Dehalogenation electrochemical

Highly reactive metal complexes serve as electrocatalysts for a number of detoxification reactions. An example is the use of Co(II) N, N -bis(salicylidene)ethylene (CoSalen) to facilitate the electrochemical reductive elimination of chlorine from hexachlorobenzene (HCB) [15]. Even though more environmentally friendly conditions have yet to be developed to scale up this process, the CV voltammogram in Fig. 6 shows separate dehalogenation electrochemical steps from the sequence below. 

Dehalogenating reduction Salt elimination Disproportionation Electrochemical formation Dehydrogenative catalytic coupling... 

Electrochemical methods are available for the direct dehalogenation of organic halides to a limited extent fluorides and monochlorides are generally not reducible [1], In the presence of transition-metal complexes as mediators (Med), however, the electrolysis of halocarbons (RX) can be performed more effectively and selectively under various conditions [155-158]. Mediated electroreduction is most efficient when the electron transfer step E° (Med/Med -) is more negative than E° (RX/RX -) [157] (cf. Section 18.4.1). 

Pletcher and associates [155, 159, 160] have studied the electrochemical reduction of alkyl bromides in the presence of a wide variety of macrocyclic Ni(II) complexes. Depending on the substrate, the mediator, and the reaction conditions, mixtures of the dimer and the disproportionation products of the alkyl radical intermediate were formed (cf. Section 18.4.1). The same group [161] reported that traces of metal ions (e.g., Cu2+) in the catholyte improved the current density and selectivity for several cathodic processes, and thus the conversion of trichloroacetic acid to chloroacetic acid. Electrochemical reductive coupling of organic halides was accompanied several times by hydrodehalogena-tion, especially when Ni complexes were used as mediators. In many of the reactions examined, dehalogenation of the substrate predominated over coupling [162-165]. 

Coordinatively unsaturated complexes and those giving easily such species by ligand dissociation favor pathways related to that described in Eqs. (10) and (13). Coordinatively saturated complexes reduce halocarbons via outer-sphere ET [193, 194]. In cases of electrochemical dehalogenations, the species formed by one-electron reduction of the mediators on the cathode often react in this way [156, 157, 198], For example (Eq. (14)) [157, 166] ... 

In outer-sphere SET reductions (e.g., in electrochemical dehalogenations), hydrogen abstraction by R leads to the product RH (i.e., no step related to (ii) is required to occur). Process (ii) follows generally the activation of the substrate in the proposed hydrodehalogenation cycles, but we know also of opposite examples [77, 82, 106, 112],... 

Toxic compounds are frequently rendered less toxic by electrochemical treatment, for instance dehalogenation of chlorinated derivatives such as PCBs or AOX (performed in a divided cell or in the absence of Cl ions in a monocell) odors are eliminated or greatly reduced, i.e. reduction of nitrotoluene which can be a serious odor nuisance biodegradability is improved. Elimination of colloids and surfactants is possible. 

Electrochemical dehalogenation (applicable to pentachlorophenol, trichlorobenzene, hexachlorobenzene, etc.)... 

Organochalcogen(II) compounds, 100-102 Organochalcogen(IV) compounds, 100-102 Organoselenium compounds dehalogenation reactions, 96 electrochemical reduction, 113-117 haloperoxidase-like activity, 108-113 with odd number of ligands, 100-102 one-electron oxidation, 117-118 oxidation of thiols, 102-106 redox reactions, 79-80 thioperoxidase-like activity, 108-113 Organotellurium compounds... 

The electroreductive dehalogenation of a-haloacetic acids has been achieved with cobalamin [387]. The hydrophobic vitamin B12 Co complex immobilized on a glassy carbon electrode (252) may catalyze the electrochemical carbon-skeleton rearrangements of... 

In several examples the reductive halide-hydrogen exchange has been studied on a preparative scale. For example, the indirect electroreduction of 2-chloropyridine in DMF using anthracene as mediator gives pyridine in 83-86 % yield 2 . For the dehalogenation of 1-chlorohexane (80% yield), naphthalene is applied as redox catalyst. Similarly, 6-chloro-hexene yields 1-hexene (60%) and methylcyclopentane (25%), which is the product of the radical cyclization . The indirect electrochemical reduction of p- and y-bromocarboxylic esters forms coupling and elimination products besides the dehalogenated products... 

Dehalogenations, including dehalodefluorinations (e. g., formation of l)159 or didefluorinations to give fluoroarenes,160 can be accomplished electrochemically on a cathode. The method is very sensitive to the electrolyte composition. 

Selective dehalogenation of halopyridines is an important industrial process for the same reason that reduction of carboxylic acids, esters, amides, and nitriles are also important. There is a dearth of selective oxidation technologies whether by conventional or electrochemical methods. Therefore, many intermediate oxidation stage products are made by overoxidation, i.e., overhalogenation, followed by selective reduction. 

Fox MA (1991) Photoinduced Electron Transfer in Arranged Media. 159 67-102 Freeman PK, Hatlevig SA (1993) The Photochemistry of Polyhalocompounds,Dehalogenation by Photoinduced Electron Transfer, New Methods of Toxic Waste Disposal. 168 47-91 Fuchigami T (1994) Electrochemical Reactions of Fluoro Organic Compounds. 170 1-38 Fuller W, see Grenall R (1989) 151 31 - 59... 

Electrochemical reduction processes of CFCs leading to partially or completely dehalogenated compounds for synthetic purposes have been... 

Zhang and Rusling [66] employed a stable, conductive, bicontinuous microemulsion of surfactant/oil/water as a medium for catalytic dechlorination of PCBs at about 1 mA cm-2 on Pb cathodes. The major products were biphenyl and its reduced alkylbenzene derivatives, which are much less toxic than PCBs. Zinc phthalocyanine provided better catalysis than nickel phthalocyanine tetrasulfonate. The current efficiency was about 20% for 4,4 -DCB and about 40% for the most heavily chlorinated PCB mixture. A nearly complete dechlorination of 100 mg of Aroclor 1260 with 60% Cl was achieved in 18 hr. Electrochemical dehalogenation was thus shown to be feasible in water-based surfactant media, providing a lower-cost, safer alternative to toxic organic solvents. 

Schmal D, Van Duin PJ, de Jong AMCP. Electrochemical dehalogenation of... 

ESR study of the electrochemical dehalogenation of 2-halo-5-nitrofurans showed that the first step involves the formation of radical anions the dehalogenation of which proceeds via a dianion intermediate for chloro compounds, for the iodo compounds. Both routes were involved for the bromo compounds. The stability of the intermediate anion radicals of 2-halo-5-nitrofurans increased in the order I < Br < Cl208. 

Polyhaloacetic acids and their partially hydrodehalogenated products represent a second important family of herbicide-/pesticide-derived substrates. In their review on the environmental applications of industrial electrochemistry, Juttner and co-authors (Juttner et al. 2000) documented the electroreductive dechlorination of dichloroacetic acid (a by-product of monochloroacetic acid), a way to recover the valuable compound and avoid wastes. The electrochemical reduction of polychloro- and polybromo-derivatives was performed by Korshin and Jensen (2001) on Cu and Au cathodes. Complete dehalogenation was obtained for all substrates, but for monochloroacetic acid. To overcome the intrinsic poor reactivity of the monochloro-derivative the photoelectrochemical properties of a p-doped SiC electrode were investigated (Schnabel et al. 2001) however, the dehalogenation stopped at monochloroacetic acid. 

Gassman, J., Voss, J. and Adiwidjaja, G. (1995) Electroreduction of organic compounds. 25. Electrochemical dehalogenation of chlorinated insecticides. Zeit. Natur. B Chem. Sci. 50,953-958. 

Magdesieva, T.V., Graczyk, M., Vallat, A., Nikitin, O.M., Demyanov, P.I., Butin, K.P. and Vorotyntsev, M.A. (2006) Electrochemically reduced titanocene dichloride as a catalyst of reductive dehalogenation of organic halides. Electrochim. Acta 52, 1265-1280. 

Rondinini, S., Mussini, P.R., Specchia, M. and Vertova, A. (2001a) The electrocatalytic performance of silver in the reductive dehalogenation of bromophenols. J. Electrochem Soc. 148, D102-D107. 

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