Amphoteric catalysis

During the appropriate tests phthalic anhydride was smoothly esterified with 2-ethylhexanol in the mole ratio 1 4. The reaction temperature rose to 200°C. after about 15 minutes, then rose slowly up to 210°C. till the end of the esterification. Table I shows the esterification time in hours after 99.9% conversion, while continuously removing the reaction water, according to the acid number relative to monooctyl phthalic acid. Furthermore, it indicates the ester colors according to the iodine scale in milligrams iodine/100 ml., whereby 1 mg. iodine/100 ml. can be more or less compared with a dye number of 120 APHA. Since, the values are obtained with the same starting materials, it is possible to compare the color numbers. They show that with the same times, the amphoteric catalysis achieves better colors than in the reaction course containing catalytically effective acids. 

Furthermore, with amphoteric catalysis, no olefins or ethers are formed, which means that the dehydration of the ester alcohol is completely suppressed. This advantage becomes particularly important during the conversion of secondary alcohols, as during the formation process of di-cyclohexylphthalate. 

COENEN Amphoteric Catalysis Table II. Quality Values of Hiils Plasticizers Butyl- Dibutyl- Dihexyl- Hexyl- Dioctyl- Octyl- Dinonyl- 85 Dicy-clohexyl-... 

Phenols. Phenols are unreactive toward chloroformates at room temperature and at elevated temperatures the yields of carbonates are relatively poor (< 10%) in the absence of catalysis. Many catalysts have been claimed in the patent Hterature that lead to high yields of carbonates from phenol and chloroformates. The use of catalyst is even more essential in the reaction of phenols and aryl chloroformates. Among the catalysts claimed are amphoteric metals or thek haUdes (16), magnesium haUdes (17), magnesium or manganese (18), secondary or tertiary amines such as imidazole (19), pyridine, quinoline, picoline (20—22), heterocycHc basic compounds (23) and carbonamides, thiocarbonamides, phosphoroamides, and sulfonamides (24). 

Aluminas. Aluminas, porous AI2O3, are available in many forms. They constitute the most important carrier material in heterogeneous catalysis. Alumina is amphoteric and, as a con.sequence, soluble in both acidic and basic media. Precipitation can be performed from an acid solution by adding a base or from a basic solution by adding an acid, as schematically represented in Fig. 3.18. If, for example, at a pH of less than about 3 a base is added to an aqueous solution of aluminium sulphate, a precipitate is formed. If this material is filtered, dried and calcined, an amorphous porous AI2O3 is obtained. At other pH values different porous aluminas can be synthesized. 

The species Y is also probably non-existent in most of the enzyme catalysed reactions involving only one substrate. In acidic or basic reactions, Y and W do, however, play roles. In acid catalysed reactions, where C is an acid, transfer of proton to S takes place giving Y as a conjugate base of C. W is a basic or amphoteric substance which accepts a proton from X. In base catalysis, Y is a conjugate acid to the base C while W transfers a proton to X and may be the solvent or another acidic substance. With regard to the stability of the intermediate complex X, the two possibilities, which may be considered, are ... 

The principal iron oxides used in catalysis of industrial reactions are magnetite and hematite. Both are semiconductors and can catalyse oxidation/reduction reactions. Owing to their amphoteric properties, they can also be used as acid/base catalysts. The catalysts are used as finely divided powders or as porous solids with a high ratio of surface area to volume. Such catalysts must be durable with a life expectancy of some years. To achieve these requirements, the iron oxide is most frequently dis-... 

The effect of the basicity of aldol condensation catalysts on their activity was thoroughly investigated by Malinowski et al. [372—379]. The observed linear dependence of the rate coefficients of several condensation reactions on the amount of sodium hydroxide contained in silica gel (Figs. 12 and 13) supported the view that the basic properties of this type of catalyst were actually the cause of its catalytic activity, though the alkali-free catalyst was not completely inactive. The amphoteric nature of the catalysis by silica gel, which can act also as an acid catalyst, was demonstrated [380]. By a stepwise addition of sodium acetate to a HN03-pretreated silica gel catalyst the original activity for acetaldehyde self-condensation was decreased to a minimum (when an equivalent amount of the base was added) by further addition of sodium acetate, the activity increased again because of the transition to a base... 

By way of illustration we will look at the case of the hydrolysis of mecillinam (XII), which is an antimicrobially active amidopenicillamic acid. This amphoteric dmg can exist as a cation, which we can write as MHJ, as a zwitterion MH or as an anion M. Figure 4.10 shows the pH-rate profile at zero buffer concentration. The reason this plot is so much more complex than that of codeine sulfate is that each of the species present in solution can undergo specific acid-base catalysis to var 4ng extents and so each contributes to the overall profile shown in Fig. 4.10. 

As for the reduction of the ketones, the amphoteric catalysts featuring acidic-basic sites have been found to be very effective for the enantioselective catalysis of C-C bond formation. Thus, Soai et al. were the first to report the enantioselective addition of dialkylzincs to aldehydes using enantiomerically pure phosphin-amides and analogues as chiral catalysts in the presence of titanium tetraiso-propoxide. Numerous chiral organophosphorus compounds have been prepared and applied in a test reaction between benzaldehyde and diethylzinc [48, 49]. An important difference in terms of enantioselectivity was observed between the behavior of P=S (47-48) and P=0 (49) groups. Thus, the enan-... 

The series of 10 chapters that constitute Part 3 of the book deals mainly with the use of adsorption as a means of characterizing carbons. Thus, the first three chapters in this section complement each other in the use of gas-solid or liquid-solid adsorption to characterize the porous texture and/or the surface chemistry of carbons. Porous texture characterization based on gas adsorption is addressed in Chapter 11 in a very comprehensive manner and includes a description of a number of classical and advanced tools (e.g., density functional theory and Monte Carlo simulations) for the characterization of porosity in carbons. Chapter 12 illustrates the use of adsorption at the liquid-solid interface as a means to characterize both pore texture and surface chemistry. The authon propose these methods (calorimetry, adsorption from solution) to characterize carbons for use in such processes as liquid purification or liquid-solid heterogeneous catalysis, for example. Next, the surface chemical characterization of carbons is comprehensively treated in Chapter 13, which discusses topics such as hydrophilicity and functional groups in carbon as well as the amphoteric characteristics and electrokinetic phenomena on carbon surfaces. 

However, due to the amphoteric character of alumina, acid catalysis due to OH surface groups or to A1 atoms can take place in a bifunctional catalysis mechanism [Eq. (13)] [24]. 

Lowry and co workers141,222 studied the mutarotation of tetra-O-methyl-a-D-glucopyranose, and found that the rate of reaction is low in dry pyridine or in dry cresol, but high in a mixture of the two solvents or in either solvent when moist. Lowry and Smith57 concluded that the mutarotation requires an acid catalyst and a base catalyst, and that amphoteric solvents are complete catalysts for the process, whereas aprotic solvents are not. They also showed that molecules of undissociated acids, cations of weak bases, and anions of weak acids have catalytic properties. Much the same concept was developed independently by Bronsted and Guggenheim,189,223 and came to be known as generalized acid and base catalysis. It was found that the rate of mutarotation of a sugar in the presence of a mixture of several catalysts may be represented by an equation of the type ... 

In the liquid phase the topics of principal concern are adsorption and proton and/or electron transfer across the electric donble layer. Carbon materials are unique in these applications becanse they are insolnble over the entire practical range of pH, are amphoteric, and can exhibit either acidic or basic properties this was illustrated in Fignre 1.10. Furthermore, because of their more or less extensive delocalized k-electron system in the graphene layer, they can either accept or donate electrons. Snch remarkable flexibility offers, on the one hand, a nniqne opportnnity to tailor carbon s properties to specific needs in adsorption, catalysis, and electrocatalysis but, as argued in detail elsewhere [24], it is also responsible for the persistent lack of fundamental nnderstanding in the increasingly important field of carbon electrochemistry, despite the tremendous amount of research and development focused on carbon-based capacitors, batteries, and fnel cells. 

P-Lactams are sensitive to acids and bases, and this sensitivity varies with the nature of the sidechain. The maximum stability of monobasic compounds such as Pen G is exhibited in the pH range 6-7, whereas for ampicillin (an amphoteric compound), the maximum stability occurs at its isoelectric point of pH 5. The highly susceptible f)-lactam nitrogen is prone to attack by nucleophiles such as methanol. Furthermore, this nucleophilic attack is accelerated by acid catalysis and application of heat. They are also readily isomerized in an acidic environment. f)-lactams are typically extracted with water and/or polar organic solvents from solid matrices. 

The first chapter of the book deals with enzyme-like eatalysis by synthetic polymers - catalysis by polymeric acids and bases, amphoteric polyelectrolytes and nonionic polymers. Because coordination compounds of metal ions with macromolecular ligands are interesting with regard to bioinorganic chemistry, this book elucidates some problems involving the catalysis by water-soluble polymer-metal complexes. Ester hydrolysis, hydrogen peroxide decomposition, oxidation of disubstituted phenols, hydroquinones, mercaptoalcohols and other types of reaction are chosen as model processes. A section devoted to interfacial catalysis is also included. 

Equations (7) and (8) are special cases for aqueous solutions of the equation for generalized acid-base catalysis. As shown by Lowry 54a), the muta-rotations of sugars are reactions involving simultaneous catalysis by both acids and bases, in the generalized concept of acids and bases proposed by Lowry and by Bronsted. Water functions as a complete catalyst because of its amphoteric dissociation into ions H20<- H+ + OH. Acids or bases alone are not effective catalysts but in mixture are complete catalysts. 

Water is an amphoteric compound, and thus it can lend all types of assistance, whichever is required in a given process, or even a combination of several. It may itself be a general acid or base catalyst, or, in the presence of other acids and bases, serve as an environment deploying proton or hydroxide ion for specific acid or base catalysis. 

The entities Y and W (in the equations above, H2O) play a big role since it is essentially a question of the transfer of protons from the catalyst to one of the reactants and vice versa the substance Y is in fact the conjugate particle of the catalyst C. In the same way, the substance W in acid catalysis acts as a basic or amphoteric substance, capable of removing a proton from the complex X, and in basic catalysis capable of adding a proton to X. This role can be held by a molecule of solvent in the two cases, but equally by other species in solution. 

The presence of the different functionalities on the various oxide surfaces leads to different reactivity properties. When molecules, metal salts, or metal complexes are adsorbed on the Si02 surface, for example, the anchoring sites are the more reactive isolated Si-OH groups rather than the less reactive bridged Si-O-Si groups. Acid and base sites can often be present simultaneously on oxide surfaces and they can work independently or in a concerted way. Alumina is the best known example of amphoteric oxide widespread used in catalysis (Scheme8.2) [51]. 

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