Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Synthesis of Core-Modified Porphyins and Studies of Their Temperature-dependent Tautomerism

  • Published : 1999.03.20
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Abstract

The different core-modified porphyrins 21-thia-23-carba-12-aza-5,10-dimesityl-15,20-diphenylporphyrin (6), and their N(12)-methyl derivatives (8) were synthesized by acid-catalyzed [3+1] condensation of the corresponding 16-thia-5,10-dimesityltripyrromethanes and 2,4-bis[(α-hydroxy-α-phenyl)methyl]pyrrole. Spectroscopic evidence indicates the existence of two different tautomeric forms at room temperature in porphyrin (6). A third form of tautomer was observed when the temperature was lowered to 223 K. The most stable tautomer is one in which the nitrogenic proton resides outside the core of the macrocycle. The ratio of the three different tautomers (outer N-H/ two inner N-H, i.e. 6/12/13) was 1/l/0.5 in the case of (6) while the ratio of 1/l/0.3 was observed in the case of (10). In the case of 21-oxa-23-carba-12-aza-5,10,15,20-tetraphenylporphyrin (7), the only stable tautomeric form observed by 1H NMR was the one that nitrogenic proton resides inside the core on

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