Synthesis and Spectral and Coordination Properties of Perhalogenated Tetraphenylporphyrins

Russian Journal of General Chemistry - The reaction of [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) with N-halosuccinimides in chloroform–methanol,...     

Synthesis and Electrochemistry of Soluble Phthalocyanine Complexes Containing Four Peripheral Dihexyl and Dihexylhexylmalonate Residues

Summary.  Tetrasubstituted phthalocyanines bearing four dihexylmalonate or dihexylhexylmalonate residues on the periphery (M[Pc(CH(COOC₆H₁₃)₂)₄] or M[Pc(C(COOC₆H₁₃)₂ C₆H₁₃)₄]; M = Pd(II), Cu(II), Co(II)) were synthesized from the anhydrous metal salts and the corresponding phthalonitriles. The complexes were only slightly soluble in polar solvents such as methanol and ethanol, but more soluble in less polar solvents such as benzene, toluene, and even hexane. The spectroscopic properties of the complexes were affected strongly by the electron withdrawing malonate units. Cyclic voltammetry on a platinum electrode in dichloromethane showed ligand-based one-electron transfers for Cu and Pd compounds, whereas the Co complex displayed metal-based or/and ligand-based one-electron transfers depending on the supporting electrolyte anion. The structures were confirmed by elemental analysis, ¹H NMR, ¹³C NMR, IR, mass (EI and FAB), and UV/Vis spectroscopy. Received November 24, 2000. Accepted (revised) January 2, 2001     

Synthesis, Characterization, and Electrochemistry of Ruthenium Porphyrins Containing a Nitrosyl Axial Ligand

Two ruthenium nitrosyl porphyrins have been synthesized and characterized by spectroscopic and electrochemical methods. The investigated compounds are represented as [(TPP)Ru(NO)(H(2)O)]BF(4) and (TPP)Ru(NO)(ONO) where TPP is the dianion of 5,10,15,20-tetraphenylporphyrin. (TPP)Ru(NO)(ONO) crystallizes in the tetragonal space group I4, with a = 13.660(1) ?, c = 9.747(1) ?, V = 1818.7(3) ?(3), and Z = 2, 233 K. The most chemically interesting feature of the structure is that the nitrosyl and O-bound nitrito groups are located axial and trans to one another. Both complexes undergo an irreversible reduction at the metal center which is accompanied by dissociation of the axial ligand trans to NO. The addition of 1-10 equiv of pyridine to [(TPP)Ru(NO)(H(2)O)]BF(4) in CH(2)Cl(2) containing 0.1 M TBAP leads to the formation of [(TPP)Ru(NO)(py)](+), a species which is reversibly reduced at E(1/2) = -0.29 V. The electrochemical data indicate that (TPP)Ru(NO)(ONO) can also be converted to [(TPP)Ru(NO)(py)](+) in CH(2)Cl(2) solutions containing pyridine but only under specific experimental conditions. This reaction does not involve a simple displacement of the ONO(-) axial ligand from (TPP)Ru(NO)(ONO) but occurs after reduction of (TPP)Ru(NO)(ONO) to (TPP)Ru(NO)(py) followed by reoxidation to [(TPP)Ru(NO)(py)](+).     

Tetraphenylporphyrins monosubstituted with glycerol diester units. Synthesis and characterization

Summary A novel 1-monoglyceryl ether of 5-(4-hydroxyphenyl)-10,15,20-tritolylporphyrin and related diacid esters with very high solubility in hydrophobic solvents were synthesized.

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Glycerindiester-monosubstituierte Tetraphenylporphyrine. Synthese und Charakterisierung

Zusammenfassung Es wurde ein neuer 1-Monoglycerylether von 5-(4-Hydroxyphenyl)-10,15,20-tritolylporphyrin und verwandte Disäuren-ester mit hoher Löslichkeit in hydrophoben Lösungsmitteln synthetisiert.

     

Synthesis and Selected Reactions of Hydrazides Containing an Imidazole Moiety

The preparation of two types of imidazole derivatives bearing a hydrazide group was achieved by treatment of the corresponding esters with NH₂NH₂?H₂O in MeOH at room temperature. In the case of 4‐(ethoxycarbonyl)‐1H‐imidazole 3‐oxides 3 , hydrazides of type 1 were formed with retention of the N‐oxide structure (Scheme 1). Interestingly, due to a strong H‐bonding, no deoxygenation of the N→O function could be achieved even by treatment of 3 with Raney‐Ni. The second type, 2‐[(1H‐imidazol‐2‐yl)sulfanyl]acetohydrazides 2 , was obtained from 1H‐imidazole‐2(3H)‐thiones 4 in two steps via S‐alkylation with methyl bromoacetate, followed by treatment with NH₂NH₂?H₂O (Scheme 2). An imidazole 7 , containing both types of hydrazide groups, was prepared analogously from ethyl 2,3‐dihydro‐2‐thioxo‐1H‐imidazole‐4‐carboxylate 4d (Scheme 4). Both types of hydrazides, 1 and 2 , were transformed successfully to the corresponding acylhydrazones 8 and 9 , respectively (Scheme 5). Furthermore, it has been shown that hydrazides of type 1 are useful starting materials for the synthesis of 1,2,4‐triazole‐3‐thiones 11 and 1,3,4‐thiadiazole‐2‐amines 12 , bearing an imidazole 3‐oxide moiety (Scheme 7).     

Synthesis and Perfume Characteristics of Acetals Containing an Aromatic Ring

Aromatic acetals were prepared by condensation of 2-methyl-3-(4-R-phenyl)propanals (R = Me, i-Pr, i-Bu) with ethanol, methanol, ethylene glycol, 1,2-propanediol, methyl Cellosolve, and Cellosolve. The perfume characteristics of the acetals were studied.     

具多重氢键寡聚芳酰胺的合成及自组装

含六重氢键寡聚芳酰胺双分子链在没有相应互补链的情况下, 其中一条链发生自组装. 通过紫外-可见(UV-Vis)光谱、动态光散射(DLS)、扫描电镜(SEM)和透射电镜(TEM)等实验手段, 对其自组装行为进行了研究. 实验结果表明, 在1,2-二氯乙烷中随温度升高在紫外区吸收发生蓝移, 说明酰胺自组装体部分解聚. 该分子链在不同极性的溶剂中都能发生自组装, 并随极性不同表现为不同的形貌. 如在甲苯中呈网状结构, 在极性相对较弱的二氯甲烷和环己烷的混合溶剂中为不规则的蜂窝状结构, 而在三氯甲烷和甲醇组成的极性混合溶剂中则组装成稳定的实心微球, 其直径随着浓度升高而增大, 通过在乙腈中的降温过程, 观察到组装体形貌由管状纤维向实心球的转变.     

Tetraphenylporphyrins monosubstituted with glycerol derivative units in the phenyl rings. Synthesis and characterization

Summary The synthesis and spectroscopic characterization of a series ofmeso-tetraphenyl substituted porphyrins appended with glycerol, diacetylglycerol, or isopropylideneglycerol units inortho,meta, orpara position of the phenylene ring is described.

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Synthese und Charakterisierung von an den Phenylresten mit Glycerinderivaten monosubstituierten Tetraphenylporphyrinen

Zusammenfassung Synthese und spektroskopische Charakterisierung einer Reihe von an den Phenylringen inortho-,meta- oderpara-Position mit Glycerin, Diacetylglycerin oder Isopropylidenglycerin substituiertenmeso-tetraphenylsubstituierten Porphyrinen wird beschrieben.

     

Tetraphenylporphyrins monosubstituted with a crown ether in one phenyl ring. Synthesis and characterization

Summary The synthesis and spectroscopic characterization of seven new tetraphenyl-porphyrins (1–7) derivatized with 12-crown-4, 14-crown-4, 15-crown-5, or 18-crown-6 ether units inortho orpara position of one of the phenyl rings is described.

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In einem Phenylring mit Kronenethern monosubstituierte Tetraphenylporphyrine. Synthese und Charakterisierung

Zusammenfassung Die Synthese und die spektroskopische Charakterisierung sieben neuer Tetraphenylporphyrine (1–7), die mit 12-Krone-4, 14-Krone-4, 15-Krone-5 oder 18-Krone-6 in derortho-oderpara-Position eines Phenylrings substituiert sind, werden beschrieben.

     

新型四硫富瓦烯-杯芳烃衍生物的合成与其电化学行为

在高度稀释条件下, 溴烷基化杯[4]芳烃1a和1b分别与二-(1,3-二硫杂环戊烯-2-硫酮-4,5-二硫)合锌酸四乙基铵盐在乙腈中回流, 得到含杯[4]芳烃单元的硫酮2a和2b. 以亚磷酸三乙酯为偶联剂, 其分别和4,5-二腈基乙硫基-1,3-二硫代环戊烯-2-酮发生交叉偶合反应, 合成了两个新颖的四硫富瓦烯–杯[4]芳烃衍生物3a和3b, 并对其进行了结构表征和电化学行为研究. 同时用X射线衍射法确认了2b的晶体结构.     

Electrochemistry as an Attractive and Effective Tool for the Synthesis and Immobilization of Porphyrins on an Electrode Surface

Magnesium(II) 10‐phenyl‐5,15‐p‐ditolylporphyrin is easily and cleanly transformed by electrolysis. A nitro group is first introduced at the free meso position by anodic substitution. Hydrogenation into the amine is then carried out electrocatalytically under ambient conditions with water as a hydrogen supplier. The synthesized porphyrin under the nickel(II) form can be covalently grafted onto a platinum electrode by electrochemical reduction of the diazonium cation, generated in situ by a reaction of the nickel(II) aminoporphyrin with sodium nitrite and trifluoroacetic acid. The electrosynthesized thin film gives an electrochemical response typical of a porphyrin material. Films grown under our conditions have a maximum surface coverage of approximately 5×10^?10 mol cm^?2. The modified electrode exhibits a reproducible electrochemical behavior and a good level of stability over potential cycling and exposition to air.     

含氮杂冠醚和核酸碱基双亲聚合物的合成及性能

设计合成了含氮杂冠醚和胸腺嘧啶的双亲聚合物聚[N,N-二乙氧基-1,10-二氮杂-18冠-6-5-甲基-胸腺嘧啶-异酞酸酯](PCTSE). 用SEM观测到其在水溶液中自发聚集成直径为150~220 nm的纳米球; 用动态光散射测得PCTSE纳米球水溶液的粒径分布主要集中在130~240 nm, 用FTIR研究了PCTSE/腺嘌呤中胸腺嘧啶与底物腺嘌呤的分子识别作用, 结果表明, 聚合物中胸腺嘧啶环上C₄=O伸缩振动峰从1670 cm^-1位移至1664 cm^-1, 表明胸腺嘧啶与腺嘌呤间形成了氢键. 变温红外光谱表明, 该峰又随温度的升高逐渐向高波数位移, 最后位移到识别前的1670 cm^-1处, 表明所形成的氢键断裂.     

Synthesis,Electrochemistry, and Hydrolysis of Anthraquinone Derivatives

Anthraquinone (AQ) derivatives, including members of the anthraquinone imide (AQI) family, have been synthesized to afford good candidates for electron-transfer studies in DNA. Electron-withdrawing groups on the AQ ring give a less negative reduction potential, as desired. As expected, the AQI derivatives have less negative reduction potentials than AQ derivatives. The AQI ring system has a half-life for hydrolysis of about 75 min in a 3:7 MeCN and 0.005 M K₂CO₃ in MeOH.     

Synthesis and Antibacterial Activity of New Acridone Derivatives Containing an Isoxazoline Fragment

A method was developed for the preparation of N-(4-R-4,5-dihydroisoxazol-5-yl)methylacridones by the reaction of aromatic aldehyde oximes with allyl acridones. For the obtained compounds, a high inhibitory activity in relation to test strains of pathogenic microorganisms was revealed, exceeding furacilin.

     

低对称性硫代烃基四氮杂卟啉的合成、表征及电化学性质研究

合成了硫代烃基四氮杂卟啉2,3,7,8,12,13-六(甲硫基)-17,18-一(二噻英)四氮杂卟啉[H₂Pz(dtn)(mt)₆]及其过渡金属配合物MPz(dtn)(mt)₆,由元素分析、质谱、¹HNMR、UV-Vis和IR光谱对其组成和结构进行了表征,通过循环伏安测试结果讨论了H₂Pz(dtn)(mt)₆的电化学性质,证明H₂Pz(dtn)(mt)₆的还原过程为单电子连续传输过程,属于CE机理.研究了H₂Pz(dtn)(mt)₆对正极材料MnO₂在锂离子电池中的修饰作用.结果表明,H₂Pz(dtn)(mt)₆对改善锂离子电池的初始充放电容量和循环次数都有明显的增加.     

螺二芴富勒烯吡咯烷衍生物的合成及电化学和光限幅性能

设计合成了3种新颖的螺二芴键联富勒烯(C₆₀/C₇₀)吡咯烷衍生物, 其结构通过IR, ¹H NMR, ¹³C NMR和MALDI-TOF进行确证, 其电化学性质用循环伏安法进行研究. 结果表明, C₇₀衍生物6的还原电位较C₆₀衍生物7分别向负电势移动0.1, 0.12和0.01 V. 同时, 使用纳秒和飞秒激光分别研究了化合物6, 7和8的光限幅性能, 其光限幅阈值分别为15.3, 23.3和13.7 J/cm², 表明材料具有优异的光限幅性能.     

Synthesis,Fluorescence and Electrochemistry of a New ECL-active Species

Recently, there has been much interest in electrochemiluminescence (ECL) generated from tris (2,2 -bipyridine) ruthenium (II) because of its application in iinmmunoassay, nucleic acid hybridization assay, and detection of other important chemical, biochemical, and biological substances. ECL is a technique by which a chemiluminescent reaction is generated from reagents produced in the vicinity of an electrode surface when a potential is applied.     

双二茂铁-钯配合物的合成，结构和电化学

本文讨论了由二茂铁的C-H…π作用组装的具有类环己烷结构的氨基硫脲钯金属配合物的结构和电化学性能。晶体结构中钯原子以顺式平面正方形的构型分别与两个氨基硫脲配体配位，两个配体中的二茂铁基团位于钯原子同一侧，每个二茂铁与相邻分子中的二茂铁基团通过环戊二烯基环间的C-H…π作用形成由类环己烷结构连结的二维网状结构。对钯的配合物及相关的镍和锌配合物的电化学研究表明，平面正方型的钯和镍可以有效的传递两个茂铁间的氧化-还原性能。     

Asymmetric Total Synthesis of Indole Alkaloids Containing an Indoline Spiroaminal Framework

The total synthesis of the indole alkaloids, neoxaline, oxaline and meleagrin A, all containing a unique indoline spiroaminal framework, was accomplished through the stereoselective introduction of a reverse prenyl group to the congested benzylic carbon of furoindoline, a two‐pot transformation of indoline (containing three nitrogen atoms at appropriate positions) to the featured indoline spiroaminal framework, and elimination of carbonate assisted by the adjacent imidazole moiety to construct the (E)‐dehydrohistidine. The absolute stereochemistry of neoxaline was elucidated through our total synthesis. In addition, we evaluated the bioactivity, especially the anti‐infectious properties, of neoxaline and oxaline, and of some synthetic intermediates.