[2, 7, 12, 18-四甲基-3, 8-二(-1-羟基乙基)-13, 17-二羧基乙基]-卟啉的改进合成

A facile Synthesis of [2, 7, 12, 18-tetramethyl-3, 8-bis (-1-hydroxy ethyl)-13, 17-dicarboxy ethyl]-porphyrin

摘要:

在酸性条件下，氯化血红素(1)与还原性铁粉作用生成原卟啉(2)，通过HBr-冰醋酸加成不经提纯直接加入NaOH溶液，OH-取代仲位Br原子制得目标产物[2, 7, 12, 18-四甲基-3, 8-二(-1-羟基乙基)-13, 17-二羧基乙基]-卟啉(血卟啉)，反应总收率达到90.6%。探讨了脱铁过程中反应温度、时间、还原剂用量等因素对原卟啉(2)合成的影响，时间和pH值对血卟啉(3)合成的影响，实验结果表明，当血红素和铁粉的摩尔比为1:1、反应温度为110?C时原卟啉的产率最高，为98.3%，当pH值为10，反应时间为6 h时，血卟啉的产率最高，为92.1%。通过IR、MS和1HNMR测试技术对产物结构进行了表征。

Abstract:

protoporhyrin(2) was prepared by the demetalation reaction of hemin using HCOOH-Fe powder in formic acid. And [2, 7, 12, 18-tetramethyl-3, 8-bis (-1-hydroxy ethyl)-13, 17-dicarboxy ethyl]-porphyrin (hemato- porphyrin) was prepared through a “one pot” reaction of a HBr-acetic acid addition reaction and a OH- nucleophilic substitution reaction from protoporphyrin without purifying of the intermediate. The total yield of (3) is 90.6%. The effects of temperature, time and the dosage of reducing agent to (2) and the effect of pH and time to the yield of (3) were studied. The reasults show that the yield of (2) reaches a maximum of 98.3% in the molar ratio of hemin to Fe powder 1:1 and the the temperature of 120?C and the optimal reaction pH and reaction time are 10 and 6 h respectively with the yield of 92.1% in synthesis of product (3). The target products were characterized with ESI-MS, FT-IR and 1HNMR.