Knoevenagel condensation of cyclic ketones with benzoylacetonitrile and N,N′-dimethylbarbituric acid. Application of sterically hindered condensation products in the synthesis of spiro and dispiropyrans by hetero-Diels-Alder reactions

Inverse-electron demand Diels-Alder cycloadditions of sterically hindered cycloalkylidene derivatives of benzoylacetonitrile and N,N′-dimethylbarbituric acid with enol ethers, cyclic enol ethers and also sterically hindered cycloalkylidenecycloalkanes were investigated. New spiro, dispirodihydropyrans, spirouracils, and dispirouracils were obtained. To confirm the experimental results, frontier orbital HOMO and LUMO energies of heterodienes and dienophiles were calculated by semi-empirical AM1, PM3 methods and ab initio Hartree-Fock calculations.

Graphical abstractThe inverse-electron demand Diels-Alder cycloadditions of sterically hindered cycloalkylidene derivatives of benzoylacetonitrile and N,N′-dimethylbarbituric acid with enol ethers, cyclic enol ether and cycloalkylidenecycloalkanes were investigated. New spiro and dispirodihydropyrans, spiro, and dispirouracils were obtained.Download full-size image