Conjugated macrocycles related to the porphyrins. 25. Proton NMR spectroscopic evidence for a preferred [18]annulene substructure in carbaporphyrins from the magnitude of selected 4J(H,H) CH=C-CH3 coupling constants

Dachun Liu; Timothy D Lash

doi:10.1021/jo020703u

Conjugated macrocycles related to the porphyrins. 25. Proton NMR spectroscopic evidence for a preferred [18]annulene substructure in carbaporphyrins from the magnitude of selected 4J(H,H) CH=C-CH3 coupling constants

J Org Chem. 2003 Mar 7;68(5):1755-61. doi: 10.1021/jo020703u.

Authors

Dachun Liu¹, Timothy D Lash

Affiliation

¹ Department of Chemistry, Illinois State University, Normal, Illinois 61790-4160, USA.

PMID: 12608788
DOI: 10.1021/jo020703u

Abstract

Two new benzocarbaporphyrins with four or five alkyl substituents have been synthesized by the "3 + 1" MacDonald methodology. At lower temperatures, the proton NMR spectrum of the asymmetrically substituted carbaporphyrin 8 gave two NH resonances, while carbaporphyrin 9, which retains a plane of symmetry, gave only one resonance of this kind. As no additional peaks were seen for the remaining protons, these data strongly support the proposal that a single tautomer predominates in solution where the two NH protons flank the interior CH. Carbaporphyrin 8, which has a CH=CMe unit on the pyrrolic ring opposite the indene moiety, gave a long-range coupling constant of 4J(Me,H) = 1.3-1.4 Hz. On the other hand, the CH=CMe units of 9, which correspond to the pyrrole rings on each side of the carbocyclic moiety, gave 4J(Me,H) = 0.9-1.0 Hz. These values are in accord with those expected if the exterior carbon-carbon bonds of the pyrrole units next to the indene ring are part of a fully delocalized 18pi electron system, while the C=C bond of the remaining pyrrole ring retains substantial olefinic character.