Acids, carboxylic sulphonic

Dilute sodium hydroxide solution. Carboxylic acids (RCOOH), sulphonic acids (RSO3H), phenols (ArOH), thiophenols (ArSH), mer-captans (RSH), imides (RCONHCOR), aryl sulphonamides (AxSOjNHj), arylsulphonyl derivatives of primary amines (AxSOjNHR), oximes (RCH=NOH), primary and secondary nitro compounds (RCH=NOOH and RjC=NOOH-oci forms), and some enols (e.g., of 1 3-diketones... 

Supplement 1950 1505-1591a acid, 269. Hydroxy-carbonyl sulphonic acids Camphor-sulphonio acid, 345. Carboxylic-sulphonic acids, 368. Se and Te acids, 422. 

Examples of liquid cation exchangers are alkyl and dialkyl phosphoric acids, alkyl sulphonic acids and carboxylic acids, although only two appear to have been used to any extent, viz. di-(2-ethylhexyl)phosphoric(V) acid and dinonylnaphthalene sulphonic acid. 

C,H,CH,—S—C—NH J The compound separates in either, sometimes as both, of two dimorphic forms, m.p. 150° and 175° respectively. The former may be converted into the higher m.p. form by dissolving it in alcohol and seeding with crystals of the form, m.p. 175° the low m.p. form when warmed to 175 gives, after solidification, a m.p. of 175 . Both dimorphic forms give identical derivatives with carboxylic acids and sulphonic ids (see Sections 111,85 and IV,33). 

RCH(OH)=CHCOR or p-keto esters RCH(OH)=CHCOOR ) dissolve in dilute sodium hydroxide solution, i.e., contain an acidic group of sufficient strength to react with the alkah. Carboxylic acids and sulphonic acids are soluble in dilute solutions of sodium bicarbonate some negatively-substituted phenols, for example, picric acid, 2 4 6-tribromo-phenol and 2 4-dinitrophenol, are strongly acidic and also dissolve in dilute sodium bicarbonate solution. 

HydrOxy-carboxylic acids, 190 In-doxylic acid, 226. Carbonyl-carboxylic acids, 284. Sulphonic acids, 386 Quinoline sul-phonic acid, 390. Amines, 419 2-Aminopyridine, 428. Amino-carboxylic acids, 541 Tryptophane, 545. Hydrazines, 563. Azo compounds, 572. Diazo compounds, 590. 

Further, by using Et3N.3HF in acetonitrile as solvent, they have demonstrated that electrolysis of benzyl nitriles, carboxylic acid esters, sulphonic acid esters and ketones give the corresponding monofluoro- or difluoro-compounds, depending on anode potential in yields of 30 - 70 %. 

Polymeric phosphonium salt-bound carboxylate, benzenesulphinate and phenoxide anions have been used in nucleophilic substitution reactions for the synthesis of carboxylic acid esters, sulphones and C/O alkylation of phenols from alkyl halides. The polymeric reagent seems to increase the nucleophilicity of the anions376 and the yields are higher than those for corresponding polymer phase-transfer catalysis (reaction 273). 

The pentachloride, trichloride and tribromide of phosphorus are also used for replacing hydroxyl by halogen in phenols, carboxylic acids and sulphonic acids. The use of phosphorus trichloride is to be preferred in the preparation of many acid chlorides, since three molecules of acid chloride are then formed per molecule of phosphorus halide, as against one molecule of acid chloride when the pentachloride is used ... 

Figure 7.7 Zeta potentials (calculated from electrophoretic mobility data) relating to particles of different ionogenic character plotted as a function of pH in acetate-veronal buffer at constant ionic strength of 0.05 mol dm 3, (a) Hydrocarbon oil droplets, (b) Sulphonated polystyrene latex particles, (c) Arabic acid (carboxylated polymer) adsorbed on to oil droplets, (d) Serum albumin adsorbed on to oil droplets...

Stable esters coming formally from alkynols and carboxylic, sulphonic or dialkyl phosphoric acids were prepared for the first time via alkynyliodonium salts with the corresponding anion. Several alkynyl carboxylates were obtained by anion exchange of alkynyl iodonium tosylates the initially formed salts, PhI+C=CR RCO2, were converted spontaneously into the esters on elution through a chromatographic column packed with an anion-exchange resin (Pol+ArCOj) ... 

Various types of surface-anchor interactions are responsible for the adsorption of a dispersant to the particle surface. These include ionic or acid/base interactions sulphonic acid, carboxylic acid or phosphate with a basic surface (e.g., alumina) amine or quaternary with an acidic surface (e.g., silica) H-bonding surface esters, ketones, ethers, hydroxyls multiple anchors-polyamines and polyols (H-bond donor or acceptor) or polyethers (H-bond acceptor). Polarizing groups (e.g., polyurethanes) can also provide sufficient adsorption energies and, in nonspecific cases, lyophobic bonding (via van der Waals attractions) driven by insolubility (e.g., PMMA). It is also possible to use chemical bonding, for example by reactive silanes. 

In fact, if we invoke this sulphonic acid/carboxylic acid analogy for heats of sublimation, the following equality looks plausible ... 

D. What Can We Now Say About Sulphonic Acid/Carboxylic Acid/Sulphinic Acid Analogies ... 

It is seen that a small degree of stabilization for gas-phase acyl species is the norm, i.e. Sl7 < 0, while destabilization was generally seen for condensed-phase sulphonyl species. Would stabilization also be seen for sulphonyl derivatives were gas-phase species considered What does our analysis say about the sulphonic acid/carboxylic acid analogies in Section VIII.A ... 

What does our analysis say about the sulphonic acid/carboxylic acid/sulphinic acid analogies enunciated in the beginning of this chapter What does our analysis tell us about the interplay of structure and energetics in the chemistry of sulphonic acids and their derivatives These questions remain unanswered. 

A new, strongly acidic product, quinaldyl(carboxyl-14C)glycyltaurine (198), a sulphonic acid urinary metabolite, has been discovered163 and its chemical structure established by subcutaneous injections and oral administrations of quinaldic acid-carboxyl-14C to hungry cats. Hydrolysis of 198 demonstrated the presence of glycine, taurine, quinaldic acid and quinaldylglycine in the hydrolysate. 

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