四(5-氟尿嘧啶-1-基乙酰氧基苯基）卟啉及其锌配合物的合成

以二环己基碳二亚胺为脱水剂,meso-四(对羟基苯基)卟啉与5-氟尿嘧啶-1-基乙酸反应,合成了一种新型meso-四[4-(5-氟尿嘧啶-1-基乙酰氧基)苯基]卟啉化合物(A),产率12.7%;将其与乙酸锌反应得到其锌配合物(B),产率30.8%。 通过1H NMR、IR、MS、UV-Vis及元素分析确证了卟啉化合物A及其锌配合物B的结构。     

新型-meso-四(4-十四氨基甲酰苯基)卟啉及其-金属（Co）配合物的合成与液晶性能

对羧基苯甲醛和吡咯经缩合反应制得meso-四(4-羧基苯基)卟啉(1); 1与氯化亚砜反应得meso-四(4-氯甲酰基苯基)卟啉(2); 2与n-十四胺反应制得meso-四(4-十四氨基甲酰苯基)卟啉(3); 3与CoC_l2经配位反应合成了meso-四(4-十四氨基甲酰苯基)卟啉钴(4)。 3和4为新化合物,其结构经U-Vis, ¹H NMR和IR表征。偏光显微镜和DSC检测结果表明： 3和4具有液晶性能。     

meso-5，10，15，20-四[3，5-二（辛酰氧基）苯基]卟啉锌（铜）配合物的合成与性能

以3,5-二甲氧基苯甲醛和吡咯为原料,经缩合反应制得meso-5,10,15,20-四（3,5-二甲氧基苯基）卟啉（1）; 1与BBr-3-反应制得meso-5,10,15,20-四（3,5-二羟基苯基）卟啉（2）; 2与辛酰氯反应制得meso-5,10,15,20-四[3,5-二（辛酰氧基）苯基]卟啉（3）; 3分别与ZnCl₂和CuCl₂经配位反应合成了meso-5,10,15,20-四[3,5-二（辛酰氧基）苯基]卟啉锌配合物（4）和meso-5,10,15,20-四[3,5-二（辛酰氧基）苯基]卟啉铜配合物（5）,其结构经FL, UV-Vis, ¹H NMR, IR和元素分析确证。采用差示扫描量热法（DSC）和偏光显微镜研究了4和5的性能。结果表明：4和5为双变液晶,初始转变温度分别为31 ℃和28 ℃。     

2-甲酰基-meso-四苯基卟啉的合成

研究了以金属四苯基卟啉为原料,经由Vilsmeier甲酰化反应制备2-甲酰基-meso-四苯基卟啉的合成方法。不同金属离子、溶剂以及Vilsmeier反应时间等因素对目标化合物的最终收率影响很大。在以铜四苯基卟啉为原料、氯仿为溶剂及Vilsmeier反应时间为5 h的反应体系中,目标化合物的收率可以高达99%以上。     

5,15-二(对-取代苯基)八烷基卟啉及其金属配合物的合成

本文报道了五种5,15-二(对-取代苯基)-2,8,12,18-四乙基-3,7,13,17-四甲基卟啉(Ⅱa—Ⅱe)和五种5,15-二(对-取代苯基)-2,3,7,8,12,13,17,18-八甲基卟啉(Ⅰa—Ⅰe)以及它们的铜、铁、镍金属配合物的合成。这些化合物的结构均经元素分析、UV、~1HNMR和MS鉴定。芳环上不同取代基对卟啉成环反应有一定影响,拉电子基团有利于反应。其顺序如下:NO_2>H>CH_3>OCH_3>N(CH_3)_2。     

水溶性meso-四咪唑基卟啉及其金属配合物的合成

通过2-和4(或5)-咪唑基甲醛分别与吡咯缩合,合成了 meso-四(2-咪唑基)卟啉和 meso-四[4(或5)-咪唑基]卟啉,并考察了它们的水溶性性质。最后用这两种四咪唑基卟啉制备了10种金属卟啉配合物。     

Meso-四(对羟基苯基)卟啉及其金属配合物的合成与表征

以丙酸为溶剂，用吡咯和对羟基苯甲醛直接合成了Meso-四（对羟基苯基）卟啉，探讨了溶剂丙酸和无水乙醇的用量对反应产率的影响；利用液相法合成了Mesc〉四（对羟基苯基）卟啉与Fe^3＋，Mn^2＋，Co^2＋，Ni^2＋，Cu^2＋和Zn^2＋ 6种金属离子形成的配合物，探讨了Meso-（对羟基苯基）卟啉与金属盐用量的比例对产率的影响；利用UV-Vis和MS对合成的物质进行表征．     

meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质

锌卟啉配合物;合成;meso-四-(对甲氧基)苯基卟啉和meso-四-(对甲氧基)苯基卟啉的电化学性质     

meso-四(间烷氧基苯基)卟啉及其金属配合物的合成、表征和液晶性能研究

1987年Gregg等[1]合成了八酯取代卟啉及其Zn配合物并研究了其液晶性,1990年Shimichi等[2]报道了对-烷氧取代型四苯基卟啉(n=10,12)及其Co,Zn配合物(n=10)的液晶性,这些现象引起了人们对卟啉类化合物液晶性能研究的极大兴趣[3],我们在前文[4～6]报道了meso-四(对烷氧苯基)卟啉及其金属配合物的合成、表征和液晶性研究,但目前仍无meso-四(间烷氧基苯基)卟啉及其金属配合物的液晶性能的报道.本文合成了meso-四(间烷氧基苯基)卟啉及其铜、钴、锌配合物四个系列40个化合物,其中未见文献报道的新化合物35个;研究了其合成、分离、纯化方法;对于长链烷氧基取代的间位卟啉配体及其金属配合物,我们采用石油醚-无水甲醇混合溶剂重结晶和冰盐浴长时间冷冻的方法,首次得到这四个系列化合物的晶体或固体,在偏光显微镜下有明显的双折射现象.我们采用1HNMR,MS,IR,UV,元素分析等分析测试表征手段确证了这些化合物的结构,研究了这四个系列化合物的结构与1HNMR,IR,UV,MS的波谱关系及判据,报道和解析了间位长链烷氧基取代的四苯基卟啉铜配合物的1H NMR研究结果.     

新型meso-四(4-十四氨基磺酰苯基)卟啉及其配合物的合成与液晶性能

以吡咯和苯甲醛为原料制得meso-四苯基卟啉(1);1经氯磺化得meso-四(4-氯磺苯基)卟啉(2);2与十四胺反应制得meso-四(4-十四氨基磺酰苯基)卟啉(3);3与醋酸镉经配位反应合成了meso-四(4-十四氨基磺酰苯基)镉卟啉(4)。3和4为新化合物,其结构经UV-Vis,1H NMR和IR表征。偏光显微镜和DSC检测结果表明:3和4均具有液晶性能。     

新型NO供体的合成及其体外释放NO性能

新型NO供体的合成及其体外释放NO性能;金属卟啉;NO载体;合成;体外释NO作用     

取代席夫碱铜金属卟啉的微波辅助合成

微波辅助合成了取代席夫碱铜金属卟啉。 实验结果表明,取代苯甲醛与四(对氨基苯基)铜金属卟啉的缩合反应速率和产率与芳香醛取代基的种类有关,含吸电子基团的芳香醛大于含给电子基团的芳香醛,且随吸电子性的增强而增加,随给电子性的增强而减少。 水杨醛席夫碱铜金属卟啉侧链可与铜离子在碱性条件下形成铜配合物,其催化氧化环己烷的转化率达到了7.68%,环己酮的选择性达到了60.87%。     

Methoxy-isoporphyrins of water-soluble porphyrins: synthesis,characterization and electrochemical properties

Abstract

Methoxy-isoporphyrins of zinc [5,10,15,20-tetrakis(4-sulfonatophenyl)]porphyrin, ZnTSPP (1a) and zinc [5,10,15,20-tetrakis(4-carboxyphenyl)]porphyrin, ZnTCPP (1b) have been synthesized and characterized using standard spectroscopic techniques (Uv-visible, ¹H NMR) , ESI-mass spectrometry and powder X-ray diffraction studies. The isoporphyrins [5-(methoxy)-5,10,15,20-tetrakis(4-sulfonatophenyl)-5H,15H-porphinato]zinc(II) (2a) and [5-(methoxy)-5,10,15,20-tetrakis(4-carboxyphenyl)-5H,21H-porphinato]zinc(II) (2b) are formed due to nucleophilic attack of the methanol to the zinc porphyrin dication. Ceric ammonium nitrate (CAN) was used to oxidize zinc porphyrin and to form zinc porphyrin dication. The electronic spectra of the isoporphyrin complexes 2a and 2b exhibit an intense peak at near IR region . Electrochemical measurements of the synthesized isoporphyrins showed a typical irreversible reduction peak at lower potential. S-containing nucleophiles, which work as reducing agents, convert the zinc isoporphyrins to their parent porphyrins, which supports the electrochemical observations. Their structural properties have been studied using powder X-ray diffraction. The luminescence properties of isoporphyrins were compared with the parent zinc porphyrins.     

New class of potent catalysts of O2.-dismutation. Mn(III) ortho-methoxyethylpyridyl- and di-ortho-methoxyethylimidazolylporphyrins

Three new Mn(III) porphyrin catalysts of O2.-dismutation (superoxide dismutase mimics), bearing ether oxygen atoms within their side chains, were synthesized and characterized: Mn(III) 5,10,15,20-tetrakis[N-(2-methoxyethyl)pyridinium-2-yl]porphyrin (MnTMOE-2-PyP(5+)), Mn(III)5,10,15,20-tetrakis[N-methyl-N'-(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTM,MOE-2-ImP(5+)) and Mn(III) 5,10,15,20-tetrakis[N,N'-di(2-methoxyethyl)imidazolium-2-yl]porphyrin (MnTDMOE-2-ImP(5+)). Their catalytic rate constants for O2.-dismutation (disproportionation) and the related metal-centered redox potentials vs. NHE are: log k(cat)= 8.04 (E(1/2)=+251 mV) for MnTMOE-2-PyP(5+), log k(cat)= 7.98 (E(1/2)=+356 mV) for MnTM,MOE-2-ImP(5+) and log k(cat)= 7.59 (E(1/2)=+365 mV) for MnTDMOE-2-ImP(5+). The new porphyrins were compared to the previously described SOD mimics Mn(III) 5,10,15,20-tetrakis(N-ethylpyridinium-2-yl)porphyrin (MnTE-2-PyP(5+)), Mn(III) 5,10,15,20-tetrakis(N-n-butylpyridinium-2-yl)porphyrin (MnTnBu-2-PyP(5+)) and Mn(III) 5,10,15,20-tetrakis(N,N'-diethylimidazolium-2-yl)porphyrin (MnTDE-2-ImP(5+)). MnTMOE-2-PyP(5+) has side chains of the same length and the same E(1/2), as MnTnBu-2-PyP(5+)(k(cat)= 7.25, E(1/2)=+ 254 mV), yet it is 6-fold more potent a catalyst of O2.-dismutation , presumably due to the presence of the ether oxygen. The log k(cat)vs. E(1/2) relationship for all Mn porphyrin-based SOD mimics thus far studied is discussed. None of the new compounds were toxic to Escherichia coli in the concentration range studied (up to 30 microM), and protected SOD-deficient E. coli in a concentration-dependent manner. At 3 microM levels, the MnTDMOE-2-ImP(5+), bearing an oxygen atom within each of the eight side chains, was the most effective and offered much higher protection than MnTE-2-PyP(5+), while MnTDE-2-ImP(5+) was of very low efficacy.     

几种新型卟啉的合成及其光敏性质

合成了４种新的卟啉配体及其锌的配合物，并用红外光谱、紫外可见光谱、元素分析等手段对它们进行了表征。初步实验表明所合成的卟啉配体和金属卟啉均具有光敏性。     

meso-四(对烷氧苯基)卟啉金属配合物的合成和性能研究(II)

合成了Zn、Pb两个系列卟啉金属配合物12个,其中6个为未见文献报道的新化合物,用元素分析、IR、UV、^1HNMR、MS确证了其结构。总结了Zn、Pb与卟啉类配体配合的IR、UV、^1HNMR判据。研究了这两个系列化合物的液晶性能,发现9个化合物具有液晶性。     

Convenient scaffold for forming heteroporphyrin arrays in aqueous media

A new methodology for preparing heteroporphyrin arrays in aqueous solution has been presented. The present method is based on the extremely strong ability of heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMe-beta-CD) to include 5,10,15,20-tetrakis(p-substituted-phenyl)porphyrins (Por) affording trans-type 1:2 complexes of the porphyrins and TMe-beta-CD. Two different Por-per-O-methylated beta-CD (per-Me-beta-CD) conjugates were synthesized. Conjugate 2 was prepared by an S(N)2 reaction of 5,10,15,20-tetrakis(p-hydroxyphenyl)porphyrin and per-O-methylated beta-cyclodextrin having one primary OTs group. Four per-Me-beta-CD moieties are attached to the meso positions of 2. Conjugate 3, synthesized from 5-(p-hydroxyphenyl)-10,15,20-tris(3,5-dicarboxyphenyl)porphyrin and monotosylated per-O-methylated beta-cyclodextrin, has one per-Me-beta-CD moiety at the periphery of the porphyrin. Conjugate 2 yields a stable 1:4 complex with the zinc complex of 5-phenyl-10,15,20-tris(3,5-dicarboxyphenyl)porphyrin (8) in the dissociated form. In this system, the energy transfer from photoexcited Zn-8 to free base 2 occurs with 85% efficiency. Conjugate 3 forms a very stable 1:1 complex with Zn-8 (K = (7.0 +/- 0.3) x 10(5) dm(3) mol(-1)) with an energy transfer efficiency (93%) larger than that obtained in the case of 2. The structure of the 3-Zn-8 complex, which can account for the efficient energy transfer, was deduced from (1)H NMR spectroscopy. Intramolecular fluorescence quenching of 2 and 3 by Fe(III)-8 also occurred through an electron-transfer process as the main quenching mechanism. The present method is a very simple and convenient means to construct various heteroporphyrin arrays in aqueous solution.     

Meso位单取代卟啉及其配合物的合成、表征和光谱性质

设计合成了一系列新型的meso位N,N-二甲氨基苯基或N-苯基咔唑基单取代卟啉(5a~c)及其锌配合物(6a~c),用高分辨质谱、¹H NMR、紫外-可见光谱及X射线单晶衍射方法等对结构进行了表征;研究了卟啉化合物及其配合物的热稳定性及荧光性质。结果表明,这些卟啉化合物及其锌配合物在400~410 nm之间具有强的吸收且具有很好的热稳定性,荧光量子产率在0.05~0.09;另外还分析了meso位不同取代基对光谱性质的影响。     

Cellular uptake and photocytotoxicity of glycoconjugated porphyrins in HeLa cells

Thirty-two glycoconjugated porphyrins were synthesized by a modification of Lindsey method in the presence of Zn(OAc)(2).2H(2)O as a template. The Zn(2+) ion template strategy improved the yield about three-fold in the case of meta-substituted tetraphenylporphyrins. In addition, free-base porphyrins were obtained almost quantitatively by demetalation with 4 M HCl. Sixteen deacetylated glycoconjugated porphyrins were tested as candidate photodynamic therapy (PDT) drugs using HeLa cells. Most of the deacetylated glycoconjugated porphyrins showed higher cellular uptake than tetraphenylporphyrin tetrasulfonic acid (TPPS), and 5,10,15,20-tetrakis[4-(beta-D-arabinopyranosyloxy)phenyl]porphyrin (p-5d) in particular showed 18.5-fold higher uptake than TPPS. The photocytotoxicity of 5,10,15,20-tetrakis[4-(beta-D-glucopyranosyloxy)phenyl]porphyrin (p-5a), p-5d and TPPS was examined with HeLa cells, using a light dose of 16 J/cm(2). These photosensitizers had no cytotoxicity in the dark, but their photocytotoxicity increased in the order of TPPS < p-5a < p-5d. These results suggest p-5d is a good candidate for a PDT drug.