5,10,15,20-四[4-(2,3-环氧丙氧基)苯基]卟啉的合成与表征

doi:10.3969/j.issn.1000-1565.2015.01.009

摘要/Abstract

摘要： 以正丙酸、冰乙酸和硝基苯为混合溶剂, 以对羟基苯甲醛和吡咯为原料, 合成了5,10,15,20-四(4-羟基苯基)卟啉(THPP)．然后以THPP与环氧氯丙烷为原料，在异丙醇中以氢氧化钠为催化剂合成了5,10,15,20-四[4-(2,3-环氧丙氧基)苯基]卟啉(TEPPP)．利用傅里叶变换红外光谱仪(FTIR)、核磁共振波谱仪(NMR)、紫外可见分光光度计(UV-Vis)和荧光分光光度计分别对THPP和TEPPP的化学结构和光学性质进行了表征与测试．结果表明:1 349 cm-1和916 cm-1处为TEPPP卟啉环中C = N键伸缩振动吸收峰和环氧化物环的(C―O―C键)不对称伸缩振动吸收峰．TEPPP的1H NMR谱图中，在δ 2.92～4.60内5个位移峰峰面积比为1:1:1:1:1，与TEPPP中环氧基团的不同氢原子数比相一致．TEPPP的UV-Vis谱图具有与卟啉结构相符合的吸收峰．通过荧光光谱研究了THPP和TEPPP的荧光性质，并计算得到了二者的荧光量子产率分别为0.08和0.16．

关键词: 卟啉, 5,10,15,20-四[4-(2,3-环氧丙氧基)苯基]卟啉, 紫外可见光谱, 荧光光谱, 荧光量子产率

Abstract: 5,10,15,20-tetra(4-hydroxylphenyl)porphyrin (THPP) was synthesized by using p-hydroxybenzaldehyde and pyrrole as raw materials, propionic acid, acetic acid and nitrobenzene as solvent. 5,10,15,20-tetra[4-(2,3-epoxypropoxy)phenyl]porphyrin (TEPPP) was prepared by using THPP and epichlorohydrin as materials in isopropanol with sodium hydroxide as catalyst. The chemical structure and optical properties of THPP and TEPPP were characterized and tested by Fourier transform infrared spectrometer (FTIR), nuclear magnetic resonance spectrometer (NMR), ultraviolet-visible (UV-Vis) spectrophotometer and spectrofluorophotometer, respectively. The absorption peaks at 1 349 cm-1 and 916 cm-1 are attributed to C = N bond stretching vibration absorption peaks of TEPPP porphyrin ring and C―O―C bond asymmetric stretching vibration absorption peak of epoxide ring in FTIR spectrum of TEPPP, respectively. In 1H NMR spectrum of TEPPP, the peak area ratio of 5 chemical shift peaks was 1:1:1:1:1 between 2.92 ppm to 4.60 ppm, which was consisted with the ratio of the hydrogen atom number of epoxy group. The absorption peaks of TEPPP were similar to those of porphyrin in UV-Vis spectrum. The fluorescence properties of THPP and TEPPP were studied by fluorescence spectroscopy and fluorescence quantum yield were 0.08 and 0.16, respectively.

Key words: porphryrin, 5,10,15,20-tetra[4-(2,3-epoxypropoxy)phenyl]porphyrin, ultraviolet-visible spectroscopy, fluorescence spectroscopy, fluorescence quantum yield

中图分类号:

O631.5

王苗苗，刘耀军，王园，王耀辉，赵洪池. 5,10,15,20-四[4-(2,3-环氧丙氧基)苯基]卟啉的合成与表征[J]. 河北大学学报(自然科学版), 2015, 35(1): 48-53.

WANG Miaomiao, LIU Yaojun, WANG Yuan, WANG Yaohui, ZHAO Hongchi. Synthesis and characterization of 5,10,15,20-tetra[4-(2,3-epoxypropoxy)phenyl]porphyrin[J]. Journal of Hebei University (Natural Science Edition), 2015, 35(1): 48-53.

参考文献

[1] 杨建东, 王都留, 卢小泉. 卟啉微纳米材料的制备及应用研究进展[J]. 应用化学, 2012, 29(10): 1099-1106.
YANG Jiandong, WANG Duliu, LU Xiaoquan. Recent development in the preparation and application of porphyrin micro-and nanomaterials[J]. Chinese Journal of Applied Chemistry, 2012, 29(10): 1099-1106.
[2] 童沈阳, 孙国斌. 卟啉在分析化学中的应用[J]. 化学试剂, 1987, 9(1): 29-38.
TONG Shenyang, SUN Guobin. Porphyrin application in analytical chemistry[J]. Chenical Reagents, 1987, 9(1): 29-38.
[3] KANTONIS G, TRIKERIOTIS M, GHANOTAKIS D F. Biocompatible protoporphyrin Ⅸ-containing nanohybrids with potential applications in photodynamic therapy[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2007, 185(1): 62-66.
[4] 蔡其洪. 荧光分析在卟啉作为肿瘤标志物研究中的应用[J]. 现代诊断与治疗, 2006, 17(2): 96-98.

CAI Qihong. Application of fluorescence analysis in study of porphyrin as a cancer marker[J]. Modern Diagnosis and Treatment, 2006, 17(2): 96-98.
[5] 沈光远. 卟啉抗癌药物的研究以及桃儿七中有效成分的超临界CO2萃取技术研究[D]. 兰州: 兰州大学, 2006.
SHEN Guangyuan. Studies on the anticancer drug bonding porphyrin and studies on the SC-CO2 techniques extraction fron podophyllum emodi wall[D]. Lanzhou: Lanzhou Univesity, 2006.
[6] DOMANS D E, FUKUMURA D, JAIN P K. Photodynamic therapy for cancer[J]. Nature Reviews Cancer, 2003, 3(5): 380-387.
[7] SESSLER J L, KARNAS E, SEDENBERG E. Porphyrins and expanded porphyrins as receptors[M]//STEED J W, GALE P A. supramolecular chemistry: from molecules to nanomaterials. volume 3: molecular recognition. John Wiley & Sons, Ltd, 2012:1045-1074.
[8] ROTHEMUND P. A new porphyrin synthesis: the synthesis of porphyrin[J]. Journal of the American Chemical Society. 1936, 58(4): 625-627.
[9] ADLER D A, LONGO F R, SHERGALIS W. Mechanistic investigation of porphyrin syntheses[J]. Journal of the American Chemical Society, 1964, 86(15): 3145-3149.
[10] RYU B Y, EMICK T. Bisphenol-1,2,3-triazole (BPT) epoxies and cyanate esters: synthesis and self-catalyzed curing[J]. Macromolecules, 2011, 44(14): 5693-5700.
[11] 李忠芳, 王宇新, 王亚权. Meso-5,10,15,20-四(对羟基苯基)卟啉及其配合物的新合成方法[J]. 山东理工大学学报: 自然科学版，2003, 17(1): 1-7.
LI Zhongfang, WANG Yuxin, WANG Yaquan. Synthesis and characterization of meso-tetrakis(4-hydroxylphenyl) porphyrin and its complexes[J]. Journal of Shandong University of Technology: Sci & Tech, 2003, 17(1): 1-7.
[12] LAKSHMI M. S., REDDY B. S. R. Synthesis and characterization of new epoxy and cyanate ester resins[J]. European Polymer Journal, 2002, 38(4): 795-801.
[13] JAIN P., CHOUDHARY V., VARMA I. K. Effect of structure on thermal behaviour of epoxy resins[J]. European Polymer Journal, 2003, 39(1): 181-187.
[14] MERTZEL E., KOENIG J. L. pplication of FT-IR and NMR to epoxy-resins[J]. Advances in Polymer Science, 1986, 75: 73-112.
[15] 赵洪池, 王耀辉, 王畅, 等. 5-[4-(2,3-环氧丙氧基)苯基]-10,15,20-三苯基卟啉的合成与表征[J]. 河北大学学报: 自然科学版, 2013, 33(2): 148-153.
ZHAO Hongchi, WANGYaohui, WANG Chang, et al. Synthesis and characterization of 5-[4-(2,3-epoxypropoxy)phenyl]-10,15,20-triphenylporphyrin[J]. Journal of Hebei University：Natural Science Edition, 2013, 33(2): 148-153.
[16] 蔡晓莹, 肖义. 5,10,15,20-四(4-羟基苯基)卟啉的合成及光谱性质的研究[J]. 染料与染色, 2006, 43(5): 30-33.
CAI Xiaoying, XIAO Yi. A study on the synthesis and spectral properties of 5,10,15,20-tetrakis(4-hydroxyphenyl)-porphyrin [T(4-OH P)P][J]. Dyestuffs and Coloration, 2006, 43(5): 30-33.
[17] 郭喜明, 师宇华, 张忆华, 等. 系列羟基苯基卟啉的合成及其荧光光谱研究[J]. 有机化学, 2006, 26(2): 247-251.
GUO Ximing, SHI Yuhua, ZHANG Yihua, et al. Synthesis of p-hydroxylphenylporphyrin arrays and their fluorescence spectrum study[J]. Chinese Journal of Organic Chemistry, 2006, 26(2): 247-251.
[18] 王杏乔, 王丛笑, 王清民, 等. 光诱导下卟啉蒽醌分子内电子转移过程的研究(Ⅰ)-荧光法[J]. 高等学校化学学报, 1997, 18(6): 834-839.
WANG Xingqiao, WANG Congxiao, WANG Qingmin, et al. A study of intramolecular electron transfer process of porphyrin-anthraquinone under photoinduction (Ⅰ)–fluorescence method[J]. Chemical Journal of Chinese Universities, 1997, 18(6): 834-839.