含单个(4-对羧基苯氧基苯)取代不对称含硫四氮杂钴卟啉的合成及与磁性纳米粒子的共价连接

摘要

首先以4-硝基邻苯二腈和对羟基苯甲酸乙酯为原料合成前驱体4-对甲酸乙酯苯氧基邻苯二腈(Ⅰ),以马来二腈二硫二钠盐和正溴丁烷为原料合成前驱体双正丁硫基马来二腈(Ⅱ);将上述2种前驱体通过镁模板法合成镁卟啉;再通过酸化脱镁、接金属钴得到六(正丁硫基)-(4-对羧基苯氧基苯)四氮杂钴卟啉[CoPz(S-Bu)6(COOH),Ⅳ];然后将合成的钴卟啉负载在磁性纳米粒子Fe3O4@SiO2@NH2(ASMNP)上;得到一种共价键结合的负载型催化剂ASMNP@CoPz(S-Bu)6(COOH)(Ⅴ),通过UV-Vis、1HNMR、13CNMR、MALDI-TOF-MS、FTIR等对中间体及目标产物进行了表征.%Using 4-nitrophthalonitrile and ethyl p-hydroxybenzoic acid as raw materials,a precursor 4-phenoxy phthalic nitrile(Ⅰ) was synthesized,and using dithiomaleonitrile disodium salt and 1-bromobutane as raw materials,another precursor 2,3-bis(butylthio)maleonitrile(Ⅱ) was synthesized.Then,magnesium porphyrin was synthesized by magnesium template method of the two prepared precursors.Hexa-(n-butylthio)-(4-p-carboxylphenoxy)benzo cobalt porphyrazine(Ⅳ) was synthesized by acidizing,de-magnesium and grafting-cobalt of magnesium porphyrin.The covalent-bonded catalyst ASMNP@CoPz(S-Bu)6(COOH)(Ⅴ)was obtained by loading cobalt porphyrazine on the magnetic nanoparticles Fe3O4@SiO2@NH2(ASMNP).The intermediates and final products were characterized by UV-Vis,1HNMR,13CNMR,MALDI-TOF-MS,FTIR,etc.