AbstractWith an aim of creating new, high affinity dopaminergic ligands, six different 3‐ and 4‐substituted 1‐{2‐[5‐(1H‐benzimidazole‐2‐thione)]ethyl}piperidines and nine related heterocyclic congeners were synthesized and evaluated forin vitrobinding affinity at D1and D2dopamine receptors. Synaptosomal membranes prepared from fresh bovine caudate nuclei were used as a source of the dopamine receptors. Only 4‐[bis‐(4‐fluorophenyl)methylene]‐piperidines, compounds9e, 10d, and11d, expressed moderate affinity for the D1receptors, while all other compounds were inactive competitors of [3H]SCH 23390. Compounds9c, 9d, 10c, 11a, and11cwere inactive in the D2receptor binding assay, as well. Derivatives of 4‐phenylpiperidine (9–11b) and 3‐phenyl‐piperidine (10a) expressed a moderate to low affinity for the D2receptors. However, racemic (±)‐1‐{2‐[5‐(1H‐benzimidazole‐2‐thione)]ethyl}‐3‐phenylpiperidine9aand its enantiomer (+)‐9abehaved as selective, high affinity D2receptor ligands, the latter