Sulfonic acids from olefins

General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may be used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, aHenes, and ketenes, as shown in Figure 1 (10). Sulfonic acids may be converted to sulfonamides via reaction with an amine in the presence of phosphoms oxychloride [10025-87-3] POCl (H)- Because sulfonic acids are generally not converted directiy to sulfonamides, the reaction most likely involves a sulfonyl chloride intermediate. Phosphoms pentachlotide [10026-13-8] and phosphoms pentabromide [7789-69-7] can be used to convert sulfonic acids to the corresponding sulfonyl haUdes (12,13). The conversion may also be accompHshed by continuous electrolysis of thiols or disulfides in the presence of aqueous HCl [7647-01-0] (14) or by direct sulfonation with chlorosulfuric acid. Sulfonyl fluorides are typically prepared by direct sulfonation with fluorosulfutic acid [7789-21-17, or by reaction of the sulfonic acid or sulfonate with fluorosulfutic acid. Halogenation of sulfonic acids, which avoids production of a sulfonyl haUde, can be achieved under oxidative halogenation conditions (15). 

Commercially, sulfonic acid ion-exchange resins are used in fixed-bed reactors to make these tertiary alkyl ethers (14). Since the reaction is very selective to tertiary olefins and also reversible, a two-step procedure is also used to recover commercially pure tertiary olefins from mixed olefin process streams. The corresponding tertiary alkyl ether is produced in the olefin mixture and then easily separated from the unreacted olefins by simple fractionation. The reaction is then reversed in a second step to make a commercially pure tertiary olefin, usually isobutylene or isoamylene. 

Olefins, sultones, alkanes, and alkenesulfonates may be separated by liquid chromatography on silica gel using hexane, trichloromethane-hexane, ethanol-dime thy lcarbonate, and ethanol-ammonium hydroxide as the eluents. Pueschel and Prescher [110] achieved the separation of alkene-1,4-sultone and alkene-1,3-sultone from each other and from other sulfonic acid esters in AOS by thin-layer chromatography on silica gel G with 4 1 diethylcarbonate-ligroine as the... 

Neutralization of the sulfonation product from a-olefins is more complex than neutralization of the corresponding products of alkylbenzenes. This is because the S03-a-olefin acid product contains about 50% free sulfonic acid, the rest being C(l,3) and D(l,4) sultones, assuming that with acid aging the 0(1,2) sultones have disappeared. In the case of a-olefins an excess of caustic (1.5-2.0% excess) must be added to neutralize both the sulfonic acid initially present and that formed on subsequent hydrolysis of the C(l,3) and D(l,4) sultones. The sultones (ring-structured esters) cannot be converted to their proper salts by a simple neutralization but need a hydrolysis step. 

A dispersant that can be used in drilling fluids, spacer fluids, cement slurries, completion fluids, and mixtures of drilling fluids and cement slurries controls the rheologic properties of and enhances the filtrate control in these fluids. The dispersant consists of polymers derived from monomeric residues, including low-molecular-weight olefins that may be sulfonated or phosphonated, unsaturated dicarboxylic acids, ethylenically unsaturated anhydrides, unsaturated aliphatic monocarboxylic acids, vinyl alcohols and diols, and sulfonated or phosphonated styrene. The sulfonic acid, phosphonic acid, and carboxylic acid groups on the polymers may be present in neutralized form as alkali metal or ammonium salts [192,193]. 

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General Reaction Chemistry of Sulfonic Acids. Sulfonic acids may he used to produce sulfonic acid esters, which are derived from epoxides, olefins, alkynes, allenes, and kelenes, as shown in Figure 1. Phosphorus pentachloride and phosphorus pentabromide can be used to convert sulfonic acids to the corresponding sulfonyl halides. 

If the released electrophile HS03 is not intercepted during the protodesulfonyla-tion as in Figure 5.5, it attacks the defunctionalized aromatic compound again. In this way an isomer of the original sulfonic acid may be obtained. The best-known example of such an isomerization is the conversion of naphthalene-l-sulfonic acid into naph-thalene-2-sulfonic acid (Figure 5.6). Naphthalene-l-sulfonic acid is destabilized by the so-called peri-interaction, that is, the steric interaction between the C8—H bond of the naphthalene and the substituent on Cl. The peri-interaction is thus a cix-olefin strain. Because naphthalene-2-sulfonic acid does not suffer from this interaction, it becomes the only reaction product under conditions of thermodynamic control. 

Carbocyclic compounds can be formed by the nucleophilic intramolecular capture of a seleniranium intermediate of an olefinic bond. The carbonium ion which is formed as intermediate can react with another nucleophile or with the solvent. The first examples of these carbocyclization reactions were observed with dienes. Clive [105] reported that the reaction of the diene 203 with phenyl-selenyl chloride in acetic acid afforded the intermediate 204 which reacted with the solvent to give the bicyclic compound 205 (Scheme 31). Carbocyclization reactions were efficiently promoted by phenylselenyl iodide produced by diphenyl diselenide and iodine. As indicated in Scheme 31,Toshimitsu reported that the reaction of 1,5-hexadiene 206, in acetonitrile and water, afforded the acetamido cyclohexane derivative 209, derived from the cyclization of the seleniranium intermediate 207 followed by the reaction of the carbocation 208 with acetonitrile [106]. In several cases, carbocyclization reactions can be more conveniently effected by independently generating the seleniranium intermediates. A simple procedure consists of the reaction of trifluoromethane-sulfonic acid with j9-hydroxyselenides, which can be easily obtained from the... 

An anionic mlcroemulslon system was based on blends of monoethanolamlne salts of bilinear dodecyl benzene sulfonic acid and branched pentadecyl o-xylene sulfonic acid. The bilinear structure results from the alkylation of benzene with a linear a-olefin. The former acts as a surfactant hydrophile (H) while the latter acts as a surfactant lipophile (L) at room temperature for the oil and water phases used in this study. The hydrophile tends to form water-continuous emulsions while the lipophile forms oil-continuous emulsions. The hydrophile-lipophile characteristics were varied by changing the weight ratio of H/L from 0.5 to 0.8. Decane was used as the oil phase and 2.0 wt. X NaCl In water as the aqueovis phase. The water-oil ratio was fixed at 95/5 and the total surfactant content was fixed at 2 g/dl. 

Some work [5] has been performed on the photochemical reaction between sulfur dioxide and hydrocarbons, both paraffins and olefins. In all cases, mists were found, and these mists settled out in the reaction vessels as oils with the characteristics of sulfuric acids. Because of the small amounts of materials formed, great problems arise in elucidating particular steps. When NO and O2 are added to this system, the situation is most complex. Bufalini [3] sums up the status in this way The aerosol formed from mixtures of the lower hydrocarbons with NO , and SO2 is predominantly sulfuric acid, whereas the higher olefin hydrocarbons appear to produce carbonaceous aerosols also, possibly organic acids, sulfuric or sulfonic acids, nitrate-esters, etc. ... 

First of all, these properties were used to separate the sulfonated phosphine from the excess of sulfuric acid affer sulfonation by forming a triisooctylammo-nium salt in toluene, which is totally insoluble in water [1], Later it was discovered, that the re-immobilized ligand in toluene as well as the immobilized ligand in water are useful and remarkably stable catalyst systems. As classical homogeneous catalysts they are very active, e. g., for the hydroformylation of higher olefins and olefins with internal double bonds. 

RCH=CHi — RCH CH Hi. Brown and co-workers " found that an alkylborane resulting from hydroboration of an olefin reacts readily with either chloramine or hydroxylamine-O-sulfonic acid to form the corresponding amine in yield of 50-60%. For example, norbomene yields exo-norbornylamine. 

Absorphon of CO2 in aqueous solutions of MEA absorption of H2S and mercaptans in aqueous soluhons of alkanolatnines and caushc soda absorption of carbon monoxide in aqueous cuprous ammonium chloride solutions absorphon of lower olefins in aqueous soluhons of cuprous ammonium compounds absorption of pure chlorine in aqueous solutions of sodium carbonate or sodium hydroxide conversion of dithiocarbamates to thiuram disulfides sulfonation of aromatic compounds with lean SO3 recovery of bromine from lean aqueous solutions of bromides reactions of importance in pyrometallurgy absorphon of CO2 in aqueous solutions of caustic alkahes and amine absorption of O2 in aqueous solutions of sodium dithionite absorphon of O2 in aqueous sodium sulfite soluhons absorption of O2 in alkaline solutions containing the sodium salt of 1,4-napthaquinone- 2-sulfonic acid (NQSA) special case role of diffusion in the absorption of gases in blood in the human body. 

The synthesis of the C1-C7 fragment, which corresponds to the lactone, starts with the homoallylic alcohol 2 which was prepared from 1. The existing stereocenter and the conjugate addition method of Evans [21] allow the control of the C5 stereocenter. The homoallylic alcohol 2 was oxidatively cleaved and homologated to the trans enoate 3 by a Wittig olefination. Treatment of 3 with benzaldehyde and a catalytic amount of KHMDS provided acetal 4. The internal Michael addition of the hemiacetal intermediate proceeds with complete stereoselectivity [22]. After deprotection and oxidation, the corresponding aldehyde was treated with Amberlyst-15 and then with camphor sulfonic acid (CSA), to yield pyrane 5 as a mixture of (3- and a-anomers (1.8/1). This compound was converted to the thiophenyl acetal 6 (4 steps) as this compound can be hydrolyzed later under mild conditions (Hg +) with subsequent oxidation of the lactol to the desired lactone. Compound 6 represents the C1-C7 fragment of discodermolide (Scheme 1). 

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