MICHAEL REACTIONS OF 2-FLUORO-2,2-DINITROETHANOL AND 2,2-DINITROPROPANOL WITH OLEFINIC AND ACETYLENIC ACCEPTORS

Michael reactions of 2,2-dinitro alcohols were found to take place with or without prior deformulation, depending on the reaction conditions and the nature of the acceptor. 2-Fluoro-2,2-dinitroethanol and ethyl acrylate, methyl vinyl ketone, or acrylonitrile in aqueous alkali gave fluorodinitromethane adducts, whereas ethyl propiolate gave both fluorodinitromethane and alcohol 1:1 adducts, and dimethyl acetylenedicarboxylate gave only the 1:1 alcohol adduct. These acetylenes and 2-fluoro-2,2-dinitroethanol in pyridine gave 1:1 alcohol adducts. Ethyl propiolate and 2,2-dinitropropanol in pyridine gave 1:1 alcohol adduct, and in aqueous solution the salt of 1,1-dinitroethane gave the 1:1 adduct. © 1969, American Chemical Society. All rights reserved.