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%。     

Novel family of triphenylamine‐containing,hole‐transporting,amorphous, aromatic polyamides with stable electrochromic properties

We report the preparation and characterization of a series of novel electrochromic, aromatic poly(amine amide)s with pendent triphenylamine units. The synthesis proceeded via direct phosphorylation polycondensation between a novel diamine, N,N‐bis(4‐aminophenyl)‐N′,N′‐diphenyl‐1,4‐phenylenediamine, and various aromatic dicarboxylic acids. All the poly(amine amide)s were amorphous and readily soluble in many common organic solvents and could be solution‐cast into transparent, tough, and flexible films with good mechanical properties. They exhibited good thermal stability and 10% weight‐loss temperatures above 540 °C. Their glass‐transition temperatures were 263–290 °C. These polymers in N‐methyl‐2‐pyrrolidinone solutions exhibited strong ultraviolet–visible absorption peaks at 307–358 nm and photoluminescence peaks around 532–590 nm in the green region. The hole‐transporting and electrochromic properties were studied with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of poly(amine amide) films prepared by the casting of polymer solutions onto an indium tin oxide coated glass substrate exhibited two reversible oxidation redox couples at 0.65 and 1.03 V versus Ag/AgCl in an acetonitrile solution. All the poly(amine amide)s showed excellent stability with respect to their electrochromic characteristics; the color of the films changed from pale yellow to green and then blue at 0.85 and 1.25 V, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2085–2098, 2005     

DFT investigation of sites of protonation of antitumor of 2‐(4‐aminophenyl)benzazoles in the gas phase and in solution

The proton affinity on each of the possible sites in the antitumor 2‐(4‐aminophenyl)benzazoles has been calculated at the B3LYP/6‐311G** level of theory in the gas phase and in solution. The N₃‐site of protonation is found to be strongly favored over the NH₂‐site for the studied compounds both in gas phase and in solution. The stability of N₃‐protonated species is explained by the resonance interaction of the NH₂‐group with the heterocyclic ring. The potential energy surface (PES) for the protonation process was studied at the density functional theory (DFT)/B3LYP/6‐311++G** level of theory. Solvent effects on the PES were also examined using two models: Onsager self‐consistent field and polarizable continuum model (PCM). © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

A comparative study between para‐aminophenyl and ortho‐aminophenyl benzothiazoles using NMR and DFT calculations

Ortho‐substituted and para‐substituted aminophenyl benzothiazoles were synthesised and characterised using NMR spectroscopy. A comparison of the proton chemical shift values reveals significant differences in the observed chemical shift values for the NH protons indicating the presence of a hydrogen bond in all ortho‐substituted compounds as compared to the para compounds. The presence of intramolecular hydrogen bond in the ortho amino substituted aminophenyl benzothiazole forces the molecule to be planar which may be an additional advantage in developing these compounds as Alzheimer's imaging agent because the binding to amyloid fibrils prefers planar compounds. The splitting pattern of the methylene proton next to the amino group also showed significant coupling to the amino proton consistent with the notion of the existence of slow exchange and hydrogen bond in the ortho‐substituted compounds. This is further verified by density functional theory calculations which yielded a near planar low energy conformer for all the o‐aminophenyl benzothiazoles and displayed a hydrogen bond from the amine proton to the nitrogen of the thiazole ring. A detailed analysis of the ¹H, ¹³C and ¹⁵N NMR chemical shifts and density functional theory calculated structures of the compounds are described. Copyright © 2014 John Wiley & Sons, Ltd.     

6-(3-氨基苯基)-4, 5-二氢哒嗪-3(2H)-酮的合成

以苯、丁二酸酐为原料,经傅克酰基化,硝化,与水合肼反应三步反应合成6-(3-氨基苯基)-4,5-二氢哒嗪-3(2H)-酮(1),总收率为58.3%。由3-(3-硝基苯甲酰基)丙酸(3)合成化合物1的过程中,在雷尼镍(Raney Ni)的催化下与水合肼反应,一步完成了苯环上硝基的还原和成环。重点考察了该步反应的物料配比、反应时间对产率的影响。结果表明,水合肼与化合物3的摩尔比11.7∶1,回流反应4 h,产率为82.7%。     

Aminophenyl Benzimidazole as a New Reagent for the Estimation of NO2/Nitrite/Nitrate at Trace Level: Application to Environmental Samples

Abstract

A simple and sensitive spectrophotometric method for the determination of nitrogen dioxide in ambient air and nitrite/nitrate in water and soil samples has been developed. Nitrogen dioxide in air has been fixed as nitrite ion using alkaline sodium arsenite as absorbing medium. The method is based on the reaction of nitrite with aminophenyl benzimidazole in acid medium to form diazonium ion, which is coupled with N‐(1‐naphthyl)ethylenediamine dihydrochloride to form an azo dye with an absorption maximum at 555 nm in aqueous phase. The method obeys Beer's law in the concentration range 0–10 µg of nitrite in 25 ml solution. The molar absorptivity has been found to be 6.3×10⁴ l mol^?1 cm^?1. The dye can be extracted quantitatively into isoamyl alcohol under alkaline condition and the addition of methanolic hydrochloric acid restores the original dye colour. Beer's law is obeyed in the concentration range 0–2 µg of nitrite with a detection limit of 0.009 µg. The effect of interfering species has been studied and the developed method has been applied to determine trace levels of nitrogen dioxide in ambient air and the results have been compared with the standard method. It is also applied to measure the nitrite/nitrate levels of surface and ground water samples collected from lakes, tube wells as well as soil samples.     

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］．...     

Synthesis and evaluation of photoluminescent and electrochemical properties of new aromatic polyamides and polyimides with a kink 1,2‐phenylenediamine moiety

A series of novel triphenylamine‐containing aromatic polyamides and polyimides having a crank and twisted noncoplanar structures were synthesized in inherent viscosities of 0.14–0.64 dL/g and 0.11–0.67 dL/g, respectively. These polymers had useful levels of thermal stability associated with relatively high glass‐transition temperatures (174–311 °C). They exhibited strong UV–Vis absorption bands at around 300 nm in NMP solutions. The PL spectra of these polymers in NMP solutions (1 × 10^?5 M) showed maximum peaks around 396–479 nm. The hole‐transporting and electrochromic properties were examined by electrochemical and spectroelectrochemical methods. Cyclic voltammetry (CV) of the polymer films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited two reversible oxidation redox couples at potentials of 0.70–1.01 V and 1.10–1.46 V, respectively, vs. Ag/AgCl in acetonitrile solution. The polymer films revealed electrochromic characteristics, with a color change from neutral pale yellowish to green and then to a blue oxidized form at applied potentials ranging from 0.00 to 1.75 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2587–2603, 2006     

Mechanistic insight on (E)‐methyl 3‐(2‐aminophenyl)acrylate cyclization reaction by multicatalysis of solvent and substrate

The reaction mechanism of (E)‐methyl 3‐(2‐aminophenyl)acrylate ( A ) with phenylisothiocyanate ( B ) as well as the vital roles of substrate A and solvent water were investigated under unassisted, water‐assisted, substrate A ‐assisted, and water‐ A ‐assisted conditions. The reaction proceeds with four processes via nucleophilic addition, deprotonation and protonation, intramolecular cyclization with hydrogen transfer, and keto–enol tautomerization. According to the different H‐shift mode, two possible types of H‐shift P1 and P2 are carefully investigated to identify the most preferred pathway, differing in the ? NH₂ group deprotonation and ? CH group of A protonation processes. It is found that substrate A and water not only act as reactant and solvent, but also as catalyst, proton shuttle, and stabilizer in effectively lowering the energy barrier. Therefore, the results demonstrate that the strong donating and accepting ability of ? NH₂ group on A and the presence of bulk water are the keys to the title reaction proceed. © 2016 Wiley Periodicals, Inc.     

One saccharide sensor based on the complex of the boronic acid and the monosaccharide using electrochemical impedance spectroscopy

A novel saccharide sensor based on the covalent interaction between the boronic acid and saccharides was developed. Poly (aminophenylboronic acid) (PABA) was prepared by electropolymerizing 3-aminophenylboronic acid on gold electrode surface in acidic solution. The boronic acid group of the PABA film can form covalent-bond with different saccharides, which can change the dielectric characteristics of the PABA film, and the change of the dielectric characteristic was saccharides concentration dependent. Four kinds of saccharides could be detected by using electrochemical impedance spectroscopy. Good linear relationship and high sensitivity were obtained by this method.