This study represents the synthesis of dibenzo and dibenzodiaza crown ether precursors with various functional groups in good yield by employing four different methods using polar protic and aprotic solvents with high boiling points. Also the complexation abilities of all synthesized ligands with Cu2+, Zn2+, and Ag+ were studied by conductometry; thus the conductometric behavior of Cu(NO3)(2), ZnCI2, and AgNO3 in 80% dioxane-water mixture was investigated in the presence of these ligands. The order of formation constant for complexes of the ligands with Cu2+, Zn2+, and Ag+ ions was found to be: Cu2+ > Zn2+ > Ag+ for the ligands of VI, VIL XI, and XII; Cu2+ > Ag+ > Zn2+ for the ligands of III and VIII; and Zn2+ > Cu2+ > Ag+ for the ligands of I, II, IV, V, IX, and X. (C) 2003 Wiley Periodicals, Inc.