3,8双-乙酰基次卟啉二甲酯的合成  

Synthesis of 3,8-Bisacetyl Deuteroporphyrin Dimethyl Ester

作　　者：徐士超[1] 胡炳成[1] 崔巧利[1] 周维友[1] 罗海滔[1] 刘祖亮[1] 

机构地区：[1]南京理工大学化工学院,南京210094

出　　处：《应用化学》2011年第6期657-661,共5页Chinese Journal of Applied Chemistry

基　　金：江苏省自然科学基金(BK2009386);南京理工大学科技发展基金(2010GJPY043)资助项目

摘　　要：以氯化血红素(Ⅰ)为原料,经过溴化氢-冰醋酸加成反应、羟基亲核取代反应和无水氯化氢催化酯化反应制得3,8双--(1羟-基乙基)次卟啉二甲酯(Ⅲ),然后通过琼斯试剂氧化反应制备了3,8双-乙酰基次卟啉二甲酯(Ⅳ)。考察了血红素与溴化氢-冰醋酸饱和溶液反应过程中温度和时间对3,8双--(1羟-基乙基)次卟啉二甲酯(Ⅲ)产率的影响;改进了酯化反应的实验条件;选用了廉价易得、选择性较好的羟基选择性氧化剂。实验结果表明,当反应温度为35℃、反应时间为25 h时,血卟啉(Ⅱ)的产率最高,为98.5%;当催化剂为无水氯化氢时产物(Ⅲ)的产率最高,为72.1%;使用琼斯试剂做氧化剂使实验成本大大降低。通过1H NMR、MS和IR测试技术对产物结构进行了表征。3,8-Bis-（1-hydroxyethyl）deuteroporphyrin dimethyl ester（Ⅲ） was prepared from hemin（I） by the ways of HBr-H3CCOOH addition reaction,OH-nucleophilic substitution reaction and anhydrous hydrogen chloride catalyzed esterification.It was then oxidized by Jones reagent to form 3,8-bisacetyl deuteroporphyrin dimethyl ester（Ⅳ）.The effects of reaction temperature and reaction time on the yield of 3,8-bis-（1-hydroxy-ethyl） deuteroporphyrin dimethyl ester（Ⅱ） were studied.The conditions of esterification reaction were modified.A cheaper and selective oxidant was used in the synthesization of 3,8-bisacetyl deuteroporphyrin dimethyl ester（Ⅳ）.The results showed that the yield of hematoporphyrin（Ⅱ） reaches to the highest of 98.5% when the temperature is 35 ℃ and the reaction time is 25 h.The yield of hematoporphyrin dimethyl ester is 72.1% when the catalyst is anhydrous hydrogen chloride.The cost of 3,8-bisacetyl deuteroporphyrin dimethyl ester（Ⅳ） was decreased greatly when the oxidant is Jones reagent.The target products were characterized with 1H NMR,IR and MS.

关 键 词：血红素 血卟啉 卟啉衍生物 合成 

分 类 号：O629.9[理学—有机化学]