Synthesis and Diels–Alder Reactions of Some New (Phthalocyanine)nickel Complexes

✍ Scribed by Bernd Hauschel; Reiner Jung; Michael Hanack

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 367 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199904)1999:4<693::aid-ejic693>3.0.co;2-q

✦ Synopsis

The octasubstituted (phthalocyanine)nickel complexes 4a,b, synthesized using a statistical approach. Their tetracyclone adducts 17, 18a,b,c can be used for the synthesis of ladder-soluble in common organic solvents, bearing four dienophilic functionalities were synthesized from the corresponding type phthalocyanine dimers. The dimer 22 was synthesized from 18c and p-benzoquinone via the isobenzofuran phthalodinitriles 3a,b and nickel(II) acetate. Reaction of 4a with tetracyclone 5 led to the phthalocyanine-tetracyclone intermediate 19 and the benzoquinone adduct 21. For dehydration experiments the naphthoquinone monoadduct adduct 6 which is a precursor for an intermediate phthalocyanine 7 containing four isobenzofuran moieties. 23 was synthesized from 18c. Dehydration of 22 and 23 was carried out successfully with p-toluenesulfonic acid. The The capability of 7 to react as tetrakis(diene) was demonstrated by its reaction with naphthoquinone. Diels-Alder reactions are discussed with respect to the occurring exo/endo ratio. Furthermore, the unsymmetrical phthalocyanines 13 and 16a,b,c containing one dienophilic functionality were tetrakis(dienophilic), octaalkoxy-substituted PcNi com- [a]