Donor proton

Many solids have foreign atoms or molecular groupings on their surfaces that are so tightly held that they do not really enter into adsorption-desorption equilibrium and so can be regarded as part of the surface structure. The partial surface oxidation of carbon blacks has been mentioned as having an important influence on their adsorptive behavior (Section X-3A) depending on conditions, the oxidized surface may be acidic or basic (see Ref. 61), and the surface pattern of the carbon rings may be affected [62]. As one other example, the chemical nature of the acidic sites of silica-alumina catalysts has been a subject of much discussion. The main question has been whether the sites represented Brpnsted (proton donor) or Lewis (electron-acceptor) acids. Hall... 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

These species are less stable than R88=C=8(Li)-XR in the presence of a sufficiently acidic proton donor, e.g. amtnonia or dicyclohexylamine, they are... 

Terminal alkynes are only reduced in the presence of proton donors, e.g. ammonium sulfate, because the acetylide anion does not take up further electrons. If, however, an internal C—C triple bond is to be hydrogenated without any reduction of terminal, it is advisable to add sodium amide to the alkyne solution Hrst. On catalytic hydrogenation the less hindered triple bonds are reduced first (N.A. Dobson, 1955, 1961). 

Selective reduction of a benzene ring (W. Grimme, 1970) or a C C double bond (J.E. Cole, 1962) in the presence of protected carbonyl groups (acetals or enol ethers) has been achieved by Birch reduction. Selective reduction of the C—C double bond of an a,ft-unsaturated ketone in the presence of a benzene ring is also possible in aprotic solution, because the benzene ring is redueed only very slowly in the absence of a proton donor (D. Caine, 1976). 

A more general theory of acids and bases was devised independently by Johannes Br0n sted (Denmark) and Thomas M Lowry (England) m 1923 In the Brpnsted-Lowry approach an acid is a proton donor, and a base is a proton acceptor The reaction that occurs between an acid and a base is proton transfer... 

Section 1 13 According to the Brpnsted-Lowry definitions an acid is a proton donor and a base is a proton acceptor... 

Organohthium and organomagnesium compounds find their chief use m the prepa ration of alcohols by reaction with aldehydes and ketones Before discussing these reac tions let us first examine the reactions of these organometallic compounds with proton donors... 

Organohthium and organomagnesium compounds are stable species when prepared m suitable solvents such as diethyl ether They are strongly basic however and react instantly with proton donors even as weakly acidic as water and alcohols A proton is transferred from the hydroxyl group to the negatively polarized carbon of the organometallic compound to form a hydrocarbon... 

But ethers lack OH groups and cannot act as proton donors in forming hydrogen bonds... 

Step 1 The carboxylic acid is protonated on its carbonyl oxygen The proton donor shown in the equation for this step is an aUtyloxonium ion formed by proton transfer from the acid catalyst to the alcohol... 

Section 27 21 Often the catalytically active functions of an enzyme are nothing more than proton donors and proton acceptors In many cases a protein acts m cooperation with a coenzyme, a small molecule having the proper func tionahty to carry out a chemical change not otherwise available to the protein itself... 

A useful definition of acids and bases is that independently introduced by Johannes Bronsted (1879-1947) and Thomas Lowry (1874-1936) in 1923. In the Bronsted-Lowry definition, acids are proton donors, and bases are proton acceptors. Note that these definitions are interrelated. Defining a base as a proton acceptor means an acid must be available to provide the proton. For example, in reaction 6.7 acetic acid, CH3COOH, donates a proton to ammonia, NH3, which serves as the base. 

A species that can serve as both a proton donor and a proton acceptor is called amphiprotic. Whether an amphiprotic species behaves as an acid or as a base depends on the equilibrium constants for the two competing reactions. For bicarbonate, the acid dissociation constant for reaction 6.8... 

The dissociation, or autoprotolysis constant for a solvent, SH, relates the concentration of the protonated solvent, SH2, to that of the deprotonated solvent, S . For amphoteric solvents, which can act as both proton donors and proton acceptors, the autoprotolysis reaction is... 

Acids that are better proton donors than the solvent are leveled to the acid strength of the protonated solvent bases that are better proton acceptors than the solvent are leveled to the base strength of the deprotonated solvent. 

Cocatalysts of two types occur (/) proton-donor substances, such as hydroxy compounds and proton acids, and (2) cation-forming substances (other than proton), including alkyl and acyl haUdes which form carbocations and other donor substances leading to oxonium, sulfonium, halonium, etc, complexes. 

If the initiation reaction is much faster than the propagation reaction, then all chains start to grow at the same time. Because there is no inherent termination step, the statistical distribution of chain lengths is very narrow. The average molecular weight is calculated from the mole ratio of monomer-to-initiator sites. Chain termination is usually accompHshed by adding proton donors, eg, water or alcohols, or electrophiles such as carbon dioxide. 

The kinetics of reactions cataly2ed by very strong acids are often compHcated. The exact nature of the proton donor species is often not known, and typically the rate of the catalytic reaction does not have a simple dependence on the total concentration of the acid. However, sometimes there is a simple dependence of the catalytic reaction rate on some empirical measure of the acid strength of the solution, such as the Hammett acidity function Hq, which is a measure of the tendency of the solution to donate a proton to a neutral base. Sometimes the rate is proportional to (—log/ig)- Such a dependence may be expected when the slow step in the catalytic cycle is the donation of a proton by the solution to a neutral reactant, ie, base but it is not easy to predict when such a dependence may be found. 

Hydrogen bonding to the nitrogen lone pair leads to an upheld shift, the extent of which depends on the proton-donor ability of the solvent, and the acceptor ability of the base shifts of some 20 p.p.m. are commonly found. 

The reactions of pyrroles with dimethyl acetylenedicarboxylate (DMAD) have been extensively investigated. In the presence of a proton donor the Michael adducts (125) and (126) are formed. However, under aprotic conditions the reversible formation of the 1 1 Diels-Alder adduct (127) is an important reaction. In the case of the adduct from 1-methylpyrrole, reaction with a further molecule of DMAD can occur to give a dihydroindole (Scheme 48) (82H(19)1915). 

The acid-base properties of isoxazole and methylisoxazoles were studied in proton donor solvents, basic solvents or DMSO by IR procedures and the weakly basic properties examined (78CR(Q(268)613). The basicity and conjugation properties of arylisoxazoles were also studied by UV and basicity measurements, and it was found that 3-substituted isoxazoles were always less basic than the 5-derivatives. Protonation increased the conjugation in these systems (78KGS327). 

The relative basicity and acidity of isothiazole and its methyl derivatives have been compared by IR spectroscopy (77MI41702). The isothiazoles, dissolved in inert solvents (e.g. CCI4, CS2) containing traces of butanol (a proton donor), interact with the butanol OH... 

The possible mechanism of ionization, fragmentation of studied compound as well as their desoi ption by laser radiation is discussed. It is shown that the formation of analyte ions is a result of a multi stage complex process included surface activation by laser irradiation, the adsoi ption of neutral analyte and proton donor molecules, the chemical reaction on the surface with proton or electron transfer, production of charged complexes bonded with the surface and finally laser desoi ption of such preformed molecules. 

For example, nylon 66 will dissolve in formic acid, glacial acetic acid, phenol and cresol, four solvents which not only have similar solubility parameters but also are capable of acting as proton donors whilst the carbonyl groups on the nylon act as proton acceptors (Figure 5.6). 

Proton donors include highly halogenated compounds such as choloroform and pentachlorethane. Less halogenated materials are weaker donors. 

Some materials such as water, alcohols, carboxylic acids and primary and secondary amines may be able to act simultaneously as proton donors and acceptors. Cellulose and poly(vinyl alcohol) are two polymers which also function in this way. 

It is interesting to note that these crystalline materials do not dissolve in tetrahydrofuran or cyclohexanone at room temperature, indicating that PVC is too weak a proton donor to overcome extensive crystallisation. Crystalline PVC has a greater tensile strength and creep resistance than conventional polymer. It is, however, brittle, and whilst most conventional impact modifiers appear ineffective, EVA polymers are said to be quite useful. Plasticised compounds may also be prepared although mixing temperatures of up to 190°C are necessary. 

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