A Diels-Alder reaction between 5-substituted 1,4-naphthoquinones and 1-acetoxy-1,3-butadiene was carried out. The optimization of reaction conditions [4 + 2] –cycloaddition were carried out. The dependence of the nature of the substituent in the 5th position of 1,4-naphthoquinone on the regioselectivity of Diels-Alder reaction was established. Tricarbocyclic derivatives of 5-R-1,4-naphthoquinones were synthesized.