[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

在酸性条件下,氯化血红素(Ⅰ)与还原性铁粉作用生成原卟啉(Ⅱ),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制得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,Ⅲ),反应总产率达到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(Ⅱ)合成的影响,反应时间和pH对血卟啉(Ⅲ)合成的影响。结果表明,当氯化血红素和铁粉的摩尔比为1∶1、反应温度为110℃时,原卟啉的产率最高达98.3%;当pH=10,反应时间为6 h时,血卟啉的产率最高达92.1%。通过IR、MS和1HNMR对产物结构进行了表征。

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

Protoporhyrin(Ⅱ) was prepared by the demetalation reaction of hemin using HCOOH-Fe powder.And the target product of2,7,12,18-tetramethyl-3,8-bis(1-hydroxy ethyl)-13,17-dicarboxy ethyl]-porphyrin(hematoporphyrin) was prepared through the "one pot" reaction of an HBr-acetic acid addition reaction and an OH-nucleophilic substitution reaction from protoporphyrin without purifying the intermediate.The total yield of hematoporphyrin(Ⅲ) is 90.6%.The effects of temperature,time and the dosage of reducing agent to Ⅱ and the effect of pH and time on the yield of Ⅲ were investigated.The results show that the yield of Ⅱ reaches a maximum of 98.3% in the molar ratio of hemin to Fe powder 1∶ 1 and at the the temperature of 110 ℃ and the optimal reaction pH and reaction time are 10 and 6 h respectively with a maximum yield of 92.1% in the synthesis of product Ⅲ.The target products were characterized with FT-IR,ESI-MS and 1HNMR.