Tetranitroethylene. In Situ Formation and Diels-Alder Reactions

Article abstract of DOI:10.1021/jo01302a024

The reaction of hexanitroethane with dienes gave the Diels-Alder adducts of tetranitroethylene.Thus, the reaction in refluxing benzene of hexanitroethane with anthracene gave 11,11,12,12-tetranitro-9,10-dihydro-9,10-ethanoanthracene.Similarly, 9-methylanthracene and 9,10-dimethylanthracene gave 9-methyl-11,11,12,12-tetranitro-9,10-dihydro-9,10-ethanoanthracene and 9,10-dimethyl-11,11,12,12-tetranitro-9,10-dihydro-9,10-ethanoanthracene, respectively.Cyclopentadiene reacted with hexanitroethane in methylene chloride at -10 deg C to give 5,5,6,6-tetranitro-2-norbornene.Reaction of the anthracene adduct of tetranitroethylene with sodium iodide gave the sodium salt of 12-nitro-9,10-dihydro-9,10-ethanoanthracen-11-one, which was protonated with acetic acid to give the corresponding nitro ketone.Treatment of the sodium salt with clorine and bromine gave 12-chloro-12-nitro-9,10-dihydro-9,10-ethanoanthracen-11-one and 12-bromo-12-nitro-9,10-dihydro-9,10-ethanoanthracen-11-one, respectively.