Amination electrochemical

Oxo- and 3,5-dioxo-pyrrolizidines can be regarded as mono- and di-lactams, respectively, and hence exhibit typical amide properties. They are readily reduced to amines electrochemically (see, e.g. refs. 29 and 31) or with lithium aluminum hydride (see, e.g., refs. 30 and 33). 

Z. Chen, J. Liu, K. Amine, Electrochem. Solid-State Lett. 2007, 10, A45-A47. Lithium difluoro(oxalato)borate as salt for lithium-ion batteries. 

Many perfluoroaUphatic ethers and tertiary amines have been prepared by electrochemical fluorination (1 6), direct fluorination using elemental fluorine (7—9), or, in a few cases, by fluorination using cobalt trifluoride (10). Examples of lower molecular weight materials are shown in Table 1. In addition to these, there are three commercial classes of perfluoropolyethers prepared by anionic polymerization of hexafluoropropene oxide [428-59-1] (11,12), photooxidation of hexafluoropropene [116-15-4] or tetrafluoroethene [116-14-3] (13,14), or by anionic ring-opening polymeriza tion of tetrafluorooxetane [765-63-9] followed by direct fluorination (15). 

Carbonyl sulfonyl fluorides of the formula FC0(CF2) S02F have been prepared by electrochemical fluorination of hydrocarbon sultones (41,42). More commonly in a technology pioneered by Du Pont, perfluoroalkanecarbonyl sulfonyl fluorides are prepared by addition of SO to tetrafluoroethylene followed by isomerization with a tertiary amine such as triethylamine (43). 

In the reduction of nitro compounds to amines, several of the iatermediate species are stable and under the right conditions, it is possible to stop the reduction at these iatermediate stages and isolate the products (see Figure 1, where R = CgH ). Nitrosoben2ene [586-96-9] C H NO, can be obtained by electrochemical reduction of nitrobenzene [98-95-3]. Phenylhydroxylamine, C H NHOH, is obtained when nitrobenzene reacts with ziac dust and calcium chloride ia an alcohoHc solution. When a similar reaction is carried out with iron or ziac ia an acidic solution, aniline is the reduction product. Hydrazobenzene [122-66-7] formed when nitrobenzene reacts with ziac dust ia an alkaline solution. Azoxybenzene [495-48-7], C22H2QN2O, is... 

Electrochemical fluonnation ot N,N dialkylammo-substituted carboxylic acids as their methyl esters produces the analogous perfluonnated tertiary amine carboxylic acid derivatives in 18-30% yields as well as cyclic amine ethers [JOO]... 

The following supplements the article on Azoxymethane in Vol 1, A670-L. It has been prepd by the electrochem redn of nitromethane in IN aq K hydroxide, with N-methylhydroxyl-amine as an intermediate, yield 60% (Ref 4). 

It is readily reduced to Me amine, and a number of chem, catalytic, and electrochem procedures have been used (Ref 10). 2) In most cases the redns can be stopped at the hydroxyl-amine stage to give N-Me hydroxylamine (Ref 10). 3) The action of strong acids on salts of NMe gives derivs of formaldehyde (Ref 10). 

Proton electrochemical gradient. 6,714 Proton exchange amine ligands, 2, 24 Proton loss catalysis... 

Electropolymerization is also an attractive method for the preparation of modified electrodes. In this case it is necessary that the forming film is conductive or permeable for supporting electrolyte and substrates. Film formation of nonelectroactive polymers can proceed until diffusion of electroactive species to the electrode surface becomes negligible. Thus, a variety of nonconducting thin films have been obtained by electrochemical oxidation of aromatic phenols and amines Some of these polymers have ligand properties and can be made electroactive by subsequent inincorporation of transition metal ions... 

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