Reduction of Halogen Compounds

Complex (16), which has a similar structure to Co11 salen, catalyzes the electrocarboxylation of arylmethyl chlorides.274 The enhancement of the catalytic life of (16) as compared to Co-salen may be due to the absence of imino bond in its ligand. The catalytic reduction of halogenated compounds has also been attempted at poly[Mn(salen)]-coated electrodes (M = Ni,253 Co275), which might have potential use for determination of organohalide pollutants.275... 

Schmal D, van Erkel J, van Duin PJ (1986) Electrochemical reduction of halogenated compounds in process wastewaters, Inst Chem Eng Symp Ser 1986,98 (Electrochem Eng) 281 Chem Abstr 105 158252e... 

Reaction LXII. Direct Reduction of Halogen Compounds. (J. C. S.,... 

Schmal, D., van Erkel, J. and van Duin, P. J. (1986) Electrochemical reduction of halogenated compounds in process waster water. Ichem. Symp. Ser. 98, 259-269. 

The question also arises how far the comparison may be extended to reactions which are not ionic. In the first instance we can only say that reactions must at least exist which are related to the polar nature of the linkage, e.g. the hydrolysis of halogen compounds or esters, but not (as one might expect) the reduction of halogen compounds with hydrogen. 

Various stereoselective and stereospecific reductions of halogen compounds have been reported. 

The introduction of tritium into molecules is most commonly achieved by reductive methods, including catalytic reduction by tritium gas, PH2], of olefins, catalytic reductive replacement of halogen (Cl, Br, or I) by H2, and metal pH] hydride reduction of carbonyl compounds, eg, ketones (qv) and some esters, to tritium-labeled alcohols (5). The use of tritium-labeled building blocks, eg, pH] methyl iodide and pH]-acetic anhydride, is an alternative route to the preparation of high specific activity, tritium-labeled compounds. The use of these techniques for the synthesis of radiolabeled receptor ligands, ie, dmgs and dmg analogues, has been described ia detail ia the Hterature (6,7). 

Mazur DJ, Weinberg NL (1987) Methods for the electrochemical reduction of halogenated organic compounds, US, US 4,702,804 Chem Abstr 108 (1988) 175949s... 

CHEC-II(1996) <1996CHEC-II(8)345> covered a range of reactions of substituents, including hydrolyses of esters to carboxylic acids and geminal dihalides to aldehydes, reduction of aldehydes and halogens directly attached to the ring, O-methylation with diazomethane, and reduction of nitroso compounds. A selection of reactions which have... 

In this part of the chapter, the discussion is focused on the direct cathodic reduction of halogenated organic compounds, although the last section will address the increasingly active area of catalytic reductions of carbon-halogen bonds. 

Two types of electrogenerated carbon bases have commonly been used (1) dianions derived from activated alkenes, and (2) carbanions formed by reductive cleavage of halogen compounds or by direct reduction of weak carbon acids. In both cases, the efficiency of the proton transfer reaction relies on a thermodynamically favored proton transfer or a fast follow-up reaction of the deproto-nated substrate. 

A similar process may take place in the reduction of polar compounds with single bonds. A halogen, hydroxy, sulfhydryl or amino derivative by accepting an electron dissociates into a radical and an anion. In aprotic solvents the two radicals combine. In the case of halogen derivatives the result is Wurtz synthesis. In the presence of protons the anion is protonated and the radical accepts another electron to form an anion that after protonation gives a hydrocarbon or a product in which the substituent has been replaced by hydrogen. 

In a fashion similar to that of cobalt salen, distinct redox chemistry can be observed for each of the two cobalt centers of (28). Coulometric studies showed that the complex can undergo a one-electron reduction as well as a one-electron oxidation of each cobalt center and that there is no interaction between those cobalt centers. Thus, the two metal centers can be used as separate catalytic sites for the reduction of halogenated organic compounds. In the same article [147] is a hst of literature citations of work done over the past 20 years by the group of Hisaeda on the catalytic behavior of electroreduced vitamin B12 derivatives. 

The reductions of halogenated organic compounds (RX) involve the cleavage of carbon-halogen bonds [62]. Depending on the solvent, supporting electrolyte, electrode material and potential, it is possible to electrogenerate either alkyl radicals (R ) or carbanions (R ), which then can lead to the fonnation of dimers (R-R), alkanes (RH) and olefins [R(-H)] ... 

Studying the electrochemical reduction of halogenated organic compounds has practical importance, especially related to organic syntheses [62], Moreover, the reductive cleavage of the C-X bond is applicable as a method to convert hazardous chlorinated compound for example, polychlorinated biphenyls (PCBs) to biphenyl by reducing in DMF at -2.8 V vs SCE [63],... 

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