Sulfonic acids cleavage

Attempts to prepare the diprOpylamino-5-sulfonic acid by sulfonation in oleum failed (385). With 2-piperidino-4-methylthiazole Ochiai reports cleavage of the 2-piperidino ring (391). 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

Because of the electron-withdrawing sulfonic acid substituent, cleavage occurs under milder conditions than needed for the Fmoc group (0.1 N NH4OH 1% Na2C03, 45 min). ... 

In contrast to phosphorus esters, sulfur esters are usually cleaved at the carbon-oxygen bond with carbon-fluorine bond formation Cleavage of esteri nf methanesulfonic acid, p-toluenesidfonic acid, and especially trifluoromethane-sulfonic acid (tnflic acid) by fluoride ion is the most widely used method for the conversion of hydroxy compounds to fluoro derivatives Potassium fluoride, triethylamine trihydrofluoride, and tetrabutylammonium fluoride are common sources of the fluoride ion For the cleavage of a variety of alkyl mesylates and tosylates with potassium fluoride, polyethylene glycol 400 is a solvent of choice, the yields are limited by solvolysis of the leaving group by the solvent, but this phenomenon is controlled by bulky substituents, either in the sulfonic acid part or in the alcohol part of the ester [42] (equation 29)... 

Compounds i, ii, and iii can be prepared by an acid-catalyzed reaction of a diol and the cycloalkanone in the presence of ethyl orthoformate and mesitylene-sulfonic acid. The relative ease of acid-catalyzed hydrolysis [0.53 M H2SO4, H2O, PrOH (65 35), 20°] for compounds i, iii, acetonide, and ii is C5 C7 > acetonide C (e.g., t.//s for 1,2-O-alkylidene-a-D-glucopyranoses of C5, C7, acetonide, and C derivatives are 8, 10, 20, and 124 h, respectively). The efficiency of cleavage seems to be dependent upon the electronic environment about the ketal. ... 

It was not until 1940 that the sulfonation of alkylisoxazoles by heating them with chlorosulfonic acid was reported. This gave a mixture of isoxazole-4-sulfonic acids (58) and their acid chlorides (59). The position of the sulfonic group in derivatives of monomethyl isoxazoles has been proved by nucleophilic cleavage of the isoxazole ring (60 61). Recently it proved possible to sulfonate isoxazole... 

In these compounds the following substituents can be present alkyl,alkenyl,aryl, halogen,sulfonic acid, amino, hydroxyalkyl, acyl, and carboxyl. The cleavages of 5,5 - (109) and 3,5 -diisoxazolyl (111) proceed similarly both isoxazole rings are cleaved in the former (109—> 110). ... 

Sulfonyl chlorides as well as esters and amides of sulfonic acids can be hydrolyzed to the corresponding acids. Sulfonyl chlorides can by hydrolyzed with water or with an alcohol in the absence of acid or base. Basic catalysis is also used, though of course the salt is the product obtained. Esters are readily hydrolyzed, many with water or dilute alkali. This is the same reaction as 10-4, and usually involves R —0 cleavage, except when R is aryl. However, in some cases retention of configuration... 

Cleavage of phenolic ethers with sulfonic acids... 

Sulfate monoesters can react by dissociative paths, and this is the favored path. Whether such reactions are concerted or involve a very short-lived sulfur trioxide intermediate has been the subject of debate. ° Benkovic and Benkovic reported evidence suggesting that the nucleophile is present (though there is little bond formation) in the transition state for the reaction of amines with p-nitrophenyl sulfate. Alkyl esters of sulfuric or sulfonic acids normally react with C-0 cleavage only when this is disfavored, as in aryl esters, does one see S-0 cleavage. Sulfate diester... 

Proteases are enzymes that break peptide bonds in proteins. As such they lend themselves to a variety of homogeneous assay techniques. Most employ labeling both ends of the substrate with a different tag, and looking for the appearance (disappearance) of the signal generated in the intact substrate (product). As an example, for a fluorescence quench assay, the N-terminal of a peptide is labeled with DNP and the C-terminal with MCA. As such, the peptide is fluorescently silent since the fluorescence from DNP is quenched by absorption by the MCA. Another very popular donor/acceptor pair is EDANS 5-[(2-aminoethyl)amino] naphthalene-1-sulfonic acid and DABCYL 4-(4-dimethylaminophenylazo)benzoic acid) (a sulfonyl derivative (DABSYL) [27], Upon peptide cleavage, the two products diffuse, and due to a lack of proximity, the fluorescence increases. 

To reach the reductive step of the azo bond cleavage, due to the reaction between reduced electron carriers (flavins or hydroquinones) and azo dyes, either the reduced electron carrier or the azo compound should pass the cell plasma membrane barrier. Highly polar azo dyes, such as sulfonated compounds, cannot pass the plasma membrane barrier, as sulfonic acid substitution of the azo dye structure apparently blocks effective dye permeation [28], The removal of the block to the dye permeation by treatment with toluene of Bacillus cereus cells induced a significant increase of the uptake of sulfonated azo dyes and of their reduction rate [29]. Moreover, cell extracts usually show to be more active in anaerobic reduction of azo dyes than whole cells. Therefore, intracellular reductases activities are not the best way to reach sulfonated azo dyes reduction the biological systems in which the transport of redox mediators or of azo dye through the plasma membrane is not required are preferable to achieve their degradation [13]. 

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. 

Antibacterial sulfonamides contain two N-atoms, the sulfonamido (N1) and the para primary amino (N4). The sulfonamido group, in contrast to a carboxamido group, is chemically and metabolically stable. In other words, hydrolytic cleavage of sulfonamides to produce a sulfonic acid and an amine has never been observed. We, therefore, focus our discussion on the primary amino group, acetylation of which is one of the major metabolic pathways for some sulfonamides. Hydrolysis of the N4-acety luted metabolites back to the parent sulfonamide can occur in the liver, kidney, and intestinal tract. The reaction is strongly influenced by the structure of the parent amine e.g., N4-acetylsulfisoxazole (4.121) was deacetylated by intestinal bacteria whereas /V4-acctyIsulI anilamide (4.122) under identical conditions was not [78][79],... 

Another concern for polystyrene- and some aromatic-based PEMs is hydrolysis of fhe sulfonic acid group from aromatic rings as well as hydrolytic cleavage of polymer backbone under fuel cell conditions for aromafic polymers including polyimides, poly(arylene ethers), poly(ether ketones), and poly(ether sulfones). It is well known that the sulfonation of aromafic rings is a reversible process especially at low pH and at elevated temperature (Scheme 3.3). The reversibility of sulfonation, for example, is used in fhe preparafion of trinitrotoluene or picric acid. Por the simplest membrane of the class of arylsulfonic acids (i.e., benzenesulfonic acid), fhe reacfion occurs upon freatment with a stream of superheated steam at 180°C.i ... 

The development of sulfone linkers, the exploration of sulfone based chemical transformations and cleavage strategies are an important objective in soHd-phase organic synthesis. This kind of Hnker (Tab. 3.7) has been used with thioethers [108], sulfoxides [109], sulfones [110], sulfonic acids and their corresponding derivatives [111]. Because carbon-sulfur bonds can be cleaved under very mild conditions, some Hnkers have been based on this effect. They can be cleaved under reductive conditions ]112, 113], photolytic conditions [114, 115] or with strong bases [116]. Various safety catch Hnkers have been developed based on the fact that thiols can be oxidized to sulfoxides and sulfones [112, 113]. 

Polymer supported persulfonic acids can be prepared by treating polymer-bound sulfonic acids with H2O2 or K2S20g. The resulting resin was found to display an activity of 2.5 mole equivalents per gram of wet resin. This persulfonated resin was successively applied for the oxidation of carboxylic acids, ketones, olefins and for the cleavage of disulfide linkage and of A-formylamino acids. 

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