Preparation from Sulfonates

This reaction is reminiscent to the autoxidation of cytochrome b5 and described reductions of cytochromes b and c with hyperoxide. In order to study further analogy of osmochrome systems to the cytochromes, water-soluble osmochromes have been prepared from sulfonated precursors. Due to the acidity of pure water, osmochrome systems cannot be held in water, but the osmichrome salt Na3[Os[TPPS4) (1-Meim)2] was isolated [51]. 

As base. Both sulfides and aryl ethers are readily prepared from sulfonates using CsF as a base. A route to cyclopropanolactone involves the CsF-mediated reaction of a malonic ester and glycidyl nosylate. ... 

Ldpez, M.L., Compan, V., Garrido, J., Riande, E. and Acosta, J.L. 2001. Proton transport in membranes prepared from sulfonated polystyrene-poly (vinylifluoride) blends. J. Electrochem. Soc. 148 E372-E377. 

J. Lukkari, A. Viinikanoja, J. Paukkunen, M. Salomaki, M. Janhonen, T. Aaritalo, J. Kankare, Oxidation induced variation in polyelectrolyte multilayers prepared from sulfonated self-dopable poly(alkoxythiophene), Chemical Communications 2000, 571. 

When the base is hydroxide and the reaction is done in water, as in the preparation of 189, this reaction is known as the Schotten-Baumann reaction, after Carl Schotten (Germany 1853-1910) and Eugen Baumann (Germany 1846-1896). Just as amides are prepared from the reaction of carboxylic acid esters with amines or ammonia, so sulfonamides are prepared from sulfonate esters. An example is the reaction of ethyl butanesulfonate (190) with ammonia to give butanesulfonamide, 191. 

Bikson, B. and Nelson, J.K., Fluid Separation Composite Membranes Prepared from Sulfonated Aromatic Polymers in Lithium Salt Form US 5364454, 1994. (Praxair Technology Corp.)... 

Bikson B, Nelson JK. Fluid separation composite membranes prepared from sulfonated aromatic polymers in lithium salt form. US Patent 5,364, 454 (1994). 

The higjily water-soluble dienophiles 2.4f and2.4g have been synthesised as outlined in Scheme 2.5. Both compounds were prepared from p-(bromomethyl)benzaldehyde (2.8) which was synthesised by reducing p-(bromomethyl)benzonitrile (2.7) with diisobutyl aluminium hydride following a literature procedure2.4f was obtained in two steps by conversion of 2.8 to the corresponding sodium sulfonate (2.9), followed by an aldol reaction with 2-acetylpyridine. In the preparation of 2.4g the sequence of steps had to be reversed Here, the aldol condensation of 2.8 with 2-acetylpyridine was followed by nucleophilic substitution of the bromide of 2.10 by trimethylamine. Attempts to prepare 2.4f from 2.10 by treatment with sodium sulfite failed, due to decomposition of 2.10 under the conditions required for the substitution by sulfite anion. 

Sulfones and sulfoxides (145) are obtained usually from the corresponding sulfide by oxidation (Scheme 75) (341). though some of them were prepared from a halothiazole and metal sulfinate (342). 2-Amino-5-acetamidophenylsulfonylthiazole has been prepared by direct heterocycli-zation (343. 344). 

DiaminO 4,4-dimethyl-l,3,5-thiadiazine hydrobromide was isolated as by-product (418). Benzene sulfonates of cyanohydrin prepared from sodium cyanide and an halobenzoaldehyde, when treated with thiourea or its derivatives, afford 2,4-diamino-5-(p-halogenophenyl)-thiazole benzene sulfonates (447). Similarly, cyanoamido thiocarbamates obtained from cyanamide and isothiocyanates yield substituted 2,4-diaminothiazoles (598). 

DihaIogenothiazoIes (271) thus can be prepared from sodium acetylaminomethane sulfonate (270) and thionyl halide, but this reaction proceeds in low yield. With X — Cl, the yield is 20%, while with X = Br the yield decreases to 2% (Scheme 140). 

When benzene is prepared from coal tar it is contaminated thiophene from which it cannot be separated by distillation because of very similar boiling points Shaking a mixture of benzene and thiophene with sulfuric acid causes sulfonation of the thiophene ring but leaves benzene untouched The sulfonation product of thiophene dissolves m the sulfuric acid layer from which the benzene layer is separated the benzene layer is then washed with water and distilled Give the structure of the sulfonation product of thiophene... 

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 series of water-soluble fiber-reactive xanthene dyes has been prepared from the reaction of ben2oxanthenedicatboxylic acid anhydride disulfonic acid with, for example, 3-aminophenyl-P-hydtoxyethyl sulfone to yield dyes, with high brilliance and good fastness properties for dyeing of or printing on leather, wool, sHk, or ceUulosic fibers (53). 

Direct, acid catalyzed esterification of acryhc acid is the main route for the manufacture of higher alkyl esters. The most important higher alkyl acrylate is 2-ethyIhexyi acrylate prepared from the available 0x0 alcohol 2-ethyl-1-hexanol (see Alcohols, higher aliphatic). The most common catalysts are sulfuric or toluenesulfonic acid and sulfonic acid functional cation-exchange resins. Solvents are used as entraining agents for the removal of water of reaction. The product is washed with base to remove unreacted acryhc acid and catalyst and then purified by distillation. The esters are obtained in 80—90% yield and in exceUent purity. 

Copolymers of sodium acrylate with sodium 2-acrylamido-2-methylpropane sulfonate (AMPS) or /V, /V- dim ethyl acryl am i de (52) have been used to prepare cross-linked systems at high temperatures and salinity. Chromium cross-linked gels, prepared from a 3 1 blend of partially hydrolyzed... 

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. 

Most derivatives of aniline are not obtained from aniline itself, but ate prepared by hydrogenation of their nitroaromatic precursors. The exceptions, for example, /V-a1ky1ani1ines, /V-ary1ani1ines, sulfonated anilines, or the A/-acyl derivatives, can be prepared from aniline and have been discussed. Nitroanilines are usually prepared by ammonolysis of the corresponding chloronitroben2ene. Special isolation methods may be requited for some derivatives if the boiling points are close and separation by distillation is not feasible. Table 6 Hsts some of the derivatives of aniline that are produced commercially. 

The first sulfonate was prepared from paraffin and SO2CI2 by the Reed reaction (eq. 11) (58,59) ... 

Fatty JicidFster Sulfonates. Fatty acid ester sulfonates (FAES) are generally produced from methyl esters, ie, methyl ester sulfonate (MES) and prepared via sulfonation, followed by bleaching and neutralization, in a relatively difficult and complex process ... 

Poly(vinyl nitrate) has been prepared and studied for use in explosives and rocket fuel (104,105). Poly(vinyl alcohol) and sulfur trioxide react to produce poly(vinyl sulfate) (106—111). Poly(vinyl alkane sulfonate)s have been prepared from poly(vinyl alcohol) and alkanesulfonyl chlorides (112—114). In the presence of urea, poly(vinyl alcohol) and phosphoms pentoxide (115) or phosphoric acid (116,117) yield poly(vinyl phosphate)s. 

Tetrachlorotoluene, C H Cl (mol wt 229.93) (1,2,3,5-tetrachloro-4-methylben2ene), is prepared from the Sandmeyer reaction on 3-arnino-2,4,6-trichlorotoluene. 2,3,4,5-Tetrachlorotoluene (l,2,3,4-tetrachloro-5-methylben2ene) is the principal isomer in the further chlorination of 2,4,5-trichlorotoluene. Exhaustive chlorination of -toluenesulfonyl chloride, followed by hydrolysis to remove the sulfonic acid group yields... 

It is prepared from the polycondensation of the disodium salt of bisphenol A and 4,4-dichlorodiphenyl sulfone in a polar aprotic solvent such as dimethyl sulfoxide (26). 

Efforts to raise the alpha-selectivity have been made. Thus nitration of anthraquinone using nitrogen dioxide and ozone has been reported (17). l-Amino-4-bromoanthraquinone-2-sulfonic acid (bromamine acid) [116-81 -4] (8) is the most important intermediate for manufacturing reactive and acid dyes. Bromamine acid is manufactured from l-aminoanthraquinone-2-sulfonic acid [83-62-5] (19) by bromination in aqueous medium (18—20), or in concentrated sulfuric acid (21). l-Aminoanthraquinone-2-sulfonic acid is prepared from l-aminoanthraquinone by sulfonation in an inert, high boiling point organic solvent (22), or in oleum with sodium sulfate (23). 

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