With three-component condensation of 1,2,4-triazol-3-amine, hydroxy-substituted aromatic aldehyde (2-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-hydroxy-3-methoxybenzaldehyde, 2-naphthalene-carbaldehyde), cyclohexanone, the aldehyde component has a defining impact on the shaping of triazologic hydroquinazolines with different types of rings articulation and the position of the double bond in them (C4a–C5 and C4a–C8a). When salicylic aldehyde is used, the positional isomers of the triazologic hexahydroquinazolines of angular and linear structure are formed in an equimolar ratio.