ADDITION OF ELECTROCHEMICALLY-GENERATED ANIONS TO ALDEHYDES AND OLEFINS - EFFECT OF REACTION MEDIUM AND ANION BASICITY

The electrochemically-induced addition of nitroalkenes to mono and dia ldehydes as well as mono and diolefins was investigated. The reactivit y was highly dependent on the solvent. Selectivity of addition has bee n made possible by controlling the charge injected upon electrolysis o f a pure nitromethane solution in the presence of 1,3- or 1,4-benzened icarboxaldehyde to direct the reaction toward the mono- or bis-(nitroa lcohol). Dehydration of the latter resulted in almost quantitative yie lds of 1,4-bis(2-nitroethenyl)benzene. This diolefin was further submi tted to attack of various electrochemically generated nucleophiles. Wh ether polymerization, double Michael addition or no reaction occurred, depended greatly on the pK(a) and on the structure of the starting an ion. (C) 1997 Elsevier Science Ltd.