TY - JOUR
T1 - A non-obvious reaction pathway in the formation of 2-aminobenzene-1,3-dicarbonitriles from α,β-unsaturated ketones or aldehydes
AU - Victory, Pedro
AU - Alvarez-Larena, Angel
AU - Germain, Gabriel
AU - Kessels, Raoul
AU - Piniella, Joan F.
AU - Vidal-Ferran, Anton
PY - 1995/1/2
Y1 - 1995/1/2
N2 - Key intermediates demonstrating a non-obvious reaction pathway leading to 2-aminobenzene-1,3-dicarbonitriles from enones have been isolated and characterised in the reaction between (E)-4-phenyl-3-butene-2-one and propanedinitrile in a basic hydro-alcoholic medium. (E)-4-Phenyl-3-butene-2-one reacts with three molecules of propanedinitrile to give a 6-amino-2-iminobicyclo[2.2.2]-5-octene-1,3,3,5-tetracarbonitrile system which evolves to a substituted cyclohexadiene by elimination of the sodium salt of 1,1,1-tricyanomethane. Further oxidation leads to the final 2-aminobenzene-1,3-dicarbonitrile. The proposed pathway involves more steps and more difficult transformations than previously presented for similar systems. We can not exclude a simpler reaction pathway derived from the double Michael and Knoevenagel adduct of (E)-4-phenyl-3-butene-2-one and propanedinitrile, however we have not found any evidence for this simpler process. © 1994.
AB - Key intermediates demonstrating a non-obvious reaction pathway leading to 2-aminobenzene-1,3-dicarbonitriles from enones have been isolated and characterised in the reaction between (E)-4-phenyl-3-butene-2-one and propanedinitrile in a basic hydro-alcoholic medium. (E)-4-Phenyl-3-butene-2-one reacts with three molecules of propanedinitrile to give a 6-amino-2-iminobicyclo[2.2.2]-5-octene-1,3,3,5-tetracarbonitrile system which evolves to a substituted cyclohexadiene by elimination of the sodium salt of 1,1,1-tricyanomethane. Further oxidation leads to the final 2-aminobenzene-1,3-dicarbonitrile. The proposed pathway involves more steps and more difficult transformations than previously presented for similar systems. We can not exclude a simpler reaction pathway derived from the double Michael and Knoevenagel adduct of (E)-4-phenyl-3-butene-2-one and propanedinitrile, however we have not found any evidence for this simpler process. © 1994.
U2 - https://doi.org/10.1016/0040-4020(94)00937-P
DO - https://doi.org/10.1016/0040-4020(94)00937-P
M3 - Article
VL - 51
SP - 235
EP - 242
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
ER -