Metal-Promoted Reactivity of Cyanogen toward Compounds Containing Active Hydrogen Atoms on Carbon. 2. Synthesis of a Fully Functionalized Substituted Pyrimidine from Cyanogen and Acetylacetone Catalyzed by Acetylacetonate Complexes of Transition Metals

The reactivity of various metal acetylacetonate complexes [M(acac)n] (n = 2 for = MnII, FeII, CoII, CuII, PdII; n = 3 for M = Crm, MnIII, Fem) has been tested toward C2N2 at ambient conditions in CH2C12. All [M(acac)2] complexes, except [Pd(acac)2], react with cyanogen to give addition compounds which are found to be unstable for Mn, Fe, and Co and quite stable for Cu. The Cu complex displays a stoichiometric composition [Cu(acac-C2N2)2] and is found to be isostructural with the complex bis(3-(cyanoiminomethyl)-2,4-pentanedionato)nickel(II). Crffl and Fera complexes are found to be unreactive in the employed conditions, and [Mn(acac)3] behaves similarly to [Mn(acac)2], The complexes found to be reactive with cyanogen are seen to be effective catalysts for the addition reaction of cyanogen to Hacac in mild conditions. On the basis of X-ray data, the organic compound obtained has been identified as a heavily functionalized pyrimidinic compound of stoichiometry (Hacac.C2N2)2. X-ray structure and IR, NMR, visible-UV, and mass spectra, referring to this novel compound, are given and discussed. © 1981, American Chemical Society. All rights reserved.