Part I: Dibenzotetraaza crown ethers. Part II: Synthesis and characterization of chlorophenylplumbates

Part I. Dibenzotetraaza (DBTA) crown ethers were prepared from benzimidazole. They are tetraaza analogues of dibenzo crown ethers, containing o-phenylenediamine moieties. Overall yields were generally high. No high-dilution conditions were required for the ring-closing step. Unsubstituted crown ethers ranging from 18-crown-6 to 42-crown-14 were prepared and characterized. They are stable under ambient conditions.; The synthesis was extended to include crown ethers with modified ether bridges (i.e.; bridges containing sulfur, and catechol-, and 2,3-naphtalenediol-moieties).; Crown ethers with substituents at the aromatic rings were prepared. Compounds with electron-donating substituents were obtained as stable solids. Compounds with strongly electron-withdrawing substituents are prone to oxidation, especially in solution.; Several benzimidazolidine crown ethers were synthesized. They are DBTA crown ether analogues with methylene-bridges between neighboring nitrogen atoms.; The N-alkylation of unsubstituted DBTA crown ethers was investigated. Direct alkylation with alkyl iodides proceeded smoothly in the presence of K₂CO₃. Tetra(N-organyl) crown ethers are stable under ambient conditions.; X-ray crystal structures were obtained for three macrocycles.; The general synthesis was also applied to the formation of N,N ′-diorganyl-o-phenylenediamines. They were sensitive towards oxidation.; Unsubstituted and tetra(N-alkyl) DBTA crown ethers were included in corrosion protection studies of certain steels and aluminum alloys. They were not as effective as commercially available crown ethers.; Picrate extraction studies were performed to determine the complexation ability of some representative benzoaza crown ethers. Within the group of metals tested, tetra(N-methyl)DBTA-18-crown-6 extracted moderate to high amounts of all alkaline earth-, transition-, and lanthanide-metal ions. The N-H crown ethers tested showed good selectivity, with high extraction values for Pb2+, and somewhat smaller values for Dy 3+. Their extraction-values for the other ions were very low.; Part II. [PBun₄]+ ₂[PCl₄Ph₂]2− is formed in the reaction of [PBun₄]+ Cl − with Ph₂PbCl₂ at 180°C. [PPh ₄]+ Cl− and Ph₂PbCl ₂ form [PPh₄]+[PbCl₂Ph₃] − at 260°C. Both compounds were studied spectroscopically. X-ray crystal structures and mass-spectroscopy data were obtained. The compounds consist of isolated cations and anions.