While most of porphyrins and related macrocycles have been synthesized by classical acid-catalyzed condensation and oxidation reactions, nucleophilic aromatic substitution reactions have recently emerged as a new protocol to construct novel porphyrinoids. αα′-Dibromotripyrrin 3 was developed as a useful building block composed of three pyrrolic segments and two meso-carbons, which was allowed to react with various nucleophiles. Herein, we applied this strategy to synthesize carbaporphyrinoids containing two nitrogen atoms at the meso-positions. Reaction of αα′-dibromotripyrrin 3 with meta- and para-phenylenediamine gave diazabenziporphyrins 8 and 9in good yields. Their oxidized species 12 and 13 were generated by facile oxidation with lead dioxide. While diaza-meta-benziporphyrin 12 exhibited nonaromatic characteristics, diaza-para-benziporphyrin 13 was revealed to be aromatic in view of 1H NMR, bond-alternation, and nucleus-independent-chemical-shift calculations. Curiously, aza-meta-benzicorrole 11 was obtained in a low yield by intramolecular cyclization reaction of α-anilino-α′-bromotripyrrin with potassium carbonate.

中文翻译：

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SN Ar 反应合成氮杂苯并卟啉

虽然大多数卟啉和相关大环化合物是通过经典的酸催化缩合和氧化反应合成的，但最近出现了亲核芳族取代反应作为构建新型卟啉的新方案。αα'-二溴三吡喃3被开发为一种有用的构件，由三个吡咯链段和两个中观-碳，允许与各种亲核试剂反应。在此，我们应用该策略合成了含有两个氮原子的碳卟啉。中观-职位。的反应αα'-二溴三吡喃3和元和对-苯二胺产生二氮杂苯并卟啉8和9在良好的产量。他们的氧化物种12和13用二氧化铅容易氧化生成。虽然二氮杂元-苯并卟啉12表现出非芳香特征，二氮杂对-苯并卟啉13被认为是芳香的1H NMR、键交替和与核无关的化学位移计算。奇怪的是，阿扎——元-苯并考罗11通过分子内环化反应以低收率获得α-苯胺-α'-溴三吡喃与碳酸钾。