|Budget Amount *help
¥3,200,000 (Direct Cost : ¥3,200,000)
Fiscal Year 1999 : ¥600,000 (Direct Cost : ¥600,000)
Fiscal Year 1998 : ¥2,600,000 (Direct Cost : ¥2,600,000)
1. Synthesis of Tetraazaannulene 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 Tetraazaannulene 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 Tetraazaannulene 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 Tetraazaannulene 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.