Methyl pyridinium ions

Proton-proton coupling constants in a-D-xylopyranosyl-4-methyl-pyridinium ion and methyl-P-D-galactopyranoside. Note the differences between coupling constants associated with very similar dihedral angles and the lower couplings experienced when the proton-attached carbon atoms have multiple electron-withdrawing groups. 

Fall et al. investigated the role of the mitochondrial transition pore (MTP) in apoptosis induced by the Parkinsonism producing toxin N-methyl pyridinium ion (MPP+) by using cyclosporin A (CSA) alone or in combination with the phospholipase A2 (PLA2) inhibitor aristolochic acid (5) (ARA). In this experiment, aristolochic acid alone inhibited MPP+ induced apoptosis at 24 hours but did not alter the mitochondrial effects of MPP+, suggesting that ARA inhibits MPP+ induced apoptosis downstream of the initiation event. Thus, ARA may prove to be another useful tool for understanding apoptosis [455,456]. 

O-acetyl-a-D-glucopyranosyl-4-methyl pyridinium ion adopts the B2 5 conformation... 

Pyridinium iodide, 4,4 (l,3,4-thiadiazole-2,5-diyl)-bis(l-methyl)-reduction, 6, 564 Pyridinium ion, Af-methyl-as metabolite of pyridine, 1, 234 Pyridinium ions hydrogen bonding to water mass spectrometry, 2, 135 magnetic circular dichroism, 2, 129 NMR, 2, 121... 

A large number of examples of redox polyelectrolyte monolayers have been reported [42[. Anson described the adsorption of poly(acrylic acid) onto glassy carbon with electrostatic binding of Ru(NH3)6 and Co(NH3)6 ions from solution [43]. Finklea [44] adsorbed poly(4-vinyl-I-methyl-pyridinium methylsulfate) on self-assembled mercapto-undecanoic self-assembled monolayer (SAM) on gold electrodes to... 

On co-adsorbing phenol and methanol, the protonation of methanol occurs on the active acid sites as the labile protons released from the phenol reacted with methanol. Thus protonated methanol became electrophilic methyl species, which undergo electrophilic substitution. The ortho position of phenol, which is close to the catalyst surface, has eventually become the substitution reaction center to form the ortho methylated products (Figure 3). This mechanism was also supported by the competitive adsorption of reactants with acidity probe pyridine [79]. A sequential adsorption of phenol and pyridine has shown the formation of phenolate anion and pyridinium ion that indicated the protonation of pyridine. 

Another experiment in which sequential adsorption of phenol and pyridine then followed by methanol shows formation of pyridinium ion and phenolate anion whereas no traces of methanol or electrophilic methyl species or formation of methylated products were identified on the catalysts surface. This result was supposedly confirmed from another experiment in which anisole and methanol were co-adsorbed on the catalyst. The spectra were referred to the molecular species of methanol and anisole without any significant interaction among them and above 200°C they simply desorbed from the catalyst. 

The spectra of substituted pyridinium iodides are characterized by charge transfer bands involving the interaction of pyridinium and iodide ions. Mukerjee and Rayt showed that this band is shifted about 90 nm toward the red for dodecyl pyridinium iodide, which forms micelles, compared to methyl pyridinium iodide, which does not. They measured max for the micelles in mixed solvents of variable relative dielectric constant and obtained the following results ... 

An analogous cation radical chain process has been proposed for cis to trans isomerization of N-methyl-4-(6-stryl)-pyridinium ions via electron-transfer sensitization by Ru(bpy)-j2+ and metalloporphyrins (145). Quantum yields for isomerization are substantially higher in aqueous anionic micelles versus homogeneous solution due to the higher concentration of cis-styrylpyridinium ions. A radical cation chain mechanism may also account for previous reports of selective cis to trans sensitized photoisomerization of stilbene (25,26). 

These chiral acyl donors can be used for quite effective kinetic resolution of racemic secondary alcohols. For example, enantiomeric aryl alkyl ketones are es-terified by the acyl pyridinium ion 8 with selectivity factors in the range 12-53 [10], In combination with its pseudo-enantiomer 9, parallel kinetic resolution was performed [11], Under these conditions, methyl l-(l-naphthyl)ethanol was resolved with an effective selectivity factor > 125 [12]. Unfortunately, the acyl donors 8 and 9 must be preformed, and no simple catalytic version was reported. Furthermore, over-stoichiometric quantities of either MgBr2 or ZnCI2 are required to promote acyl transfer. In 2001, Vedejs and Rozners reported a catalytic parallel kinetic resolution of secondary alcohols (Scheme 12.3) [13]. 

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