Controlled potential electrolysis at a mercury cathode was used to effect two-electron reductive cleavages of carbon tetrachloride, ethyl trichloroacetate, ethyl bromoacetate, allyl chloride and bromide, benzyl chloride and bromide, ethyl 4-bromobutyrate, 4-bromobutyronitrile, and chloroacetonitrile in the presence of acrylonitrile, ethyl acrylate, diethyl fumarate, and diethyl maléate. The electrochemically generated anion nucleophilically attacked the acceptor to yield adduct anions. The latter evolved into final products by several routes: (a) by protonation, e.g., 4-trichlorobutyronitrile from CCh and acrylonitrile, (b) by cyclization-displacement of halide, e.g., diethyl l-c,hloro-l,2-cyclopropanedicarboxylate from ethyl trichloroacetate and ethyl acrylate, (c) by displacement on halogen of a polyhalo starting material, e.g., diethyl 2,2,4-trichloroglutarate also from ethyl trichloroacetate and ethyl acrylate. The factors that must be considered in the design of these electrochemical syntheses are discussed. Reduction of benzyl chloride in the presence of carbon dioxide led directly to benzyl phenylacetate. Similarly, allyl chloride produced allyl crotonate. Reductive dehalogenative coupling of allyl halides and of ethyl bromoacetate alone are also reported.

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Acrylonitrile has been reductively coupled with acetone, styrene, 1,1-diphenylethylene, benzophenone, and benzaldehyde. When the reduction is carried out at the cathode voltage required for the more difficultly rather than the more easily reduced partner (a) current efficiencies for the mixed products are increased, (b) couplings which otherwise fail can occur, (c) by-product polymer formation may be suppressed, and (d) when either of two by-product hydrodimers must be accepted, the more useful one may be chosen. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.88.90.140 Downloaded on 2015-03-30 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 130.88.90.140 Downloaded on 2015-03-30 to IP

Salze aus aliphatischen Carbonsäuren und tertiären Aminen reagieren mit Alkylhalogeniden zu den entsprechenden Estern.