An efficient pseudo four-component reaction between substituted 2-hydroxybenzaldehydes, ammonium acetate and different dialkyl but-2-ynedioates for the preparation of (2 E)-2-(6 H,12 H-6,12-epiminodibenzo[ b,f][1,5]dioxocin-13-yl)but-2-enedioates in moderate to good yields (60–83%) was developed. This method uses a variety of cheap and readily available reactants and a wide range of substrates. The structure of a typical product was confirmed by X-ray crystallography.