双(对-氨基苯基)-2,3,7,8,12,13,17,18-八甲基卟啉及其金属衍生物的合成与表征

从3-甲基-2,4-戊二酮出发,经多步反应合成了3,3′,4,4′-四-甲基-2,2′-二吡咯基甲烷(TMDPM),改进了合成TMDPM的脱羧反应.研究了TMDPM与对-硝基苯甲醛反应合成meso-5,15-双-苯基-卟啉反应,发现对-甲基苯磺酸是卟啉原合成的良好催化剂,2,3-二-氯-5,6二氰基-1,4-苯醌是将卟啉原转化为卟啉的良好氧化剂;硝基卟啉经SnCl₂还原成氨基卟啉后,用固-液抽提进行氨基卟啉的纯化,得到了5,15-双(对-硝基苯基)-2,3,7,8,12,13,17,18-八甲基卟啉、5,15-双(对-氨基苯基)-2,3,7,8,12,13,17,18-八甲基卟啉及其金属衍生物,并表征了其结构

Synthesis and Characterization of meso-5,15-Bis(p-aminophenyl)-2,3,7,8,12,13,17,18-octamethyl-porphyrin and Its Metal Derivatives

An important compound of 3,3′,4,4′-tetramethyl-2,2′-dipyrrolylmethane (TMDPM, 6) was synthesized through multi-step-reaction starting from 3-methyl-2,4-dipentadione.Therein, the reaction for converting 3,3′,4,4′-tetramethyl-2,2′-dipyrrolylmethane-5,5′-dicarbonate(5) to TMDPM waSImproved by substituting hydrazine witHEthanolamine as decarboxylation agent.The synthesis of meso-15,15-bis-phenyl-porphyrin by dipyrrolylmethane procedure waSInvestigated.It was found that p-toluenesulfonic acid was the efficient catalyst for condensation of compound 6 with nitrobenzaldehyde to porphyrinogen (7), and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone(DDQ) was effective reagent for oxidizing of compound 7 to nitroporphyrin.After the hydrogenation of nitro-groups by SnCl₂/concentrated HCl system to amino-groups, the extraction of the resulted aminoporphyrin by solid-mixture/chloroform process conducted better effects than aqueous-mixture/chloroform process.Following the methods aforesaid, several new porphyrin compoundSIncluding 5,15-bis(4-nitrophenyl)-2,3,7,8,12,13,17,18-octamethyl-porphyrin(BNPP, 8),5,15-bis(4-aminophenyl)-2,3,7,8,12,13,17,18-octamethyl-porphyrin(BAPP, 9) and metal-BAPP were synthesized.Their structures and absorption properties were characterized as well.