New 5-cyanotroponoid liquid crystals with a 3,4-dialkoxybenzoyloxy and a 3,4-dialkoxybenzoylamino substituent at the C-2 position were prepared. These derivatives exhibited interdigitated bilayer smectic A phases while the corresponding benzenoids were non-mesogenic. Thermal stabilities of these troponoids were lower than those of 2-(4-alkoxybenzoyloxy)-5-cyanotropones and 2-(4-alkoxybenzoylamino)-5-cyanotropones.