To explore the electrosynthesis of coumarins, cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the reduction of the carbon-chlorine bond of five substituted phenyl 2-chloroacetates at silver cathodes in dimethylformamide (DMF) containing 0.10 M tetra-n-butylammonium tetrafluoroborate (TBABF 4 ) as supporting electrolyte; the five substrates are 2-formylphenyl 2-chloroacetate (1a), 2-acetylphenyl 2-chloroacetate (2a), methyl 2-(2-chloroacetoxy)benzoate (3a), 2-formyl-5-methoxyphenyl 2-chloroacetate (4a), and 2-formyl-3,5-dimethoxyphenyl 2-chloroacetate (5a). We have examined (a) the effects of substituents on the benzene ring of the substrate as well as the nature of the aryl carbonyl moiety on the formation of the coumarin product and (b) the effect of solvent-namely, DMF, acetonitrile (CH 3 CN), benzonitrile (PhCN), and propylene carbonate (PC)-and substrate concentration on the yield of the coumarin. It was found that the most unsubstituted substrate (1a) afforded the highest yield (41%) of the desired coumarin in a DMF-TBABF 4 medium. A mechanistic scheme is proposed to account for the formation of the coumarin. Furthermore, the only other products seen in these reductions are 2-substituted phenols, which are precursors for synthesis of the various substrates.Coumarins have become important in many fields such as biology, medicine, and organic chemistry; for example, coumarins have been employed as polymers for industry. 1 Coumarin and its derivatives exhibit biological activity and could possibly be used as anti-coagulant, 2 antitumor, 3 anti-inflammatory, 4 antibiotic, 5 anti-HIV-1, 5 anti-diabetic, 6 and anti-depressant drugs. 6 Two of the most well-known coumarin derivatives are (RS)-4-hydroxy-3-(3-oxo-1-phenylbutyl)-2H-chromen-2-one (Warfarin) and its sodium salt (Coumadin), both of which are prescribed as anti-coagulants. Additionally, optical properties of coumarins allow them to be employed in applications such as laser devices, light-emitting diodes, and fluorescent markers in biomedical imaging. 7 There are many classic processes for the synthesis of coumarins, 8-12 including the use of transition-metal catalysts; 13-19 however, among all of these methods, the most commonly employed is the Pechmann reaction. 8 Classic approaches allow a large range of derivatives to be prepared, but these methods usually require harsh conditions, such as addition of strong acids, and can afford mixtures of products that are difficult to separate.Despite the many applications of coumarins mentioned above, very few publications can be found that deal with the electrosynthesis of these compounds. In comparison with traditional methods, electrosynthesis can provide many advantages, such as short reaction times, mild reagents, low energy cost, and easily isolated products; and, in most cases, the reaction can be conducted at room temperature. Batanero and co-workers 20-22 studied the electrochemical reduction of various substituted phenyl 2,2,2-trichloroacetates at a mercur...