Solvents, acidic function

Certain expressions describing a solvent acidity function, where S is a base that is protonated by an aqueous mineral acid solution. The equations describe a linear free-energy relationship between log([SH+]/[S]) + Ho and Ho + log[H ], where Ho is Hammett s acidity function and where Ho + log[H+] represents the activity function log(7s7H+/ysH ) for the nitroaniline reference bases to build Ho. Thus, log([SH+]/[S]) log[H+] = ( 1)... 

SOLVENT-ACCESSIBLE SURFACE AREA Solvent acidity function,... 

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. 

Once a metal surface has been conditioned by one of the above methods, a coupling agent composed of a bifimctional acid—methacrylate similar to a dentin adhesive is appHed. This coupling material is usually suppHed as a solvent solution that is painted over the conditioned metal surface. The acidic functional group of the coupling molecule interacts with the metal oxide surface while the methacrylate functional group of the molecule copolymerizes with the resin cement or restorative material placed over it (266,267). 

We consider first the Sn2 type of process. (In some important Sn2 reactions the solvent may function as the nucleophile. We will treat solvent nucleophilicity as a separate topic in Chapter 8.) Basicity toward the proton, that is, the pKa of the conjugate acid of the nucleophile, has been found to be less successful as a model property for reactions at saturated carbon than for nucleophilic acyl transfers, although basicity must have some relationship to nucleophilicity. Bordwell et al. have demonstrated very satisfactory Brjinsted-type plots for nucleophilic displacements at saturated carbon when the basicities and reactivities are measured in polar aprotic solvents like dimethylsulfoxide. The problem of establishing such simple correlations in hydroxylic solvents lies in the varying solvation stabilization within a reaction series in H-bond donor solvents. 

Acid catalysis is an important kinetic phenomenon, and its study often requires the use of concentrated acid solutions, in which the conventional pH scale is not applicable. In sueh solutions (e.g., sulfuric acid-water mixtures covering the full range of compositions) the acid component simultaneously functions both as an acid and as a solvent thus, a medium effect is superimposed on the acidity effect. In this section we briefly describe the acidity function approach to coping with this problem. (A comparable approach can be taken to the study of highly... 

Ho, the acidity function introduced by Hammett, is a measure of the ability of the solvent to transfer a proton to a base of neutral charge. In dilute aqueous solution ho becomes equal to t d Hq is equal to pH, but in strongly acid solutions Hq will differ from both pH and — log ch+. The determination of Ho is accomplished with the aid of Eq. (8-89) and a series of neutral indicator bases (the nitroanilines in Table 8-18) whose pA bh+ values have been measured by the overlap method. Table 8-19 lists Ho values for some aqueous solutions of common mineral acids. Analogous acidity functions have been defined for bases of other structural and charge types, such as // for amides and Hf for bases that ionize with the production of a carbocation ... 

A useful diagnostic tool for investigating possible hydration of cations of bases for which pA is greater than about one is the measurement of their ultraviolet spectra in aqueous acid solutions and also in an anhydrous acidic solvent such as dichloroacetic acid (for which the Hammett acidity function, Hq, is — 0.9, and in which hydration of the cation cannot occur). This technique has been used with quinazoline to obtain spectra approximating those of the hydrated and anhydrous cations, respectively. For weaker bases, spectral measurements in sulfuric acid-water mixtures of increasing acid content may be used to reveal a progressive conversion of hydrated into anhydrous species as the thermodynamic activity of the water decreases. 

The UV absorption spectra of sodium nitrite in aqueous solutions of sulfuric and perchloric acids were recorded by Seel and Winkler (1960) and by Bayliss et al. (1963). The absorption band at 250 nm is due either to the nitrosoacidium ion or to the nitrosyl ion. From the absorbancy of this band the equilibrium concentrations of HNO2 and NO or H20 —NO were calculated over the acid concentration ranges 0-100% H2S04 (by weight) and 0-72% HC104 (by weight). For both solvent systems the concentrations determined for the two (or three) equilibrium species correlate with the acidity function HR. This acidity function is defined for protonation-dehydration processes, and it is usually measured using triarylcarbinol indicators in the equilibrium shown in Scheme 3-15 (see Deno et al., 1955 Cox and Yates, 1983). 

In 1988 Masoud and Ishak demonstrated that ( -arenediazo methyl ethers do not react with 2-naphthol in dry organic solvents such as dioxan, ethanol, 2-propanol, but only in the presence of water. The reactions are catalyzed by hydrochloric acid (even in the absence of water). Under such conditions almost quantitative yields of azo compounds were obtained. A careful and extensive kinetic investigation of the HCl-catalyzed dediazoniation of substituted benzenediazo methyl ethers, varying the HC1 concentration and the diazo ether/2-naphthol ratio (the latter either absent or in large excess), and comparing the observed rate constants with Hammett s acidity functions for dioxane and ethanol (see Rochester, 1970) indicated the mechanism shown in Schemes 12-8 to 12-10 (DE = diazo methyl ether, D+ = diazonium ion). 

In this, as in many catalysed reactions, the protonated substrate is postulated as an intermediate, and although the proposed reaction scheme in fact accords with all the known experimental facts it perhaps would be instructive to determine the dependence of the rate coefficient on the Hammett acidity function at high acid concentration and also to investigate the solvent isotope effect kD2JkH20. Both these criteria have been used successfully (see Sections 2.2-2.4) to confirm the intermediacy of the protonated substrate in other acid-catalysed aromatic rearrangements. 

The kinetic data based on the demonstration of specific acid catalysis in buffers, solvent isotope effects and acidity functions all support mechanisms where the proton-transfers are fast. It is possible to write equations which accommodate these facts together with the first-order dependence on hydrazo-compound and the concurrent first and second-order dependence on acidity. These are... 

Another catalytic system which has been successfully applied to the autoxidation of substituted toluenes involves the combination of Co/Br" with a quaternary ammonium salt as a phase transfer catalyst (ref. 20). For example, cobalt(II) chloride in combination with certain tetraalkylammonium bromides or tetraalkylphosphonium bromides afforded benzoic acid in 92 % yield from toluene at 135-160 °C and 15 bar (Fig. 19). It should be noted that this system does not require the use of acetic acid as solvent. The function of the phase transfer catalyst is presumably to solubilize the cobalt in the ArCH3 solvent via the formation of Q + [CoBr]. ... 

When a solute is added to an acidic solvent it may become protonated by the solvent. If the solvent is water and the concentration of solute is not very great, then the pH of the solution is a good measure of the proton-donating ability of the solvent. Unfortunately, this is no longer true in concentrated solutions because activity coefficients are no longer unity. A measurement of solvent acidity is needed that works in concentrated solutions and applies to mixed solvents as well. The Hammett acidity function is a measurement that is used for acidic solvents of high dielectric constant. For any solvent, including mixtures of solvents (but the proportions of the mixture must be specified), a value Hq is defined as... 

Although most acidity functions have been applied only to acidic solutions, some work has also been done with strongly basic solutions. The H function, which is used for highly acidic solutions when the base has a charge of — 1, can also be used for strongly basic solvents, in which case it measures the ability of these solvents to abstract a proton from a neutral acid BH. When a solvent becomes protonated, its conjugate acid is known as a lyonium ion. 

Nonaqueous Systems In nonaqueous (nonpolar) solvent systems, nitrosatlon also proceeds. In these solvents, alpha-tocopherol acts as a lipid soluble blocking agent in much the same fashion as ascorbic acid functions in the aqueous phase. Alpha-tocopherol reacts with a nitrosating agent and reduces it to nitric oxide. At the same time, alpha-tocopherol is oxidized to tocoquinone, which is the first oxidation product of vitamin E and also a normal metabolite in vivo. 

However, when considering the use of acid or base in organic solvents for sample extraction, care must be taken to avoid potential artifacts that may arise from side reactions. For example, methylation of active hydroxyl groups or acidic functions on the analyte may sometimes occur when acidic methanol is used as the extractant. Another example is acetylation of an active alcohol on the analyte following partition of the analyte into ethyl acetate from aqueous solution acidified with glacial acetic acid. 

Ribonucleotide reductase differs from the other 5 -deoxyadenosyl-cobalamin requiring enzymes in a number of respects. Hydrogen is transferred from coenzyme to the C2-position of the ribose moiety without inversion of configuration. Also since lipoic acid functions in hydrogen transfer, exchange with solvent protons takes place. Furthermore, exchange between free and bound 5 -deoxyadenosylcobalamin occurs rapidly during catalysis. Evidence for a Co(I)-corrin as an intermediate for this reduction is presented in our section on electron spin resonance. 

Acid-base reactions also include those in which the solvent itself functions as an acid or base. This can be shown as follows. Sodium hydride reacts with water to produce a basic solution,... 

There are two general classes of naturally-occurring antibiotics which influence the transport of alkali metal cations through natural and artificial membranes. The first category contains neutral macrocyclic species which usually bind potassium selectively over sodium. The second (non-cyclic) group contains monobasic acid functions which help render the alkaline metal complexes insoluble in water but soluble in non-polar solvents (Lauger, 1972 Painter Pressman, 1982). The present discussion will be restricted to (cyclic) examples from the first class. 

In a related study this group also demonstrated the use of non-volatile solvents in CEC-MS without compromising the quality of spectra that has also been demonstrated using polymer-based monolithic column prepared by in situ copolymerization of butyl methacrylate with sulfonic acid functionalities. 

The photoactive compounds, or sensitizers, that are used in the formulation of positive photoresists, are substituted diazonaphthoquinones shown in Figure 17. The substituent, shown as R in Figure 17, is generally an aryl sulfonate. The nature of the substituent influences the solubility characteristics of the sensitizer molecule and also influences the absorption characteristics of the chromophor (79). The diazonaphthoquinone sulfonates are soluble in common organic solvents but are insoluble in aqueous base. Upon exposure to light, these substances undergo a series of reactions that culminate in the formation of an indene carboxylic acid as depicted in Figure 17. The photoproduct, unlike its precursor, is extremely soluble in aqueous base by virtue of the carboxylic acid functionality. 

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