N-错位卟啉的研究进展

N-错位卟啉既是卟啉的同分异构体又是异卟啉的典型代表,也是一类非常重要的卟啉类化合物.因其独特的化学结构及反应活性,近年来引起化学工作者的广泛关注.介绍了N-错位卟啉研究的意义、N-错位卟啉的结构和性质.重点综述了N-错位卟啉的合成及其在催化化学、生物化学和材料化学领域的应用进展.同时对N-错位扩展卟啉和其它错位异卟啉的发展现状作了简要概述,并对N-错位卟啉化学的发展进行了展望.     

四(4－N-吡啶基)卟啉衍生物的合成及表征

阳离子卟啉配体;配合物;还原电位;四(4－N-吡啶基)卟啉衍生物的合成及表征     

一种合成四(4-N,N-二甲胺基苯基)卟啉的新方法

提出了一种四(4-N,N-二甲胺基苯基)卟啉合成的新方法.该法以氮气为载气携带吡咯蒸气向反应体系中引入定量吡咯,通过降低体系中吡咯浓度,抑制部分副反应,达到提升卟啉合成产率的目的.在研究催化剂用量和反应温度对产物产率影响的基础上,确定了最优化条件:在130℃,二氯乙酸为催化剂,4-N,N-二甲胺基苯甲醛与催化剂的物质的量比为37.3时,四(4-N,N-二甲胺基苯基)卟啉的产率可高达57.0%,这是目前该卟啉最高的合成产率报道.     

几种卟啉及其配合物合成方法的改进

本文首先改进了meso位有强推电子基团的四-[4-(N,N-二甲基)苯胺基]卟啉(TDMAPPH~2)的合成方法.在此基础上, 改进了最近报道的一种新型水溶性卟啉四-[4-(N,N,N-二甲基, 丙磺酸基)苯胺基]卟啉(TDMAPPTPSH~2)的合成, 进而合成了系列水溶性金属卟啉(M'TDMAPPTPS, M'=Co,Cu,Zn,Mg,Mn,Ni).并由IR,UV-vis光谱法和元素分析得到确证.     

卟啉化聚(L-谷氨酸-γ-十八烷酯)的合成及其静电纺纤维膜制备

以单氨基卟啉作为引发剂,引发L-谷氨酸-γ-十八烷酯N-羧基内酸酐(SLGNCA)开环聚合合成卟啉化聚(L-谷氨酸-γ-十八烷酯)(PSLG),进一步通过静电纺丝制备其纤维膜.相比于自由氨基卟啉,金属氨基卟啉尤其是钴氨基卟啉引发得到的PSLG具有更高的分子量.紫外-可见光谱和荧光光谱研究表明,卟啉化PSLG依然具有卟啉独特的光谱性能,静电纺后可以制备具有均匀红色荧光的微米级纤维.     

Meso位单取代卟啉及其配合物的合成、表征和光谱性质（英文）

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。     

在交联聚苯乙烯微球表面同步合成与固载吡啶基卟啉及固载化钴卟啉的催化氧化性能

先通过季铵化反应将吡啶甲醛(PyAL)基团键合于交联聚苯乙烯微球(CPS)表面,制得改性微球PyAL-CPS,再通过Adler反应,成功地实现了吡啶基卟啉(PyP)在CPS微球表面的同步合成与同载,制得功能微球PyP-CPS,它再与碘甲烷发生季铵化反应制成N-甲基吡啶基卟啉(MPyP)季铵盐,从而制得固载有阳离子卟啉的...     

单取代色氨酸四苯基卟啉及其配合物的合成、结构表征及催化性质研究

模拟细胞色素 P- 4 5 0的活性中心金属卟啉及周围氨基酸残基的结构 ,研究以其共轭大 π电子体系和中心金属原子价改变为基础的金属卟啉的氧化还原性质 ,以及中心金属对轴向配体的配位能力是当前人们感兴趣的课题[1 ] 。本文报道了 5 - [(对 - N-色氨酸丁氧基 )苯基 ]- 10 -15 - 2 0 -三 (对氯苯基 )卟啉及其铁、钴、锰配合物的合成、结构表征和对芳醛的催化氧化行为。实　验　部　分合成1.色氨酸四苯基卟啉 (H2 L )的合成 :　按文献 [2 ]先合成单对羟基卟啉 (收率 4 .2 % ) ,再与1,4二溴丁烷反应得单对溴丁氧基四苯基卟啉 (收率 6 0 % ) ,…     

一种新型卟啉-脂质体衍生物的合成及表征

采用人工合成的N,N-二.十六烷基-6-溴代-L-甘氨酰胺(BrC5Gly2C16H33)与5,10,15-三苯基-20-对羟基苯基卟啉(HPTPP)相连接,合成了一种新型卟啉-脂质体衍生物(P-L),用元素分析、紫外可见光谱、核磁共振、红外光谱以及荧光光谱等方法进行了表征,并对其谱学性质进行了研究.     

含氟卟啉的研究进展

综述了近几年国内外含氟卟啉的合成及其研究进展. 含氟卟啉合成方法分为直接氟化法和间接氟化法. 直接法主要采用无机氟化试剂直接对卟啉环进行氟化; 间接法主要采用含氟砌块法引入氟基团. 由于合成卟啉环比较复杂, 目前氟化学家主要采用间接氟化法合成含氟卟啉化合物.     

Regulation of NH-tautomerism in N-confused porphyrin by N-alkylation

A variety of internally N-alkylated N-confused porphyrins were prepared in a stepwise manner through the protection of the reactive peripheral nitrogen atom. NH-Tautomerism in N-confused porphyrins was found to be regulated by N-alkylation, which enabled us to obtain discrete information on two important NH-tautomers of an N-confused porphyrin.     

C-fused norrole: a fused corrole isomer bearing a N,C-linked bipyrrole unit

Oxidative cyclization of a doubly N-confused bilane afforded a N-confused N,C-linked corrole (N-confused norrole), which was readily oxidized to form a C-fused N,C-linked corrole (C-fused norrole).     

Synthesis and reactivity of 5,10,15-triaryl doubly N-confused bilanes

A series of 5,10,15-tris(pentafluorophenyl) doubly N-confused bilanes were synthesized in a stepwise manner with the aid of sterically demanding N-protecting groups, in which the difference in reactivity between regular pyrrole and N-confused pyrrole plays a crucial role in the synthetic strategy. Some doubly N-confused bilanes were converted into porphyrinoids or a unique 2:2 copper(II) complex with a helical structure. In addition, the conformations and electronic states of the doubly N-confused bilanes were investigated theoretically, giving fruitful information about the effect of confusion on the bilane skeleton.     

Diels-Alder reactions of nickel(II) N-confused porphyrins as dienophiles

Diels-Alder reactions of nickel(II) N-confused tetraarylporphyrins as dienophiles with o-benzoquinodimethane yield nickel(II) N-confused isoquinoporphyrins.     

Demetalation of the regioselective oxygenation product of an N-confused porphyrin complex

[structure: see text] The demetalation of M(III)(HCTPPO)Br (M = Mn or Fe) afforded two hydroxylated N-confused porphyrinoids. CTPPOH retains the tautomer form of the N-confused porphyrin with a hydroxyl group substituted in the inner-core carbon. The further attack of OH(-) to the meso carbon afforded a dihydroxylated N-confused macrocycle, CTPP(OH)(2).     

Inverted meso-aryl porphyrins with heteroatoms; characterization of thia, selena, and oxa N-confused porphyrins.

Synthesis and characterization of inverted porphyrins containing S, Se, and O are reported. A simple 3 + 1 MacDonald-type condensation using modified tripyrrane containing the N-confused ring and diols afforded various N-confused porphyrins 6a-f in 19-30% yield. The single-crystal X-ray structure of 6b shows a ruffled conformation with tilt angles of 21.11 degrees and 31.23 degrees for the N-confused ring and the adjacent pyrrole ring III, respectively, revealing its severe nonplanarity. Significant changes in C alpha-C beta, C beta-C beta, and C alpha-X bond lengths are observed in 6b relative to free thiophene and pyrrole, suggesting the altered delocalization pathway in the modified N-confused porphyrins. The two molecules in the unit cell show a cyclophane-type noncovalent dimer with a face to face orientation of two N-confused pyrrole rings as a result of the presence of weak N-H...N and C-H...N intermolecular hydrogen bonds involving pyrrole-NH, the N atom of the N-confused ring, and the C atom of the pyrrole ring. A detailed 1H and 13C NMR study by 1D and 2D methods allowed assignments of all the peaks in the free base and protonated forms. NMR studies reveal the presence of three different tautomeric forms in solution for 6c in CDCl3 at low temperature. UV-visible studies reveal absorption band shifts upon heteroatom substitution, and the magnitudes of these shifts are dependent on the nature of the heteroatom. In all cases both monoprotonated and diprotonated species have been identified, and on addition of acid, the first proton goes to the outer N2 atom of the N-confused ring.     

Highly efficient synthesis of N-confused meso-tetraspirocyclohexyl calix[4]pyrrole using Brønsted acidic ionic liquids as catalysts

An efficient, green and novel protocol is described for high yield synthesis of N-confused meso-tetraspirocyclohexyl calix[4]pyrrole. In aqueous solution, the condensation of pyrrole and cyclohexanone in the presence of Brønsted acidic ionic liquid catalysts afforded N-confused calix[4]pyrrole in up to 62.5% yield which represents a ∼threefold yield improvement over existing protocol and makes significant quantity of N-confused calix[4]pyrrole readily available.     

Theoretical study on conformation and electronic state of Hückel-aromatic multiply N-confused [26]hexaphyrins

Conformations and electronic states of Hückel-aromatic regular, singly, doubly, and triply N-confused [26]hexaphyrins were investigated using density functional theory (DFT) calculations. A comparison of the molecular energies of 754 structures in all revealed that the most stable conformers depend on the degree of confusion, where ring strain and intramolecular hydrogen bonding would play a critical role. Consequently, regular and singly N-confused hexaphyrins prefer a dumbbell conformation, doubly N-confused hexaphyrin prefers a rectangular conformation, and triply N-confused hexaphyrin prefers a triangular conformation. Introduction of N-confused pyrrole rings into the hexaphyrin framework causes narrower HOMO-LUMO energy gaps, while it does not affect the NICS values or aromaticity significantly. The steric repulsion imposed by meso-aryl substituents largely affects the relative energies among the conformers.     

Synthesis of N-confused phlorins via an addition/cyclization pathway

The syntheses of N-confused phlorins are provided by reactions of N-confused porphyrins with nitrilimines and with dialkyl acetylenedicarboxylate. Both reactions involve zwitterionic intermediates and proceed through an addition/cyclization pathway.     

Endocyclic extension of porphyrin pi-system by interior functionalization of N-confused porphyrins

Internally alkynylated or cyanated N-confused porphyrins have been prepared, and these have been characterized by NMR, UV/Vis/NIR absorption, and X-ray analysis. The desired porphyrins have been synthesized by interconversion between an N-confused porphyrin and an N-fused porphyrin. In the case of terminal alkyne derivatives, intramolecular addition of a pyrrolic NH moiety to the triple bond occurred at ambient temperature to give etheno-bridged N-confused porphyrins. Significant bathochromic shifts in the absorbances of these compounds may be reasonably explained in terms of an increase in their HOMO energy levels due to effective overlap of the porphyrin pi-orbital and the bridged alkene pi-orbital. The corresponding rhodium(I) complexes have also been prepared, and these have been characterized by NMR and X-ray analysis.