Rational Synthesis of 5,10-Diazaporphyrins via Nucleophilic Substitution Reactions of α,α'-Dibromotripyrrin and Dihydrogenation to Give 5,10-Diazachlorins.

We report here the first rational synthesis of 5,10-diazaporphyrins via nucleophilic substitution reactions of α,α'-dibromotripyrrin. Uses of 1,3-diiminoisoindoline and 3,4-di(ethylsulfanyl)pyrrole-2,5-diimine as nucleophiles allowed for synthesis of 5,10-diazabenzoporphyrin (2) and 5,10-diaza-7,8-di(ethylsulfanyl)porphyrin (3). 3 was reduced to 5,10-diazaporphyrin (4), 5,10-diaza-2,3-dihydrogenated porphyrin (5), and 5,10-diaza-7,8-dihydrogenated porphyrin (6) with yields that were dependent upon reduction conditions. All the structures of these products were confirmed by X-ray crystallographic analysis. Their optical and electrochemical properties have been comparatively studied with those of 5,15-diazaporphyrin (7) and 5,15-diazachlorin (8). Furthermore, NH tautomers of 2 and 4 were observed as different species in solution, and the dynamic NH tautomeric behavior was studied in 4.