Department of Chemistry, Knight Chemical Laboratory, The University of Akron, Akron, Ohio 44325-3601, USA.
J Org Chem. 2012 Jul 20;77(14):6043-50. doi: 10.1021/jo300810n. Epub 2012 Jul 6.
Two monosubstituted and one tetrasubstituted N-confused porphyrins (1-3) were prepared in ca. 3-5% yields using a [2 + 2] synthesis. The monosubstituted porphyrins have carbomethoxy (1) or nitro (2) substituents on one of the meso-phenyl groups, while the meso-phenyl groups of the third NCP (3) are substituted with nitro, bromo, and methyl groups in an AB(2)C pattern. The specific regiochemistry of the aryl rings around the macrocycle in each porphyrin was definitively determined using a combination of 1D ((1)H and (13)C) and 2D (gHMBC, gHSQC and ROESY) NMR spectroscopy. The absorption spectra of 1-3 in CH(2)Cl(2) are similar to those of N-confused tetraphenylporphyrin (NCTPP) but have Soret and Q bands that are shifted to lower energies with smaller extinction coefficients in comparison to those for NCTPP.
使用[2+2]合成法，我们制备了两种单取代和一种四取代 N-稠合卟啉（1-3），产率约为 3-5%。这两种单取代卟啉在一个meso-苯基上具有甲氧基（1）或硝基（2）取代基，而第三个 NCP（3）的meso-苯基则以 AB(2)C 模式被硝基、溴基和甲基取代。通过结合使用一维（1H 和 13C）和二维（gHMBC、gHSQC 和 ROESY）NMR 光谱，明确确定了每个卟啉中环上芳环的特定区域化学。1-3 在 CH(2)Cl(2)中的吸收光谱与 N-稠合四苯基卟啉（NCTPP）相似，但与 NCTPP 相比，Soret 和 Q 带的能量更低，消光系数更小。
