四(对-甲酰基二茂铁-3-乙氧基)苯基卟啉的合成及电化学性质

设计合成了一种由卟啉与二茂铁通过共价键连接的四(对-甲酰基二茂铁-3-乙氧基)苯基卟啉化合物(Fe-PH₂), 采用红外光谱、核磁共振氢谱和紫外光谱等手段对其结构进行了表征, 证实所合成的为目标产物. 紫外光谱和荧光光谱结果表明, 该卟啉体系内部给受体之间在基态下存在弱的相互作用, 而在激发态下存在较强的相互作用. 电化学测试结果表明, 连接4个二茂铁基的Fe-PH₂具有更丰富的氧化还原性质.     

四磺基苯基卟啉的表面增强拉曼效应

以三电极电池系统在不同电位下的在位测量测得四磺基苯基卟啉钠水溶液（浓度为５×１０＾－５ｍｏｌ／Ｌ）的表面增强拉曼谱。结果表明，在接近第一还原态电位处对吸附分子活化后，可得到较大倍数的增强信号（１０＾７数量级）。对照简正坐标计量结果，发现与Ｎ原子有关的振动模式有较大的增强，在此基础上提出了增强机理。     

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。     

四(4-硝基苯基)卟啉和四(4-氨基苯基)卟啉的合成

四（４氨基苯基）卟啉（ＴＡＰＰ）是含有４个反应活性基团的卟啉衍生物,可在模拟某些生物过程或氧化还原反应的树枝状或簇状分子中作为富电子中心,也可直接用来制备光电器件或作为光电功能聚合物的功能单体和交联剂,因此,ＴＡＰＰ的合成研究具有重要意义［１］．...     

2-(2-氨基苯基)苯并噻唑与四苯基卟啉及四苯基锌卟啉的荧光共振能量转移

采用紫外光谱和荧光光谱法研究了四氢呋喃溶液中2-(2-氨基苯基)苯并噻唑(APBT)与四苯基卟啉(TPP)、四苯基锌卟啉(ZnTPP)之间的相互作用.结果表明,APBT可作为能量供体分子分别与能量受体分子TPP或ZnTPP构成荧光共振能量转移(FRET)体系,APBT的作用将使TPP和ZnTPP的荧光增强.在此FRET...     

薄层色谱法分离四苯基卟啉和四苯基钴卟啉

提出了用薄层色谱分离四苯基卟啉和四苯基钴卟啉的方法.方法中以石油醚-二甲苯(体积比为2:1)二元溶剂体系为展开剂,在硅胶薄层板上分离了四苯基卟啉和四苯基钴卟啉,所得斑点清晰、无拖尾.应用此薄层色谱法跟踪检测了四苯基钴卟啉的合成.     

卟啉环上的亲核取代：2-(2-萘酚)-5,10,15,20-四苯基卟啉的合成

为了制备2-取代卟啉，研究了2-硝基-5,10,15,20-四苯基卟啉1及其镍2，铜3，锌4配合物与2-萘酚钠在不同溶剂中的反应。在2-萘酚中，150℃的温度下反应，分别得到2-(2-萘酚)-5,10,15,20-四苯基卟啉5 （72%）, 及其镍(II) 6（78%）, 铜(II) 7（81%）, 锌(II) 8（65%）配合物。在其它质子性溶剂如一缩二乙二醇和一缩二乙二醇单甲醚中反应，得到相同的产物。当在非质子性溶剂DMF，150 ℃的温度下反应，除了得到5 (70%)，6 (34%)，7 (54%), 8 (50%)外，还分别得到微量2-(2-萘氧基)-5,10,15,20-四苯基卟啉9, 及其镍(II) 10（40%）,铜(II) 11（18%）, 锌(II)12 （2%）配合物。但室温下，无论用DMF还是DMSO做溶剂，均只得到5，6，7，8。卟啉1-4与萘酚钠的反应比与苯酚钠反应快，C-C键产物5-8的形成被认为是通过S_RN1机理进行的。     

meso-四(2-羟基-5-磺酸苯基)卟啉的合成及其酸碱平衡的研究

本文对 meso-四(2-H-5-SP)P 的提纯方法进行了改进,同时以光度法研究了该试剂在水溶液中的酸碱平衡、测得其 pKa_1、pKa_2、pKa_3、pKa_4分别为2.99,4.21,8.68,10.28。     

热液法合成四苯基卟啉

以苯甲醛和吡咯为原料,采用热液法合成了四苯基卟啉,其结构经UV, 1H NMR和IR表征.较适宜的反应条件为:苯甲醛25 mmol, n(苯甲醛) : n(吡咯) : n(水杨酸)=1 : 1 : 1,在二甲苯(80 mL)中于140 ℃反应5 h,收率15.38%.     

四磺基苯基铁卟啉催化反应研究及分析应用

用金属-有机配位化合物四磺基苯基铁卟啉(Iron-(4-sulphophenyl)porphyrin,FeTPPS4)作为辣根过氧化物酶(Horeseradish Peroxidase,HRP)模拟酶,催化活化H2O2氧化染料氢供体底物孔雀绿(MG),建立了FeTPPS4/H2O2/MG新的模拟酶催化反应体系。用该体系测定H2O2的表观摩尔吸光系数ε为5.54×103L.mol-1.cm-1,检出限为3.61×10-6mol/L。拟定的方法用于雨水中H2O2的测定,并与葡萄糖氧化酶(Glucose Oxidase,GOD)反应偶联测定葡萄糖(Glu)含量,结果令人满意。     

吸附在AgCl溶胶表面的单取代亮氨酸四苯基卟啉电子光谱和化学反应研究

结构对称且苯环上连有较小取代基 (硝基、卤素、烃基、甲氧基等 )的四苯基卟啉类化合物在酸性溶液中的光谱性质以及吸附在金属和半导体表面的化学反应研究引起人们的极大关注[1 3] 。从生命科学的角度考虑 ,卟啉环上连有氨基酸的四苯基卟啉较接近天然卟啉化合物[4 ,5] 。为了给天然酶的模拟研究提供信息 ,本文研究了这类卟啉衍生物Ｈ2 (ｐ Ｌｅｕ)ＴＰＰ在酸性溶液中的光谱性质及其吸附在ＡｇＣｌ溶胶表面的化学反应性质 ,并将之与Ｈ2 ＴＰＰ的光谱性质进行比较。1　实验部分1 1　仪器与试剂日本岛津ＵＶ 2 2 0 1紫外 可见分光光度计 ;ＰＨ…     

Theoretical studies on the structural change in the N-protonated tetraphenylporphyrin

The geometries of tetraphenylporphyrin which is a kind of important porphyrin derivatives, and its N-protonated diacid are calculated with AM1 MO method under symmetry restriction. The configurational changes and their effects on molecular aggregation are discussed by means of structure analysis, charge population analysis and frontier orbital analysis.     

Expedient synthesis of 1-vinylpyrrole-2-carbaldehydes

1-Vinylpyrrole-2-carbaldehydes and 1-vinyl-4,5-dihydrobenzo[g]indole-2-carbaldehyde were synthesized in 56-91% yields from their 1-vinyl derivatives by a modified Vilsmeier-Haack reaction. A low temperature (−78 °C) is required to avoid removal of the N-vinyl group, whereas at elevated temperature (reflux in 1,2-dichloroethane) the latter process leads to direct conversion of 1-vinylpyrroles to pyrrole-2-carbaldehydes.     

四苯基卟啉及其衍生物的合成

对四苯基卟啉及其衍生物的合成进行了大量研究，探讨了近三十种常用的有机溶剂中，选用三十五种常用的有机酸、无机酸催化吡咯和苯甲醛缩合。结果发现：吡咯与相应的取代苯甲醛在回流状态下缩合得到目标化合物。     

Supramolecular binding of amines with functional magnesium tetraphenylporphyrin for CO2 capture

In this work,magnesium tetraphenylporphyrin (MgTPP) was used as a new supramolecular amine-fixing agent. Once introduced, CO2 easily competes with MgTPP for amines, leading to the release of MgTPP. The processes can be explained by the fact that the association constant (Kassoc) values of MgTPP with amines were in the range of 0.6 (ethanolamine) to 3.9 (ethylenediamine), which are lower than the Kassoc values of CO2 with these amines. MgTPP interacted with aniline, ethanolamine, pyrrolidine, or ethylenediamine to form 1:1 adducts. Ethylenediamine presents a stronger Kassoc value for MgTPP, so it was considered an optimal agent for CO2 capture.     

Extracoordination sensitivity of tetraphenylporphyrin complexes to gaseous ammonia

The sensitivity of metal tetraphenylporphyrin complexes MTPP (M = Pt^II, Pt^IVCl₂, Re^IVO; TPP is tetraphenylporphyrin) to gaseous ammonia was studied. The gas sensitivity of MTPP is due to the heterogeneous catalytic oxidation of ammonia with the dioxygen ligands in the composition of MTPP. The influence of water vapor on the electrophysical properties of the surface layer of the complexes during adsorption of water and its participation in reactions of the coordinated ammonia and dioxygen were found. Empirical equations relating the conductivity of the MTPP surface layer to the content of water vapor and the concentration of gaseous ammonia were found.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2069–2074, October, 2004.     

Nucleophilic Substitution on Porphyrin Ring： Synthesis of 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenylporphyrin

The reactions of 2-nitro-5,10,15,20-tetraphenylporphyrin （1） and its Ni （Ⅱ） （2）, Cu （Ⅱ） （3）, Zn （Ⅱ） （4） complexes with sodium 2-naphthoxide have been investigated in different solvents for preparing 2-substituted porphyrins. 2-（2-Hydroxynaphthyl）-5,10,15,20-tetraphenyl porphyrin （5） and its Ni （Ⅱ） （6）, Cu （Ⅱ） （7）, Zn （Ⅱ） （8） complexes were obtained in 72%, 78%, 81% and 65% yields in 2-naphthol at 150 ℃ respectively. The same products were also obtained in other protic solvents such as diglycol and diglycol monomethyl ether. When the reactions proceeded in aprotic solvent DMF at 150 ℃, besides 5 （70%）, 6 （34%）, 7 （54%） and 8 （50%）, the corresponding 2-（2-naphythoxy）-5, 10,15,20-tetraphenylporphyrin （9）, and its Ni （Ⅱ） （10）, Cu （Ⅱ） （11）, Zn （Ⅱ） （12） complexes were also obtained in minor, 40%, 18% and 2% yields respectively, but only 5, 6, 7, 8 were found at room temperature in DMF or DMSO. These reactions axe much faster than those of 1-4 with sodium phenoxide. The formation of C-coupling products 5-8 was proposed via SRN 1 mechanism.     

Volumetric properties of methyl,tert-butyl, and alkoxy derivatives of tetraphenylporphyrin in benzene solution

Densities, apparent molar volumes, and partial molar volumes of benzene solutions ofmeso-tetradimethylphenyl porphyrin derivatives H₂T(i,j-CH₃)PP (where i,j = 2,3-; 2,4-; 3,4-; 2,5-; 3,5-);meso-tetra-4-alkoxyphenyl porphyrin derivatives H₂T(4-OC_nH_2n+1)PP (wheren = 2–4,6–8,10,12,16);meso-tetra-3-butoxyphenyl porphyrin H₂T(3-OC₄H₉)PP;meso-tetra-4-tert-butylphenyl porphyrin H₂T(4tBu)PP;meso-tetra-3,5-ditert-butylphenyl porphyrin H₂T(3,5-tBu)PP at 25°C and tetraphenylporphyrin, H₂TPP,H₂T(4-OC₁₀H₂₁)PP;H₂T(4-OC₁₂H₂₅)PP and H₂T(4tBu)PP at 20°C; 30°C; 40°C; 50°C were determined. The solubilities of the compounds in benzene at 25°C were measured. The solvent excluded volumes for different conformational states and the topology of dimethyl derivatives of tetraphenylporphyrin were calculated and compared with partial molar volume data. The correlation between the partial molar volumes and van der Waals volumes for the derivatives H₂TPP,n-alkanes,n-alkanols, fatty acids, cyclic compounds, and crown ethers using the equation of Terasawa was elaborated. The average increment of the methylene group for alkoxy-substituted H₂TPP was calculated as δV ₂ ^o (CH₂) = 16.6±0.4cm³-mol^-1. The volumetric expansion coefficients of benzene solutions of H₂TPP; H₂T(4-OC₁₀,H₂₁)PP; H₂T(4-OC₁₂H₂₅)PP and H₂T(4-tBu)PP were determined and discussed. The importance of packing efficiencies around the solute molecules were examined.     

Microwave-assisted synthesis of pyrazolo[3,4-d]pyrimidines from 2-amino-4,6-dichloropyrimidine-5-carbaldehyde under solvent-free conditions

The microwave-induced synthesis of pyrazolo[3,4-d]pyrimidines 4 in the reaction of N⁴-substituted-2,4-diamino-6-chloro-5-carbaldehydes 3 with hydrazine is described here. Precursors 3 have been prepared by the mono-amination of 2-amino-4,6-dichloropyrimidine-5-carbaldehyde 2 with aliphatic and aromatic amines. The reaction times with primary amines were relatively shorter than for secondary amines.     

Highly active electrocatalysis by cobalt tetraphenylporphyrin incorporated in a Nafion membrane for proton reduction

Electrocatalytic H⁺ reduction was studied with cobalt tetraphenylporphyrin (CoTPP) incorporated in a Nafion membrane coated on a Pt electrode (denoted as Pt/Nf[CoTPP]). It was found that Pt/Nf[CoTPP] shows an efficient catalytic activity to produce H₂ around the theoretical H⁺/H₂ redox potential (−0.25 V v. Ag/AgCl in a pH 1.01 aqueous solution), and that its catalytic activity is remarkably higher than a neat CoTPP film and a conventional Pt catalyst. The amount of the H₂ produced decreased with increasing CoTPP concentration in the membrane ([CoTPP]_Nf]). The ratio of electroactive Co^IITPP was independent of its concentration, showing that the present electron transfer process takes place via physical diffusion of the molecule. The intrinsic turnover number (TN_int) of the CoTPP to produce H₂, based on the electroactive amounts of the CoTPP, decreased with increasing [CoTPP]_Nf. The catalysis was discussed in terms of the characteristic of the Nafion membrane. © 1998 John Wiley & Sons, Ltd.