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.
参考文献
| [1] | WANG Shujun,PENG Yuling,FU Li.Synthesis and Nonlinear Optical Characterization of a Chiral M etalloporphyri[J].Chinese J Inorg Chem,2009,25(1):54-59(in Chinees).王树军,彭玉苓,傅丽.新型手性金属卟啉的合成及非线性光学性质研究[J].无机化学学报,2009,25(1):54-59. |
| [2] | Hu B C,Zhou W Y,Tang Y,et al.A Facile Synthesis of Deuteroporphyrins Derivatives under Ultrasound Irradiation[J].Ultrason Sonochem,2010,17:288 -291. |
| [3] | Poltowicz J,Pamin K,Haber J.Influence of Manganese Tetraarylporphyrins Substituents on the Selectivity of Cycloalkanes Oxidation with Magnesium Monoperoxyphthalate[J].J Mol Catal A:Chem,2006,257:154-157. |
| [4] | GAO Shutao,LIU Yanqin,HAN Shitian.Synthesis and Characterization of New m-Chlorophenyl Porphyrin-5-Fluorouracil Compounds[J].Chinese J Appl Chem,2007,24(11):1295-1298(in Chinese).高书涛,刘彦钦,韩士田.新型间氯苯基卟啉-5-氟尿嘧啶化合物的合成与表征[J].应用化学,2007,24(11):1295-1298. |
| [5] | WANG Jun,XIONG Dazhen,ZHANG Chaohong,et al.Damage of DNA under Irradiation of High-frequency Ultrasound in the Presence of Hematoporphyrin[J].Chinese J Appl Chem,2008,25(1):22-26(in Chinese)王君,熊大珍,张朝红,等.高频超声照射下血卟啉(HP)对脱氧核糖核酸(DNA)结构的影响[J].应用化学,2008,25(1):22-26. |
| [6] | Kim Y S,Song R,Kim D H,et al.Synthesis,Biodistribution and Antitumor Activity of Hematoporphyrin-Platinum (Ⅱ)Conjugates[J].Bioorg Med Chem,2003,11:1753-1760. |
| [7] | Liu H H,Wang Y,Shu Y J.Cyclopropanation of Alkenes Catalyzed by Metallophthalocyanines[J].J Mol Catal A:Chem,2006,246:49-52. |
| [8] | Brunner H,Amdt M R,Treittinger B.Porphyrin Platinum Conjugates-New Aims[J].Inorg Chim Acta,2004,357:1649-1669. |
| [9] | Zhou W Y,Hu B C,Liu Z L.Metallo-deuteroporphyrin Complexes Derived from Heme:A Homogeneous Catalyst for Cyclohexane Oxidation[J].Appl Catal A:Gen,2009,358:136-140. |
| [10] | ZHANG Guangming,JI Guozhen,HU Hui.Pyrolytic Degradation of Hematopo rphrin IX Ethers and Synthesis of V'myl Ether Porphrin Compounds[J].Chinese J Org Chen,1998,18:425-431 (in Chinese).张广明,计国祯,胡蕙.血卟啉醚类化合物的裂解反应及乙烯基烷氧乙基次卟啉类化合物的合成[J].有机化学,1998,18:425-431. |
| [11] | Firouzabadi H,Iranpoor N,Amani K.Solvent-Free and Selective Oxidation of Hydroxy Groups to their Corresponding Carbonyl Functions with Ferric Nitrate Activated by Heteropoly Acids[J].Synthesis,2003,3:408-412. |
| [12] | Hu B C,Zhou W Y,Ma D S,et al.Metallo-deuteroporphyrins as Catalysts for the Oxidation of Cyclohexane with Air in the absence of Additives and Solvents[J].Catal Commun,2008,10:83-85. |
| [13] | Dakin L A,Langille N F,Panek J S.Synthesis of the C1'-C11' Oxazole-Containing Side Chain of Leucascandrolide A.Application of a Sonogashira Cross-Coupling[J].J Org Chem,2002,67:6812-6815. |
| [14] | Shiau F Y,Pandey R K,Ramaprasad S,et al.Isomeric Monoacetylmono (1-hydroxyethyl)deuteroporphyrins:Synthesis,Characterization,and Use for the Synthesis of Regioselectively Methyl-and Vinyl-Deuterated Hemins[J].J Org Chem,1990,55:2190-2195. |
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