Summary.The reactive 1:1 intermediate produced in the reaction between 2,6-dimethylphenyl isocyanide and dimethyl acetylenedicarboxylate was trapped by N,N -dimethylbarbituric acid to yield the isomeric products dimethyl 7-(2,6-dimethylphenylamino)-1,3-dimethyl-2,4-dioxo-4H-pyrano[3,2-d]pyrimidine-5,6-dicarboxylate and dimethyl (E)-2-((2,6-dimethylphenylamino)-(1,3-dimethyl-2,4,6-trioxo-pyrimidine-5-ylidene)-methyl)-but-2-enedioate in a nearly 1:1 ratio and an overall yield of 85%. Dynamic effects were observed in the 1H NMR spectra of these compounds and were attributed to restricted rotation around the aryl-nitrogen single bonds and the polarized carbon-carbon double bond.