Bronsted nitrogens

It is obvious that the reaction is accelerated markedly by water. However, for the first time, the Diels-Alder reaction is not fastest in water, but in 2,2,2-trifiuoroethanol (TFE). This might well be a result of the high Bronsted acidity of this solvent. Indirect evidence comes from the pH-dependence of the rate of reaction in water (Figure 2.1). Protonation of the pyridyl nitrogen obviously accelerates the reaction. 

Figures 2.a-c show the pyridine adsorption results. Bronsted acidity is manifested by the bands at 1440-1445,1630-1640 and 1530-1550 cm . Bands at 1600-1630 cm are assigned to pyridine bonded to Lewis acid sites. Certain bands such as the 1440-1460 and 1480-1490 cm can be due to hydrogen-bonded, protonated or Lewis-coordinated pyridine species. Under continuous nitrogen purging, spectra labeled as "A" in Figures 2a-c represent saturation of the surface at room temperature (90 25 unol pyridine/g found in all three tungsta catalysts) and "F" show the baseline due to the dry catalyst. We cannot entirely rule out the possibility of some extent of weakly bound pyridine at room temperature. Nevertheless, the pyridine DRIFTS experiments show the presence of Brpnsted acidity, which is expected to be the result of water of reduction that did not desorb upon purging at the reduction temperature. It is noted that, regardless of the presence of Pt, the intensity of the DRIFTS signals due to pyridine are...

The NH4-Beta-300 (Zeolyst International, number denote Si02/Al203 molar ratio) was transformed to corresponding proton form using a step calcination procedure at 500 °C. H-Beta-300 was partially modified with Fe by repeated ion-exchange method (Fe(III)nitrate). The surface areas as well as acidities (Bronsted and Lewis acid sites) of Fe-Beta (iron content - 0.1 wt %) were determined by nitrogen adsorption and pyridine desorption at 250, 350 and 450 °C using FTIR spectroscopy [6]. 

Table 8.3 lists the base dissociation constants for several weak bases at 25°C. Nitrogen-containing compounds are Bronsted-Lowry bases, because the lone pair of electrons on a nitrogen atom can bond with H+ from water. The steps for solving problems that involve weak bases are similar to the steps you learned for solving problems that involve weak acids. 

Ammonia is adsorbed on the surface of an SCR catalyst in a diffusion limited laminar flow regime. The ammonia combines with vanadium pentoxide V2O5, a catalytic metal impregnated on the surface of the catalyst, to form a Bronsted acid site. NOx reduction takes place on this acid site to form nitrogen and water. The spent -OH site is restored to -OH via oxidation to repeat the catalytic cycle. Once the vanadium site can no longer revert back into the -1-5 oxidative state, then that site is no longer active for NO reduction. Figure 17.7 shows the catalytic cycle for the SCR reactions. 

Nucleophilicity. A distinction is usually made between nucleophilicity and Lowry-Bronsted basicity [213]. The latter involves specifically reaction at a proton which is complexed to a Lewis base (usually H2O), while the former refers to reactivity at centers other than H. Linear correlations have been shown for gas-phase basicity (proton affinity) and nucleophilicity of nitrogen bases toward CH3I in solution [214] where the solvent is not strongly involved in charge dispersal. In each case, reaction of the base/nucleophile... 

Alkyl halides react with diazines less readily than with pyridines. All the diazines are, nevertheless, more reactive toward methyl iodide than predicted by their pKa values and the Bronsted relationship. The significant although modest rate enhancements found are considered to arise from interactions between the two lone pairs on the nitrogen atoms this interaction is largest in pyridazine. Use of oxonium ions can convert the diazines into diquatemary salts. Quinoxalines and phenazines similarly yield diquatemary salts under forcing conditions. 

To determine a or (3 experimentally a plot of log kB or log kHB vs pKa (a Bronsted plot) is made and the slope is measured. Statistical corrections (Chapter 7) should be applied for dicarboxylic acids and for ammonium ions from which one of three protons may be lost from the nitrogen atom. General base or general acid catalysis implies an important feature of any mechanism for which it is observed, namely, that removal of a proton or addition of a proton is involved in the... 

The nucleophilic properties of pyridine nitrogen have been assessed in studies on pyridine-catalyzed Schotten-Baumann reactions133 and aromatic sulfonyl chloride hydrolyses,134 from which highly accurate Bronsted and Hammett treatments arise. There is some doubt as to the mechanism of this reaction.45 Equations (13) and (14) accurately express the reactivity of 3- and 4-substituted pyridines toward ethyl iodide (using rate for equilibrium constants),133 while rates of N-methylation of 2-substituted pyridines have been used to estimate both steric and electronic effects.136... 

Asymmetric Mannich reactions provide useful routes for the synthesis of optically active p-amino ketones or esters, which are versatile chiral building blocks for the preparation of many nitrogen-containing biologically important compounds [1-6]. While several diastereoselective Mannich reactions with chiral auxiliaries have been reported, very little is known about enantioselective versions. In 1991, Corey et al. reported the first example of the enantioselective synthesis of p-amino acid esters using chiral boron enolates [7]. Yamamoto et al. disclosed enantioselective reactions of imines with ketene silyl acetals using a Bronsted acid-assisted chiral Lewis acid [8]. In all cases, however, stoichiometric amounts of chiral sources were needed. Asymmetric Mannich reactions using small amounts of chiral sources were not reported before 1997. This chapter presents an overview of catalytic asymmetric Mannich reactions. 

In non-K-region epoxides like 86, second-order nucleophilic addition and water-catalyzed aromatization compete. Nitrogen and oxygen nucleophiles are not able to compete, whereas polarizable nucleophiles do. The factor most important is apparently the polarizability of the nucleophile rather than its basicity. The basicity of the thiolate species has little influence on the rate of reaction of 86 (Bronsted / -value = 0.2).138,139... 

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