be oxidized and chlorinated with /-C H OCl to give good yields of ketosteroids and chlorosteroids (264) (see Steroids). /-Butyl hypochlorite is a more satisfactory reagent than HOCl for /V-chlorination of amines (265). Sulfides are oxidized in excellent yields to sulfoxides without concomitant formation of sulfones (266). 2-Amino-1, 4-quinones are rapidly chlorinated at room temperature chlorination occurs specifically at the position adjacent to the amino group (267). Anhydropenicillin is converted almost quantitatively to its 6-methoxy derivative by /-C H OCl in methanol (268). Reaction of unsaturated hydroperoxides with /-C H OCl provides monocyclic and bicycHc chloroalkyl 1,2-dioxolanes. 

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