Cyanides electrochemical generation

Aryl radicals electrochemically generated from the cleavage of aryl halide radical anions have been observed to react with nucleophiles other than iodide (Pinson and Saveant, 1974, 1978 Saveant, 1980), a reaction known as the SrjjI reaction (Bunnett, 1978). The most commonly used nucleophiles are thiophenolate, mercaptides, and cyanide ion. The reactions observed are... 

The nucleophilic addition of cyanide ions to the electrochemically generated iminium cation is a synthetically very useful reaction and has been studied for a variety of symmetric and unsymmetric ions (Table 10) [266]. 

Hypochlorite can be produced by the reaction of chlorine gas with sodium hydroxide solution. On-site generation of hypochlorite avoids storage and transport difficulties associated with chlorine gas, and is convenient for many applications, including sewage treatment, sterilisation of water, disinfection, biological growth prevention and enhanced oxidation of, for example, cyanide wastes. The electrochemical generation of hypochlorite has been the subject of several reviews (see [84]). 

ELECTROCHEMICAL GENERATION OF SUBSTRATE-BINDING SITES IN ORGANOMETALLIC COMPLEXES WITH THE M02( i-SR)n CORE. ELECTROSYNTHESIS OF CYANIDE AND ISOCYANIDE DERIVATIVES. 

The one-electron electrochemical reduction of NP (57) is a reversible process in aqueous solution, provided the measurements are performed at pH > 8 (—0.123 V vs. NHE) (57a,57b). Different chemical reductants such as sodium in liquid ammonia, tetrahydroborate, ascorbic acid, quinol, dithionite, superoxide or thiolates are also known to generate the [Fen(CN)5NO]3 ion (48,57). However, care must be taken in the products analysis, because the negative redox potentials of some of these reductants allow for further nitrosyl reduction (57a). Also, the reduced product is unstable toward cyanide... 

The 6-substituted cyano bipyridine has been generated in 95% yield from bipyridine A-oxide by reaction with trimethylsilylcyanide and dimethylcarbamylchloride.76 This is an improvement on an earlier method that generated 6-cyano bipyridine from the A-oxide in 62% yield using potassium cyanide and benzoyl chloride.77 This ligand has been used in electrochemical studies of rhenium complexes with sterically hindered bipyridine derivatives, as well as a precursor in the synthesis of 6-carbothioamide-bpy, which showed antitumor activity against P-388 lymphocytic leukemia in mice.77... 

In the cell, electron flow in the electron transport chain must be sequential from NADH or a flavoprotein all the way to O2 to generate ATP (see Fig. 21.5). In the absence of O2, there is no ATP generated from oxidative phosphorylation because electrons back up in the chain. Even complex I cannot pump protons to generate the electrochemical gradient, because every molecule of CoQ already has electrons that it cannot pass down the chain without an O2 to accept them at the end. The action of the respiratory chain inhibitor cyanide, which binds to cytochrome oxidase, is similar to that of anoxia it prevents proton pumping by all three complexes. Complete inhibition of the b-c complex prevents pumping at cytochrome... 

The reactivity of cyanide ion with aryl radicals generated electrochemically in liquid ammonia from 2-, 3- and 4-chlorobenzonitriles was reported by Amatore and coworkers. The coupling between the aryl radicals and the nucleophile appears to be the key step of a Srn reaction. In these reactions the C—Cl bond was cleaved in the radical anion formed by electroreduction of the chlorobenzonitrile, giving a radical that then reacted with cyanide to yield dicyanobenzenes. The steps involved in the reaction sequence are described in Yoshida s review. ... 

In CHEC-I, the capture of the cation radical generated from 2,5-dimethylthiophene by a nucleophile such as cyanide or solvent methanol, was discussed. Similarly, it has been found that the electrochemical oxidation of benzo[A]thiophene generates a cation radical. This can be captured by... 

Cyanides occur in many effluents generated by industry [40], particularly metal finishing and metal treatment. The oxidation of cyanide is achieved by both electrochemical and chemical methods. Commercial electro-... 

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