Synthesis and molecular recognition for tetraaza[14]annulenes and their complexes containing hydroxy groups

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1. Synthesis of Tetraaza[14]annulene and its Nickel(II) Complex-The nickel(II) complex (1-Ni) was prepared from 1,2-diaminobenzene, acetylacetone and nickel(II) acetate tetrahydrate. The metal-free compound (1) was prepared from complex (1-Ni) by treatment of hydrochloric acid gas.2. Synthesis of Acyl Chlorides-Benzyloxybenzoic acid were synthesized from hydroxybenzoic acid and benzylbromide in the presence of sodium hydroxide. Refluxing the benzyloxydibenzoic acids with thionyl chloride gave acyl chlorides (2).3. Synthesis of Tetraaza[14]annulene and its Nickel(II) Complex with hydroxy Groups-The reaction of compounds (1,1-Ni) with various benzyloxybenzoyl chlorides (2) led to the corresponding 7,16-dibenzoylated compound (3,3-Ni) in refluxing tolunene containing triethylamine. These compounds with hydroxy groups (4,4-Ni) were obtained in reduction of the compounds (3,3-Ni).4. Molecular(Recognition of Tetraaza[14]annulene and its Nickel(II) Complex with Hydroxy Groups-The compounds (4,4-Ni) have the sizeable cavities which include some quinone compounds. The cavity needs the hydroxy groups in the 7,16-positions because the formation of hydrogen bond between compounds (4,4-Ni) and quinone compounds is of a great importance for the stability of resulting inclusion compounds. Judging from the behavior of ィイD11ィエD1H NMR and IR spectra, the compounds (4,4-Ni) are presumed to exist in inclusion compounds.5. Discussion about Molecular Recognition Tetraaza[14]annulene and its nickel(II) Complex with Hydroxy Group-The results of IR and ィイD11ィエD1H NMR spectra show very week interaction between compounds (4,4-Ni) and quinone compounds with hydrogen bonds.