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首页> 外文期刊>Chemistry: A European journal >Adaptation of the Rothemund Reaction for Carbaporphyrin Synthesis: Preparation of Meso-Tetraphenylazuliporphyrin and Related Benzocarbaporphyrins
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Adaptation of the Rothemund Reaction for Carbaporphyrin Synthesis: Preparation of Meso-Tetraphenylazuliporphyrin and Related Benzocarbaporphyrins

机译：Rothemund反应对碳卟啉合成的适应性：介孔四苯并az卟啉和相关苯甲碳卟啉的制备

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Electrophilic substitution of azulene has recently been shown to provide the means by which carbon-carbon bonds can be generated to form novel macrocyclic systems such as calixazulenes. These studies inspired us to develop a "one-pot" Rothemund-type synthesis of meso-tetraphenylazuliporphyrin. Azuliporphyrins, a group of cross-conjugated carbaporphyrinoids that exhibit intriguing chemistry and metallation properties, have previously only been available by multistep syntheses. In this work, azulene, pyrrol and benzaldehyde were shown to react in a 1:3:4 ratio in the presence of boron trifluoride etherate to give meso-tetra-phenylazuliporphyrin 7a. The free base shows only a minor diatropic ring current, but addition of TFA generates the related dication which shows greatly enhanced diatropicity where the internal CH shifts from #delta# = +3.35 to -0.5 ppm. Addition of pyrrolidine to 7a gave rise to a carbaporphyrin adduct which showed a porphyrin-like UV/Vis spectrum and the internal CH shifted further up field to give a resonance near #delta# = -5.7 ppm. Treatment of 7a with tertbutyl hydroperoxide in the presence of potassium hydroxide afforded a mixture of benzocarbaporphyrins 9a-c. These tetraphenylcarbaporphyrins wee fully aromatic by NMR spectroscopy and gave typical porphyrin-type UV/Vis spectra with a strong Soret band near 446nm. This new methodology makes these important porphyrin analogues readily available for further study.
机译：最近已经显示，对z烯的亲电取代提供了一种手段，通过该手段可以生成碳-碳键以形成新颖的大环系统，例如杯新氮烷。这些研究启发了我们开发一种“一锅”的罗特蒙德型合成中四苯基氮杂卟啉。 Azuliporphyrins是一组具有交叉作用的碳环卟啉类化合物，它们显示出令人着迷的化学和金属化特性，以前只能通过多步合成法获得。在这项工作中，显示出在三氟化硼醚化物存在下，,、吡咯和苯甲醛以1：3：4的比例反应，生成内消旋-四-苯基az杂卟啉7a。游离碱仅显示较小的变径环电流，但是添加TFA会生成相关指示，从而显着增强了变质性，其中内部CH从＃delta＃= +3.35变为-0.5 ppm。将吡咯烷加到7a上得到碳杂卟啉加合物，其显示出类似卟啉的UV / Vis光谱，并且内部CH进一步向上移动，从而在＃δ=＝-5.7ppm附近产生共振。在氢氧化钾存在下，用氢过氧化叔丁基处理7a，得到苯并碳卟啉9a-c的混合物。这些四苯基碳卟啉通过NMR光谱完全芳香化，并给出典型的卟啉型UV / Vis光谱，在446nm附近具有很强的Soret带。这种新的方法使这些重要的卟啉类似物易于进一步研究。

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