Sulfonic acids acid derivatives, Table

Sulfosahcyhc acid is prepared by heating 10 parts of sahcyhc acid with 50 parts of concentrated sulfuric acid, by chlorosulfonation of sahcyhc acid and subsequent hydrolysis of the acid chloride, or by sulfonation with hquid sulfur trioxide in tetrachloroethylene. It is used as an intermediate in the production of dyestuffs, grease additives, catalysts, and surfactants. It is also useful as a colorimetric reagent for ferric iron and as a reagent for albumin. Table 9 shows the physical properties of sahcyhc acid derivatives. 

In 1991, over 1 x 10 t sulfonic acids were produced in the United States (24). The materials, for the most part, were used as intermediates for the manufacture of sulfonates in the detergent market, dye manufacture, dispersing agents, catalysts, polymers, etc. Production of dodecjlbenzenesulfonic acids derivatives dominated the sulfonic acid market (Table 2). These had a 38% overall share. The differences between the production tons and the tons sold is accounted for by in-plant use by various manufacturers verses merchant market production. 

As already reported in Table 6, the solubility of phosphazene polymers is strongly influenced by the nature of the substituent groups attached at the phosphorus atoms along the -P=N- skeleton. Water-solubility, for instance, can be induced in polyphosphazenes by using strongly polar substituents (e.g. methylamine [84], glucosyl [495], glyceryl [496], polyoxyethylene mono-methylether [273] or sulfonic acid [497,498] derivatives), or may be promoted by acids or bases when basic (amino substituents like ethylamine [499]) or acid (e.g. aryloxy carboxylate [499] or aryloxy hydroxylate [295]) substituents are exploited. 

The balance of the compounds in Table VIII support the earlier statement that any compound containing fluorine is toxic to moths. These fluorinated hydrocarbons, phenols, acids, sulfonic acids, and sulfones probably act against moths as stomach poisons. The fluorosulfonic acid derivatives and the sulfone with a fluorinated substituent were key compounds whose toxicity to moths laid the groundwork for the deductions which led to the synthesis and testing of DDT as an insecticide. 

Table 7.4 Comparisons of carboxylic and sulfonic acid derivatives...

Compounds that are even better analogues of carboxylic acids are produced when an alkyl or aryl group replaces one of the hydroxyls in sulfuric acid. This provides compounds called sulfonic acids, which in turn give rise to a range of derivatives exactly comparable to those we have met as carboxylic acid derivatives (Table 7.4). 

Types of compounds are arranged according to the following system hydrocarbons and basic heterocycles hydroxy compounds and their ethers mercapto compounds, sulfides, disulfides, sulfoxides and sulfones, sulfenic, sulfinic and sulfonic acids and their derivatives amines, hydroxylamines, hydrazines, hydrazo and azo compounds carbonyl compounds and their functional derivatives carboxylic acids and their functional derivatives and organometallics. In each chapter, halogen, nitroso, nitro, diazo and azido compounds follow the parent compounds as their substitution derivatives. More detail is indicated in the table of contents. In polyfunctional derivatives reduction of a particular function is mentioned in the place of the highest functionality. Reduction of acrylic acid, for example, is described in the chapter on acids rather than functionalized ethylene, and reduction of ethyl acetoacetate is discussed in the chapter on esters rather than in the chapter on ketones. 

For the analytical characterization of sulfated tyrosine peptides, spectroscopic methods as well as amino acid analysis and, more recently, mass spectrometry are employed. In Table 2 the spectroscopic data of tyrosine 0-sulfate are compared to those of the related sulfonic acid derivatives as possible byproducts in the chemical sulfation of the tyrosine or tyrosine peptides.[361 In the course of the synthesis of tyrosine 0-sulfate peptides and, particularly in the final deprotection step, desulfation may occur which limits the characterization of the final compounds in terms of quantitative identification of the tyrosine 0-sulfate. This is achieved by amino acid analyses of basic hydrolysates of the sulfated tyrosine peptides or preferably by analyses of the enzymatic hydrolysates with aminopeptidase M or leucine-aminopeptidase. 

Sulfonic acids, R(Ar)S03H, form derivatives similar to those of carboxylic acids (see Table 16-3). These are sulfonyl chlorides, sulfonates (esters), and sulfonamides. The transsulfonylation reactions are similar to the transacylation reactions, except that the ester and amide cannot be made directly from the acid. See Problem 13.17 for preparation of sulfonyl chlorides and esters and Problem 13.18 for use of sulfonate esters as substrates in S l and S,42 reactions. 

CARBOXYLIC ACIDS AND THEIR DERIVATIVES Table 16-3. Comparison of Sulfonic and Carboxylic Acid Chemistry... 

TABLE 1. Physical Properties of Selected Polyhydroxyalkanoate Derivatives Containing Amide or Sulfonic Acid Components Prepared According to the Current Invention... 

The esterification of support-bound carboxylic acids has not been investigated as thoroughly as the esterification of support-bound alcohols. Resin-bound activated acid derivatives that are well suited to the preparation of esters include O-acylisoureas (formed from acids and carbodiimides), acyl halides [23,226-228], and mixed anhydrides (Table 13.15). A-Acylurea formation does not compete with esterifications as efficiently as it does with the formation of amides from support-bound acids. Esters can also be prepared from carboxylic acids on insoluble supports by acid-catalyzed esterification [152,229]. Alternatively, support-bound carboxylic acids can be esteri-fied by O-alkylation, either with primary or secondary aliphatic alcohols under Mitsu-nobu conditions or with reactive alkyl halides or sulfonates (Table 13.15). 

The physical properties of sulfonic acids vary greatly depending on the nature of the R-group. Sulfonic acids can be described as having similar acidity characteristics to sulfuric acid. Sulfonic acids are prone to thermal decomposition, i.e., desulfbnation, at elevated temperatures. However, several of the alkane-derived sulfonic acids show excellent thermal stability, as shown in Table 1. Arene-based sulfonic acids are thermally unstable. 

Trinitrobenzene sulfonic acid (TNBS) is known to react with protein lysine residues, forming colored trinitrophenylated (TNP) derivatives with absorption maxima at 345 mp, (46). When E. coli pyrophosphatase was incubated with a 400-fold molar excess of the reagent, there was progressive decay of enzymic activity accompanied by increasing absorbance of the solution at 345 mp. (Fig. 5). Half the enzymic activity had disappeared by the time 16% of the protein lysines had been modified eventually (6 hr) all 98 enzyme lysines reacted (Table III and Fig. 5). Isolation and hydrolysis of the product showed total conversion of all lysine to e-TNP-lysine without formation of any other... 

Table 7.4 Anilino sulfonic acid derivatives of bis(4,4 -triazinylamino)stilbene-2,2 -disulfonic acid...

Typical resolving agents are summarized in Table 4. Typical acidic resolving agents from natural products are malic acid, tartaric acid and its derivative, camphor sulfonic acids derived from camphor. 10-Camphor sulfonic acid is a strong acid and indicates high capability of making salts with weak bases. 

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