Sulfonic acid chlorides hydrocarbons

Sulfochlorination s. Sulfonic acid chlorides from hydrocarbons... 

As sulfonic acid cannot be vaporized, its determination by the direct gas chromatography (GC) method is not possible. To enable determination by GC, the reactivity of the S03H group is used the esterification of the S03H group with diazomethane via acid chloride is one way to transfer the sulfonic acid to volatile compounds. By conversion of the sulfonic acid with phosphoric acid at 200-210°C, the S03H group is cleaved and the hydrocarbons are obtained [184-186]. 

Hydrocarbon sulfonates, 23 531 Hydrocarbon surfactants, 24 133 Hydrocarbon waxes, 26 220 Hydrocarbyl complexes of thorium, 24 773 of uranium, 25 441-442 Hydrochloric acid, 13 808-809, 821-822. See also Hydrogen chloride in ascorbic acid manufacture, 25 757 chlorine from, 6 172-175 constant boiling, 13 814t density and concentration of, 13 808t end use of chlorine, 6 135t for fermentation, 11 38... 

A commonly used and important reaction of sulfonic acids, or sulfonates, is their conversion to sulfonyl chlorides by treatment with phosphorus halides, or sometimes with thionyl chloride. Although it is easy to postulate mechanisms for this conversion, the exact path followed has never been determined. Similarly, although mechanisms can be suggested for other known reactions involving sulfonic acids, such as the cleavage of dialkyl ethers by anhydrous sulfonic acids (Klamann and Weyerstahl, 1965), or the formation of sulfones by treatment of an aromatic hydrocarbon with a mixture of sulfonic acid plus polyphosphoric acid (Graybill, 1967), nothing truly definitive is known about the details of the actual mechanisms of these reactions. 

All the flexible polyquinolines are readily soluble in chlorinated hydrocarbons such as methylene chloride and chloroform. Semirigid polyquinolines are soluble in tetrachloroethane or / /-cresol, but rigid polyquinolines are soluble only in strong acids like sulfuric and trifluoromethane sulfonic acid. Dilute solution properties of polyquinolines have been investigated by techniques such as membrane osmometry, light scattering, viscometry, and gel-permeation chromatography (96,97). 

Chlorosulfuric acid (HSO3CI) reacts with aromatic hydrocarbons to give sulfonic acids, sulfonyl chlorides, and sulfones, with the relative yields depending on the reaction conditions. The reaction with benzene with an equimolar amount of... 

Thiazolyl sulfamic acids, rearrangement of sulfonic acid, 70 rearrangement to sulfonic acid, 75 by sulfonation, 75 2-Thiazolyl sulfenyl chloride, transformation to, thiazolyl disulfides. 412 2-Thiazolyl sulfide, in hydrocarbon synthesis, 406 oxidation of, with m-chloroperbenzoic acid, 415 with CrOj, 415 with Hj02,405,415 with KMn04,415 physical properties, infrared, 405 NMR, 404 pKa, 404 ultraviolet, 404 preparation of, from 2-halothiazoles and 5-Thiazolyl sulfides, bis-5-thiazolyl sulfide, oxidation of, 415 general, 418 5-(2-hydroxythiazolyl)phenyl sulfide case, 418 physical properties, 418 preparation of, 417-418 table of compounds, 493-496 uses of. 442 2-Thiazolyl sulfinic acid, decomposition of, 413 preparation of, from 2-acetamidothiazole sulfonyl chloride, 413 from A-4-thiazoline-2-thione and H, 0, 393,413 table of compounds, 472-473 5-Thiazolyl sulfinic add, preparation of,... 

Commercial tetralin contains naphthalene as the principal impurity and this interferes with the preparation of tetralin-1-hydroperoxide or with use of the hydrocarbon as hydrogen donor in hydrogen-transfer reactions. An early purification procedure is uninviting fractionation extraction in turn with mercury (to remove sulfur impurities), with mercuric acetate solution (to remove olefins), and with sulfuric acid fractionation. More recently Bass sulfonated the crude hydrocarbon with coned, sulfuric acid and added ammonium chloride to precipitate ammonium tetralin-6-sulfonate. The salt was crystallized until pure and hydrolyzed by steam distillation from sulfuric acid solution. Distillation from sodium gave material showing no ultraviolet bands characteristic of naphthalene. 

The addition takes place according to Markownikoff s rule. The addition of carbo lic acida to the double bonds of isobutylene and trimethyl-ethylene gives tertiary esters. A true equilibrium independent of sulfuric acid concentrations is established in the exothermic reaction. The addition does not go well with ethylene, but goes well with many of the higher alkenes, particularly with some of the terpenes. To avoid the polymerizing effects of sulfuric acid, various other catalysts, such as sulfonic acids, triethylamine, hydrofluoric acid, boron trifluoride, and cuprous chloride have been used. The addition may take place at room temperature or higher and is aided by pressure. The vapors of the acid and hydrocarbon may be passed over catalysts, such as activated carbon, heteropoly acids, or metal phosphates. ... 

The present volume is a revised and enlarged third edition of the book formerly titled Tables for Identification of Organic Compounds, Four new classes of compounds, i.e., sulfonyl chlorides, sulfonamides, thiols and thioethers were added, bringing the number of classes included in the book to twenty-six. The tables of alkanes, alkenes, alkynes, aromatic hydrocarbons, phenols, nitriles and sulfonic acids were all thoroughly revised and considerably enlarged. In all, the addition of 2400 compounds to the third edition, raised the total number of parent compounds in the book to over 8150. 

When polystyrene is sulfonated in chlorinated hydrocarbons with a complex of dioxane-SOs, the polymer precipitates from solution at low concentrations. Complexes of ketones with SO3 can also be used to sulfonate polystyrene in halogenated solvents. The ratio of sulfonation is more favorable for poly(vinyl toluene) than it is for polystyrene at the same conditions. Also, sulfur dioxide swells polystyrene. The polymer can be sulfonated in this medium with sulfur trioxide or with chlorosulfonic acid. Polystyrene, sulfonated in CS2 with aluminum chloride catalyst, is water insoluble in a free acid form. ... 

Electrohjsis/tetramethglammonium chloride Electrolytic reductions with tetramethylammonium Sulfinic acids and hydrocarbons from sulfones... 

Chlorosulfonic acid, CISO3H, is quite convenient for laboratory use, but generates a mole of HCl for each mole of sulfonic acid formed. Reaction of an aromatic hydrocarbon with 2 moles of chlorosulfonic acid will result in the formation of the sulfonyl chloride [1, p. 84]. 

Aromatic hydrocarbons also react smoothly with an equimolar amount of chlorosulfonic acid or an excess of the reagent to yield either the sulfonic acid or the sulfonyl chloride (Equations 6 and 7). The direct conversion of aromatic compounds into their sulfonyl chlorides (chlorosulfonation or chlorosulfonylation) is probably the most important reaction of chlorosulfonic acid because sulfonyl chlorides are intermediates in the synthesis of a wide range of sulfonyl derivatives. The process is of wide application because many substituents on the aromatic ring, e.g. alkyl, alkoxy, amide, carboxy, cyano, hydroxy, nitro and multiple bonds are unaffected by the reagent. 

Sulfonic acid groups (SO3H) are both bulky and electron-withdrawing consequently once one sulfonic acid group has been introduced into the aromatic nucleus, the resultant arylsulfonic acid will be more resistant towards further sulfonation. The latter will require more drastic conditions and the product will contain the two sulfonic acid groups in the 1,3-position with respect to each other. With reactive substrates, e.g. aromatic hydrocarbons, halides or ethers, mono-chlorosulfonation is often best achieved at low temperature in ftie presence of chloroform, dichloromethane or 1,2-dichloroethane to moderate the reaction and avoid disulfonation. Suter and Weston S described the experimental procedures for the sulfonation of aromatic hydrocarbons, halides and ethers and many early references and details of the synthesis of sulfonic acids and sulfonyl chlorides are included in Suter s comprehensive text." ... 

Chlorobenzene reacts with an equimolar amount of chlorosulfonic acid to give mainly the p-sulfonic acid together with a little of the sulfonyl chloride and the sulfone. With an excess of the reagent good yields of p-chlorobenzenesulfonyl chloride are obtained. The kinetics of the sulfonation of chlorobenzene with chlorosulfonic acid have been studied, and the reaction has been reported in several patents. These involved various modifications such as the use of excess reagent in hydrocarbon solvents containing alkali metal or ammonium salts, or a mixture of the reagent with thionyl chloride in the presence of sulfamic acid, sodium sulfate or dimethylformamide. In the reaction, the yield of 4,4 -dichlorodiphenyl sulfone can be increased under a variety of conditions the... 

The sulfoxidation and chlorosulfoxidation of hydrocarbons yields sulfonic acids and alkane sulfonyl chlorides, respectively. 

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). 

Reactions other than those of the nucleophilic reactivity of alkyl sulfates iavolve reactions with hydrocarbons, thermal degradation, sulfonation, halogenation of the alkyl groups, and reduction of the sulfate groups. Aromatic hydrocarbons, eg, benzene and naphthalene, react with alkyl sulfates when cataly2ed by aluminum chloride to give Fhedel-Crafts-type alkylation product mixtures (59). Isobutane is readily alkylated by a dipropyl sulfate mixture from the reaction of propylene ia propane with sulfuric acid (60). 

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