Tetraethylammonium salts oxidation

In both polarographic and preparative electrochemistry in aptotic solvents the custom is to use tetraalkylammonium salts as supporting electrolytes. In such solvent-supporting electrolyte systems electrochemical reductions at a mercury cathode can be performed at —2.5 to —2.9 V versus SCE. The reduction potential ultimately is limited by the reduction of the quaternary ammonium cation to form an amalgam, (/ 4N )Hg , n = 12-13. The tetra-n-butyl salts are more difficult to reduce than are the tetraethylammonium salts and are preferred when the maximum cathodic range is needed. On the anodic side the oxidation of mercury occurs at about +0.4 V versus SCE in a supporting electrolyte that does not complex or form a precipitate with the Hg(I) or Hg(II) ions that are formed. 

The compound K2 [Rh6(CO)15C] is a yellow powder. It is sensitive to air both in the solid state and in solution and is quite soluble in water, methanol, ethanol, acetone, THF, and acetonitrile. The salts of other cations can be obtained by metathesis, in water for the cesium salt and in methanol for the larger tetra-alkylammonium or phosphonium cations. The tetraethylammonium salt is sparingly soluble in THF, whereas the benzyltrimethylammonium and bis-(triphenylphosphine)imminium salts are soluble. All of these salts are soluble in acetone and acetonitrile. The yellow solution of the potassium salt in THF shows characteristic IR bands at 2040 (vw), 1990 (vs), 1885 (vw), 1845 (s), 1830 (sh, m) 1815 (sh, br) and 1775 (vw, br) cm-1. The IR spectral band shapes depend on solvents and cations. The oxidation of K2 [Rh6(CO)i5C] with iron-(III) ammonium sulfate in water under carbon monoxide leads to the octa-nuclear carbido carbonyl cluster Rhg(CO)i9C,6 whereas under nitrogen RhntCO sQ7 or [H30] [Rhls(CO)28C2]8 is obtained. 

The direct synthesis by anodic oxidation of a new series of electrically conducting poljnners is described.. Our polymers derive from sulfur and/or nitrogen containing hetero-cycles such as 2-(2-thienyl)pyrrole, thiazole, indole, and phthalazine. The anodic oxidation of these monomers is carried out in acetonitrile solutions containing tetrabu-tylammonium salts (TBA X ) ith X = BF, tetraethylammonium salt, TEA H C-C H -S0. Characterization of the materials by electrical conductivity, electron spin resonance, uv-visible spectroscopy, and cyclic voltammetry is discussed. 

Thiazole A -oxides can easily be alkylated on the oxygen. For example, Ar-(alkoxy)-5-(p-methoxyphenyl)-4-methylthiazole-2(377)-thiones were prepared from Ar-(hydroxy)-5-( -methoxyphenyl)-4-methylthiazole-2(3//)-thione tetraethylammonium salt and an appropriate alkyl chloride or tosylate in moderate to good yields <20060BC2313>. A -Methoxythiazole-2(377)-thiones were synthesized from the A -hydroxythiazole-2(3//)-thiones by treatment first with a tetraalkylammonium hydroxide in methanol and then methyl ra-toluenesulfonate in DMF <2005EJ0869>. 

The effect of the quaternary ammonium salt depends also on the substrate and on the electrode material [38]. Addition of tetraethylammonium salts thus sharply increases the yield of dimer product from acrylonitrile, has little effect upon the hydrodimerization of methyl acrylate, and does not affect the hydrodimerization of mesityl oxide. 

During the preparation of the quaternary oxidant tetraethylammonium iodate from the aqueous reagents, the residue after vacuum evaporation of most of the water exploded, breaking the flask. This was attributed to possible presence of excess periodic acid in the reaction mixture [1]. Further details and precautions to avoid heating the salt, normally stable in storage, are given [2],... 

A typical cyclic voltammogram is shown in Fig. 2 for a polypyrrole film. The polypyrrole film was electrochemically grown on a 0.5-cm platinum electrode in a solution of 0.1 M tetraethylammonium tetrafluoroborate in acetonitrile [46]. The oxidation wave in the anodic sweep produced a reduction wave on the reverse cathodic sweep. Different diffusion processes involved most likely account for the different shapes of the oxidation and reduction waves. For example, when lithium perchlorate is the electrolytic salt, perchlorate anions diffuse into the polymer upon oxidation. However, upon reduction the more mobile lithium cations diffuse in... 

Quaternary ammonium salts exhibit high catalytic activity in radical-chain reactions of hydrocarbons liquid phase oxidation by [1, 2]. Tetraalkylammonium halides accelerate radical decomposition of hydroperoxides [3,4] that are primary molecular products of hydrocarbons oxidation reaction. Reaction rate of the hydroperoxides decomposition in the presence of quaternary ammonium salts is determined by the nature of the salt anion [4] as well as cation [5]. The highest reaction rate of the tert-butyl hydroperoxide and cumene hydroperoxide decomposition has been observed in the case of iodide anions as compared with bromide and chloride ones [4]. tetraalkylammonium bromides tetraethylammonium... 

The scheme of the peroxides activation and decomposition in the presence of quaternary onium salt is proposed. It is substantiated by kinetic methods as well as by molecular modeling methods. It has been shown that peroxides decomposition in the presence of tetraethylammonium bromide proceeded according to supramolecular mechanism. Cyclohexanone peroxides in the presence of Et4NBr effectively initiate the radical chain cumene oxidation. 

Nucleophilic substitution, e.g. the preparation of thiocyanates from lipophilic alcohols, can be facilitated by substrate hydrophilation via ammonioethanesulfonic acid esters (betylates)i . Mercaptans can be easily prepared from alcohols with inversion of configuration via thiolic esters prepared with thioacetic acid in the presence of 2-fluoro-pyridinium salts . C-Sulfenylation of / -dicarbonyl compounds with mercaptans by air oxidation in the presence of tetraethylammonium fluoride has been reported . Activated thiolic and selenolic esters can be prepared at room temperature from carboxylic acids and aryl thiocyanates or selenocyanates in the presence of tri-n-butylphosphine i. Phenylselenolactones have been obtained under very mild conditions from unsaturated acids and benzeneselenyl chloride. ... 

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