Carboxylic sulfonic anhydrides

These authors suggest that the reaction may proceed through the formation of their mixed anhydrides , and illustrate a metal ion templated, mixed carboxylic-sulfonic anhydride. 

Sulfur compounds have also been widely studied as activating agents for polyesterification reactions. p-Toluenesulfonyl chloride (tosyl chloride) reacts with DMF in pyridine to form a Vilsmeir adduct which easily reacts with carboxylic acids at 100-120° C, giving highly reactive mixed carboxylic-sulfonic anhydrides.312 The reaction is efficient both for aromatic dicarboxylic acid-bisphenol312 and hydroxybenzoic acid314 polyesterifications (Scheme 2.31). The formation of phenyl tosylates as significant side products of this reaction has been reported.315... 

Carboxylic-sulfonic anhydrides, 80 Cardiovascular surgery, 27 Cardo diamines, 277, 278 Carothers, Wallace, 198 Carothers equation, 11, 59 Carothers group, 1 Carpet waste... 

Proton acids can be used as catalysts when the reagent is a carboxylic acid. The mixed carboxylic sulfonic anhydrides RCOOSO2CF3 are extremely reactive acylating agents and can smoothly acylate benzene without a catalyst.265 With active substrates (e.g., aryl ethers, fused-ring systems, thiophenes), Friedel-Crafts acylation can be carried out with very small amounts of catalyst, often just a trace, or even sometimes with no catalyst at all. Ferric chloride, iodine, zinc chloride, and iron are the most common catalysts when the reactions is carried out in this manner.266... 

Other less commonly used coupling reagents include EEDQ (formation of mixed carboxylic carbonic anhydrides), Bop-Cl (formation of mixed carboxylic phosphinic anhydrides [52,53]), DPPA (formation of acyl azides), DECP (formation of acyl cyanides), MSNT (formation of mixed carboxylic sulfonic anhydrides), and benzisoxazo-lium salts (generation of phenyl esters [54]). 

The synthesis of (+)-N-methylmaysenine, a preliminary for the later synthesis of the antitumor agent maytansine, was accomplished by the joining of fragments A and B, chain extension and macrolactam closure using a mixed carboxylic-sulfonic acid anhydride. 

As shown, an asymmetric carboxylic-sulfonic acid anhydride is formed, but the cellulose attack occurs on the C = O group, since a nucleophilic attack on sulfur is slow, and the tosylate moiety is a much better leaving group than the carboxylate group [193]. Similar to other acylation reactions, there is a large preference for tosylation at the 5 position, and cellulose tosylates... 

It is possible to prepare esters of phenols with carboxylic acid anhydrides or acid halides, and phenyl ethers by reaction of benzenolate anion with halides, sulfate esters, sulfonates, or other alkyl derivatives that react well by the SN2 mechanism ... 

The first (3-thiolactone was prepared according to Scheme A by Knunyants and co-workers. A mixed anhydride of )3-mercaptocarboxylic acid and carbonic-acid ester is obtained by treatment of a salt of the mercapto acid with a chlorocarbonate ester.Cyclization to the 3-thiolactone occurs during the reaction this synthetic method is exemplified by the preparation of 302 from 301. A mixed carboxylic-sulfonic acid anhydride is involved in the formation of the thiolactone ring in 303. ... 

Orthoesters react with primary amines to give imino esters (238 equation 129). The condensation proceeds usually at temperatures above 100 C and can be catalyzed by mineral acids, sulfonic acids, Lewis acids and carboxylic acid anhydrides. 

In the preparation of mixed carboxylic-perfluoroalkane sulfonic anhydrides from the corresponding acids, water formahon is responsible for the low yields of the acylation product. By removing water from the reaction mixture by azeotropic distillation and adsorption onto molecular sieves, the yield of benzoylahon of para-xylene with BAC in the presence of perfluorobutanesulfonic acid (10% mol) is improved to 90%. 

Sulfonic anhydrides are prepared from acid chlorides, in principle, by the same methods as are used for the corresponding carboxylic anhydrides. Thus Billeter692 obtained alkanesulfonic anhydrides by the action of the sulfonyl chlorides on silver alkanesulfonates benzenesulfonic anhydride is best obtained by heating 2 moles of benzenesulfonyl chloride and 1 mole of anhydrous oxalic acid slowly to 200°.693... 

Sulfur in oxidation state IV can be used to produce a variety of anionic snUbnates, as depicted in Scheme 1.5. Sodium bisulfite can be used to prepare sulfonates of a,b-unsaturated acids and esters, such as those prepared from maleic anhydride. The mechanism involves Michael addition to the activated double bond by the more nucleophilic sulfur atom, and is conducted in an aqueous two-phase system where, for example, a maleate half acid ester or diester is dispersed and heated under narrowly controlled pH conditions to minimize ester hydrolysis and avoid competitive hydroxide addition to the double bond. The resulting classes of surfactants include sulfosuccinates (which are in fact carboxylate sulfonate disalt surfactants) prepared from the maleic half acid esters of fatty alcohols or alcohol ethoxylates. Diesters of maleic are sulfonated by the same type of process to produce surfactants such as the ubiquitous dioctyl sulfosuccinate (DOSS) from the diester of 2-ethylhexyl alcohol and maleic anhydride. 

Common comonomers are those that place carboxylic, sulfonate, phosphite, polyethylene glycol, or hydrophobic groups along the backbone. They include maleic anhydride (subsequently hydrolyzed), sodium 2-acrylamido tert-butylsulfonic acid (Na-ATBS), sodium styrene sulfonate, l-allyloxy-2-hydroxypropyl sulfonate, l-allyloxy-2-hydroxypropyl phosphite, vinyl phosphonic acid, vinyl acrylate, polyethoxy acrylate, ethyl acrylate, methyl vinyl ether, and hydroxyl propyl acrylate [2,47-50]. 

Reactions with a,a-dichloromethyl ether Carboxylic acid chlorides from carboxylic acid anhydrides, carboxylic acids, and alkali carboxylates Sulfonic acid chlorides... 

A useful mild method for sulfonation of aromatic polymers involves dissolving them in chlorosulfonic acid or oleum, adding an inert organic solvent, e.g. dichloromethane, followed by a carboxylic acid anhydride, e.g. acetic anhydride and allowing the sulfonation to proceed at a temperature of < 25 °C. 

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