Esters, sulfonic acid preparation

To prepare alkyl sulfonate esters, sulfonic acids were treated with supported alkyl triazenes (entry 17).21 The acids decompose the triazenes to diazoalkanes, which subsequently alkylate the sulfonates in situ. These supported triazenes avoid the dangerous handling of pure diazoalkanes. 

A solution of trifluoroacetic acid in toluene was found to be advantageous for cydization of pyruvate hydrazoncs having nitro substituents[4]. p-Toluene-sulfonic acid or Amberlyst-15 in toluene has also been found to give excellent results in preparation of indole-2-carboxylale esters from pyruvate hydra-zoiies[5,6J. Acidic zeolite catalysts have been used with xylene as a solvent to convert phenylhydraziiies and ketones to indoles both in one-flask procedures and in a flow-through reactor[7]. 

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. 

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. 

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). 

Other Applications. Hydroxylamine-O-sulfonic acid [2950-43-8] h.2is many applications in the area of organic synthesis. The use of this material for organic transformations has been thoroughly reviewed (125,126). The preparation of the acid involves the reaction of hydroxjlamine [5470-11-1] with oleum in the presence of ammonium sulfate [7783-20-2] (127). The acid has found appHcation in the preparation of hydra2ines from amines, aUphatic amines from activated methylene compounds, aromatic amines from activated aromatic compounds, amides from esters, and oximes. It is also an important reagent in reductive deamination and specialty nitrile production. 

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 ... 

The / -(methylmercapto)phenyl ester has been prepared from an /-protected amino acid and 4-tH3SC6H40H (DCC, CH2CI2, 0°, 1 h 20°, 12 h, 60-70% yield). The p-(methylmercapto)phenyl ester serves as an unactivated ester that is activated on oxidation to the sulfone (H2O2, AcOH, 20°, 12 h, 60-80% yield) which then serves as an activated ester in peptide synthesis. ... 

Ester sulfonates will become more and more interesting in the future because the raw materials for their preparation are fatty acid esters which can be prepared from oils and fats, and thus from renewable resources. They can be used as possible substitutes for surfactants based on petrochemicals. 

Most of the technically produced a-sulfo fatty esters are prepared from unbranched saturated fatty acid esters that are derived from 8 22 carboxylic acids and Cj-C3 alcohols. In particular the C12 (lauric), C14 (myristic), C16 (palmitic), and C18 (stearic) acids are interesting because the ester sulfonates... 

In the literature a number of different techniques for the preparation of a-sulfo fatty acid esters can be found. There is equipment for small-scale and commercial scale sulfonation. Stirton et al. added liquid sulfur trioxide dropwise to the fatty acids dispersed or dissolved in chloroform, carbon tetrachloride, or tetrachoroethylene [44]. The molar ratio of S03/fatty acid was 1.5-1.7 and the reaction temperature was increased to 65 °C in the Final stage of sulfonation. The yield was 75-85% of the dark colored a-sulfonated acid. The esterification of the acid was carried out with either the a-sulfonic acid alone, in which case the free sulfonic acid served as its own catalyst, or with the monosodium salt and a mineral catalyst. 

Salts of a-sulfo fatty acid esters can work as emulsifying agents for the preparation of asphalt emulsions and asphalt-latex emulsions. The ester sulfonates improve the storage stability of the emulsions [101,102]. In the manufacture of lightweight gypsum products air bubbles have to be mixed into the slurries. The use of salts of sulfonated C10 l8 fatty acid alkyl esters as foaming agents produces uniformly distributed fine bubbles [103]. Salts of C10 16 fatty acid alkyl ester sulfonates can also be added to cement mixtures to prevent slump loss of the mixtures [104]. 

Surfactants are prepared which contain carboxylic acid ester or amide chains and terminal acid groups selected from phosphoric acid, carboxymethyl, sulfuric acid, sulfonic acid, and phosphonic acid. These surfactants can be obtained by reaction of phosphoric acid or phosphorus pentoxide with polyhydroxystearic acid or polycaprolactone at 180-190°C under an inert gas. They are useful as polymerization catalysts and as dispersing agents for fuel, diesel, and paraffin oils [69]. 

Sulfonic esters are most frequently prepared by treatment of the corresponding halides with alcohols in the presence of a base. The method is much used for the conversion of alcohols to tosylates, brosylates, and similar sulfonic esters. Both R and R may be alkyl or aryl. The base is often pyridine, which functions as a nucleophilic catalyst, as in the similar alcoholysis of carboxylic acyl halides (10-21). Primary alcohols react the most rapidly, and it is often possible to sulfonate selectively a primary OH group in a molecule that also contains secondary or tertiary OH groups. The reaction with sulfonamides has been much less frequently used and is limited to N,N-disubstituted sulfonamides that is, R" may not be hydrogen. However, within these limits it is a useful reaction. The nucleophile in this case is actually R 0 . However, R" may be hydrogen (as well as alkyl) if the nucleophile is a phenol, so that the product is RS020Ar. Acidic catalysts are used in this case. Sulfonic acids have been converted directly to sulfonates by treatment with triethyl or trimethyl orthoformate HC(OR)3, without catalyst or solvent and with a trialkyl phosphite P(OR)3. ... 

Imidazolides of aromatic sulfonic acids react much more slowly in alcoholysis reactions than the carboxylic acid imidazolides. Although the reaction with phenols is quantitative when a melt is heated to 100 °C for several hours, with alcohols under these conditions only very slight alcoholysis is observed. In the presence of 0.05 equivalents (catalytic amount) of sodium ethoxide, imidazole sodium, of NaNH2, however, imidazolides of sulfonic acids react with alcohols almost quantitatively and exothermically at room temperature in a very short time to form sulfonic acid esters (sulfonates). (If the ratio of sulfonic acid imidazolide to alcoholate is 1 2, ethers are formed see Chapter 17). The mechanism of catalysis by base corresponds to that operative in the synthesis of carboxylic esters by the imidazolide method. Because of the more pronounced nucleophilic character of alkoxide ions, sulfonates can also be prepared in good yield by alcoholysis of their imidazolides in the presence of hydroxide ions i.e., with alcoholic sodium hydroxide. 45 Examples of syntheses of sulfonates are presented below. 

In recent years, a variety of aryl boronic acids are commercially available, albeit in some cases they may be expensive for large scale purposes. During our work in the mid-1990 s boronic acid (II) was not commercially available and so two different protocols were used to prepare this acid. The first approach involved the transmetallation with n-butyl lithium of aryl bromide (I) and trapping the lithio species generated with trialkyl borate followed by an acid quench. Aryl bromide (I) is easily prepared by reaction of o-bromobenzenesulfonyl chloride with 2-propanol in the presence of pyridine as a base. The second approach was a directed metallation of isopropyl ester of benzene sulfonic acid (VII), to generate the same lithio species and reaction with trialkyl borate. The sulfonyl ester is prepared by reaction of 2-propanol with benzenesulfonyl chloride. From a long-term strategy the latter approach is... 

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