Sodium benzenesulfonate, preparation

Sulfonic acids are converted to the corresponding acid halides in much the same way as carboxylic acids. Thionyl chloride is the best reagent for the preparation of methanesulfonyl chloride (83%). By heating with a large excess of thionyl chloride, however, p-toluenesulfonic acid is converted into its anhydride (87%). Benzenesulfonyl chloride is made in 80% yield by the action of either phosphorus pentachloride or phosphorus oxychloride at 180° on sodium benzenesulfonate. Chlorosulfonic and fluorosulfonic acids are used in the conversion of sodium p-chloro-benzenesulfonate to the corresponding sulfonyl halides (85 8S>%). ... 

Preparative electrolyses of diphenyl disulfide and 4-bromophenyl 4-nitrophenyl disulfide afforded, respectively, sodium benzenesulfonate (20%) and bis(4-bromophenyl) and bis(4-nitrophenyl) disulfides with an overall yield of 80% [37]. 

Historically, phenol was produced by the distillation of coal tar. Today, phenol is prepared by one of several synthetic methods, such as the fusion of sodium benzenesulfonate with sodium hydroxide followed by acidification the hydrolysis of chlorobenzene by dilute sodium hydroxide at high temperature and pressure to give sodium phenate, which on acidification liberates phenol (Dow process) or the catalytic vapor-phase reaction of steam and chlorobenzene at 500°C (Raschig process). 

Sulfonyl chlorides. Adams and Marvel prepared benzenesulfonyl chloride by heating sodium benzenesulfonate with PCI in an oil bath at 170-180° for 15 hrs. every 4 hrs. the flask was removed from the oil bath, stoppered, and shaken until the mass became pasty. The mixture was cooled, treated with ice and water, and 170-180°, 15 hra,. 

Sodium Benzenesulfonate. Benzenesulfonic acid prepared continuously in a cascade series of six 2,000-gal cast-iron vessels is fed to a neutralizer system. Sodium sulfite slurry from reaction (3) is fed into the neutraliza tion tank at a constant rate while the benzenesulfonic acid flow is regulated to keep the reaction mixture distinctly acid. Sulfur dioxide is liberated [Eq. (2)] and piped for acidification of sodium phenoxide [Eq. (4)], and some is sent to another plant for purification and liquefaction. 

Reaction of benzenesulfonic acid with sodium hydroxide This is the oldest method for the preparation of phenol. Benzene is sulfonated and the benzenesulfonic acid heated with molten sodium hydroxide. Acidification of the reaction mixture gives phenol. 

A/,N-Dimethylaminomethylenemalonate (329, R = Me) was prepared in the reaction of diethyl malonate and DMF diethyl acetal at 130-150°C for 90 min (71S220), or in the reaction of the sodium salt of diethyl malonate and tetramethylformamidinium benzenesulfonate in ethanol at ambient temperature for 20 hr (71S220), or in the reaction of diethyl malonate and Gold s reagent (330) in the presence of sodium ethylate in ethanol at reflux temperature overnight (82SC939), in 77%, 50%, and 74% yields, respectively. 

Principally the same, but chemically simpler, sequence was used to prepare arylnitro anion-radicals from arylamines, in high yields. For instance, aqueous sodium nitrite solution was added to a mixture of ascorbic acid and sodium 3,5-dibromo-4-aminobenzenesulfonate in water. After addition of aqueous sodium hydroxide solution, the cation-radical of sodium 3,5-dibromo-4-nitro-benzenesulfonate was formed in the solution. The latter was completely characterized by its ESR spectrum. Double functions of the nitrite and ascorbic acid in the reaction should be underlined. Nitrite takes part in diazotization of the starting amine and trapping of the phenyl a-radical formed after one-electron reduction of the intermediary diazo compound. Ascorbic acid produces acidity to the reaction solution (needed for diazotization) and plays the role of a reductant when the medium becomes alkaline. The method described was proposed for ESR analytical determination of nitrite ions in water solutions (Lagercrantz 1998). 

Cleavage of the sulfonyl esters to the parent alcohols is accomplished in yields of 60-100% by treatment of the p-toluenesulfonates with 2-6 equivalents of sodium naphthalene in tetrahydrofuran at room temperature (yields 60-100%). Sodium naphthalene is prepared by stirring sodium with an equivalent amount or a slight excess of naphthalene in tetrahydrofuran for 1 hour at room temperature under an inert gas [701]. Benzenesulfonates and bromo-benzenesulfonates are also cleaved to the parent alcohols while alkyl methanesulfonates are reduced also to hydrocarbons [701]. 

Heck olefination of a diazonium salt is a key step in the industrial synthesis of sodium 2-(3,3,3-trifluoropropyl)benzenesulfonate, en route to Novartis sulfonylurea herbicide Prosulfuron (Scheme 15) [46]. Pd(dba)2 (0.5-1.5 mol%, prepared in situ from PdCl2), is used as catalyst. After completion of the arylation step, charcoal is added, thus directly providing a heterogeneous catalyst for the subsequent hydrogenation step and enabling easy removal of the now supported catalyst by filtration. 

Esters of aliphatic and aromatic sulfonic acids are conveniently prepared in high yields from alcohols and sulfonyl halides. A basic medium is required. By substituting sodium butoxide for sodium hydroxide in butanol, the yield of n-butyl p-toluenesulfonate is increased from 54% to 98%. Ethyl benzenesulfonate and nuclear-substituted derivatives carrying bromo, methoxyl, and nirro groups are prepared from the corresponding sulfonyl chlorides by treatment with sodium ethoxide in absolute ethanol the yields are 74-81%. Pyridine is by far the most popular basic medium for this reaction. Alcohols (C -Cjj) react at 0-10° in 80-90% yields, and various phenols can be converted to aryl sulfonates in this base. "... 

Snyder et al. prepared the reagent in ethanol solution by dissolving 100 mg. of sodium in 2 ml. of ethanol and adding a solution of 1,037 mg. of phenyltrimethyl-ammonium benzenesulfonate (Eastman practical trimethylphenylammonium... 

Preparation of sodium-[2-(3, 3, 3 - trifluoroprop-l -enyl)]-benzenesulfonate At that temperature sodium acetate is added and stirring is continued at room temperature. Pd(dba)2 is added and 3,3,3-trifluoropropene is bubbled in. After the end of the mildly exothermic reaction no more nitrogen is evolved. The ethanoic acid is distilled off and the residue is dissolved in water. 

Preparation of sodium-[2-(3, 3, 3 - trifluoroprop-l -yl)]-benzenesulfonate The solution is transferred into a hydrogenation flask and activated carbon is added. Under the hydrogen atmosphere the heterogeneous catalyst is formed and the catalytic hydrogenation is carried out. The palladium containing catalyst is separated by filtration and washed with water. 

Methyl ion According to Reactions (2) and (3). These methods depend on the preparation of an alcoholic solution of the phenyltrimethylammonium hydroxide directly [reaction (2)] or indirectly [reaction (3)] with the sodium salt either of the benzenesulfonate or of the toluenesulfonate being thrown out of solution. The alcoholic solution of the alkylating agent is then reacted with the compound to be methylated. 

PBI-based polymer electrolytes with pendant functional groups were proposed by Gieselman and Reynolds [133, 134], by producing N-substituted PBI with sulfonates, which could be traced back to Sansone s work [130]. In the following years, more efforts were devoted to prepare sulfonated PBI membranes by reacting PBIs with sodium (4-bromomethyl)benzenesulfonate [135, 136], arylsulfonates, or alkylsulfonates [137]. The introduction of benzylsulfonic, arylsulfonic, or alkylsulfonic acids was found to create proton conductivity in the presence of water. Using A-substitution, the sulfonation degree of the membranes could be accurately controlled [133]. 

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