Silicon-containing Schiff base and benzimidazole derivatives

Investigations were undertaken to obtain information for use in the development of new heat-stable polymers. Model silicon-containing Schiff base and benzimidazole derivatives were synthesized by reaction of p-(triphenylsilyl)-benzaldehyde with phenylenediamines. The structure and thermal stability of the products were studied. The reaction of p-(triphenylsilyl)benzaldehyde and o-phenylenediamine yielded N-p-(triphenylsilyl)benzylidene-o-phenylenediamine which readily oxidizes to form 2-p-(triphenylsilyl)phenylbenzimidazole. The di-Schiff bases, which most probably exist in trans-trans configurations, were obtained from reaction of the aldehyde derivative with m- and p-phenylenediamine. In contrast to similar Schiff bases without silicon, the products are soluble in organic solvents. The good resistance of the di-Schiff base and benzimidazole derivatives to thermal decomposition suggests that polymers with repeating units of such structures would also be heat-stable and might possess useful properties.     

Schiff base derivatives of lanthanons,La(III), Pr(III), Nd(III) and Sm(III) complexes of bifunctional tetradentateSchiff base

Reactions of La(III), Pr(III), Nd(III) or Sm(III) nitrate with bifunctional tetradentateSchiff base, [o-HOC₆H₄C(CH₃): :NCH₂]₂, having the donor system HO–N–N–OH in 12 molar ratio have been investigated and found to yield new derivatives of the type [Ln(SBH₂)₂](NO₃)₃ [whereLn=La(III), Pr(III), Nd(III) or Sm(III) andSBH₂=Schiff base molecule, [o-HOC₆H₄C(CH₃) : NCH₂]₂. On the basis of elemental analyses, conductivity and magnetic measurements and infrared spectra, plausible structures for the resulting complexes have been indicated.     

Nucleophilic reactivities of Schiff base derivatives of amino acids

Treatment of α-imino esters derived from glycine esters and benzophenone or benzaldehydes with potassium tert butoxide in DMSO gave persistent solutions of carbanions at 20?°C. The kinetics of their reactions with quinone methides and benzylidene malonates (reference electrophiles) have been followed photometrically under pseudo-first order conditions. The reactions followed second-order rate laws. Since addition of 18-crown-6 ether did not affect the reaction rates, the measured rate constants correspond to the reactions of the non-paired carbanions. Plots of the second-order rate constants against the electrophilicity parameters E of the electrophiles are linear, which allowed us to derive the nucleophile-specific parameters N and s_N, according to the linear Gibbs energy relationship lg k₂(20?°C)?=?s_N(N + E). The Ph₂C?=?N- and PhCH?=?N- groups act as very weak electron acceptors with the consequence that Ph₂C?=?N-CH^–-CO₂R and PhCH?=?N-CH^–-CO₂R have a similar nucleophilicity as Ph-CH^–-CO₂Et, the anion of ethyl phenylacetate.     

Synthesis and physico-analytical studies of some novel ferrocenyl Schiff base derivatives

A series of ferrocenyl Schiff base derivatives was synthesized by condensation reactions of 1,1′-ferrocenedicarboxaldehyde and aromatic amines containing long chain alkyl groups as free ends which were characterized by their physical properties, elemental, FTIR, ¹H NMR, ¹³C NMR spectral and thermal analysis. The thermal behaviour of the synthesized compounds was studied by differential scanning calorimetry (DSC) which revealed that these compounds may exhibit mesomorphic properties. The DSC results of aromatic amines and ferrocenyl Schiff bases were compared to study the effects of structure, i.e. rigid core and terminal chain length, on the phase transition behaviour.     

Synthesis and spectroscopic and electrochemical studies of chitosan Schiff base derivatives

Schiff derivatives were prepared by the reactions of salicylaldehyde and its derivatives (5-chloro, 5-methoxy, 5-fluoro, 5-methyl, 5-nitro) with the amino group of chitosan. The Schiff bases were studied by Fourier IR spectroscopy and by UV-visible spectroscopy. The cyclic voltammograms of the Schiff bases were analyzed and compared to those of chitosan and salicylaldehyde. The formal potential of the chitosan Schiff base derivative correlates with the Hammett parameters. The oxidation potential increases and the optical density decreases with enhancement of the electron-acceptor properties of the functional group R in the m-position to the -N=CH-group. Chitosan (Chi) is a polysaccharide whose chains consist of recurrent units of acetamido-2-deoxy-D-glucode linked by the 1,4-β-glycoside bond. This polysaccharide was widely studied as drug carrier [1, 2], because it is nontoxic, biodegradable, and well biocompatible [3].     

Studies on molecular structure of Schiff base derivatives in LB films

The present paper investigated the molecular configurations of the two novel amphiphiles with Schiff base moiety as headgroup in LB films. FTIR-ATR spectra and UV-vis electronic absorption spectra revealed the different isomers between the two amphiphiles LB film. Since z.sbnd;OH groups situate in different position of the aromic rings in Schiff base amphiphiles, the proton transfer by different ways leads to different isomers, which were reflected by monolayer and LB films behavior.     

Synthesis and physicochemical studies of metal complexes of ferrocene Schiff base derivatives

Two new Schiff bases were prepared by condensing acetylferrocene and 1,1′-diacetylferrocene with S-methyl- dithiocarbazate. Complexes of the two ligands acetylferrocene-1-hydrazono-S-methyldithiocarbazate HmaL and diacetylferrocene-1,1′-dihydrazono-S-methyldithio-carbazate H2daL, with copper(II), nickel(II) and cobalt(II) ions were isolated. The ligands coordinate to the metal ions through either their thioketone or thioenol forms. Both mono- and bis-ligand metal complexes as well as bis-metal complexes of the general formulae: [(H2daL)M]2+, [(daL)M], [(HmaL)2M]2+, [(maL)2M], [(HmaL)2MX2], [(H2daL)M2X4] and [(daL)M2X2] were prepared. All compounds under investigation were characterized and some of their physicochemical properties are reported. This revised version was published online in June 2006 with corrections to the Cover Date.     

Ratiometric fluorescence and colorimetric sensing of anion utilizing simple Schiff base derivatives

Two ratiometric fluorescence and colorimetric anion sensors were designed and synthesized according to simple Schiff base reaction. Two compounds 1 and 2 were characterized by ESI–MS, elemental analyses and ¹H NMR. The sensors could give fast and visible color changes from yellow to red upon presence of the strong basic anions such as acetate ion. In particular, two compounds exhibited marked blue shifts (about 136 nm) in their emission spectra, when interacting with anions. Accordingly, the compounds 1 and 2 could act as real-time ratiometric fluorescence and colorimetric sensors for anions.     

冠醚化Schiff碱

综述了冠醚化Schiff碱的合成、配位和某些仿生性能的研究进展。     

Schiff base derivatives of titanium(IV) and zirconium(IV)

The reactions of a few bifunctional and tridentate Schiff bases with titanium-(IV) and zirconium(IV) isopropoxides in equimolar and bimolar ratios are described. The resulting compounds have been obtained in almost quantitative yields and are of the general formulae M(SB)_x(OPrⁱ)_4?2X (where M = Ti or Zr; SB- = anion of the Schiff base SBH₂ and x = 1 or 2). Their molecular weights have been determined ebullioscopically and IR spectra recorded.     

Potentiometric performance of silver ion-selective electrodes based on tridentate Schiff base derivatives.

To examine the directivity for improving the silver ion discrimination ability of a Schiff base, three kinds of tridentate ligands were synthesized and compared with the similar quadridentate ligand as the silver ionophore. Among the Schiff base derivatives tested, 3-(2-pyridylethylimino)-2-butanoneoxime, having one oxime and a pyridine substituent, was found to be the best ionophore for a silver-ion electrode. The electrode based on this derivative exhibited good silver-ion selectivity, -log Kpot(Ag+,K+) = 3.8, comparable to that of a quadridentate Schiff base, N,N'-bis(2'-hydroxyimino-1'-phenylpropyleden)-1,3-propanediamine, reported previously, except for a pseudo Nernstian response (35.6 mV decade(-1)) with a wide silver-ion activity change in the activity change from 5.0 x 10(-7) to 7.9 x 10(-2) mol dm(-3).     

Synthesis, characterization, tautomerism and theoretical study of some new Schiff base derivatives

New Schiff base derivatives were prepared by the condensation of 5-chloro and 5-bromo salicylaldehyde with bis(o-aminophenol)ethers. Five bis(o-nitrophenol)ether compounds were synthesized using some ditosylate, 1,3-dibromopropane and 1,4-dibromobuthane with o-nitrophenol. These compounds were reduced to bis(o-aminophenol)ethers. The products have been characterized by elemental analysis, FTIR, 1H, 13C NMR, HETCOR and HMBC spectroscopic techniques. The tautomerisms of all of the Schiff bases compounds were determined in DMSO, CHCl3, C2H5OH and C6H12 solvents and in both acidic and basic media using the UV-vis spectrophotometric method. The heat of formation (ΔHf), enthalpy (ΔH), entropy (ΔS), Gibbs free energy (ΔGf and ΔG), stable isomers, conformations and tautomers of the synthesized compounds are calculated using the MOPAC2009 (PM6) program.     

硫脲及其席夫碱衍生物合成与应用研究进展

硫脲类化合物因其独特的分子结构、良好的理化性能以及广泛的生物活性,在材料、医药、农药和配位催化等领域有重要的应用。因而其合成方法受到广泛关注。近年来,微波合成、超声波合成、无溶剂合成、离子液合成、相转移催化合成等一系列高效、绿色的合成方法在硫脲类化合物的合成中得到广泛的应用。结合本课题组的研究成果,本文着重综述了硫脲和席夫碱类化合物的合成方法及其应用,并对今后的研究方向进行了展望。     

Water soluble chromone Schiff base derivatives as fluorescence receptor for aluminium(III)

A novel water-soluble chromone Schiff base derivatives bearing polyhydroxylated moiety were prepared and applied for specific recognition of metal ions in aqueous medium. Their selective fluorescence response to Al(III) over a variety of other biologically important metal ions were demonstrated. Electronic parameters of the sensors were also studied by quantum chemical computations.     

Fabrication of chiral Langmuir-Schaefer films of achiral amphiphilic Schiff base derivatives through an interfacial organization

Supramolecular chirality in the Langmuir-Schaefer (LS) films of two achiral amphiphilic Schiff bases, 2-(2'-benzimidazolyliminomethyl)-4-octadecyloxyphenol (BSC18) and 2-(2'-benzthiazolyliminomethyl)-4-octadecyloxyphenol (TSC18), was investigated. Both of these amphiphiles could form LS films from the water surface or coordinate with Ag(I) in the subphase to form Ag(I)-coordinated LS films. Although both of these amphiphiles were achiral, TSC18 formed a chiral LS film from the water surface, while BSC18 formed a chiral Ag(I)-coordinated LS film from the aqueous AgNO3 subphase. The supramolecular chirality in these LS films was suggested to be due to a cooperative stereoregular pi-pi stacking of the functional groups together with the long alkyl chains in a helical sense. The relationship between the chirality of the LS films and the molecular structures of TSC18 and BSC18 as well as their H-bond or coordination behaviors was discussed. The Schiff base films showed a reversible color change upon exposure to HCl and NH3 gas alternatively; however, the supramolecular chirality was irreversible during these processes.     

Uranyl stabilized Schiff base complex

Uranyl Schiff base complex [(UO(2))(2)(Salpro)(OH)(Solvent)(2)] (1) in the presence of excess of ethylenediamine (EDA) does not undergo nucleophilic addition (hydrolysis) and substitution (transamination) reactions due to an extended chelation [2N, 3O + OH] by the flexible backbone.     

Inhibitory study of some novel Schiff base derivatives on Staphylococcus aureus by microcalorimetry

The effect of a series of novel Schiff base compounds on Staphylococcus aureus was studied by microcalorimetric method at 37 °C The results showed that all of the organic compounds had the capacity to inhibit the growth of S. aureus in different extent. And the extent and duration of the inhibitory effect on the growth of S. aureus, judged from the rate constant (k), varied with the different structure of the Schiff base compounds. According to the power-time curves, the multiplication rate constant and inhibition ratio were calculated. The growth rate constant of S. aureus (in log phase) in the presence of Schiff base compounds decreased with the increasing of the concentrations of these compounds regularly. The experimental results revealed that the hydrophilicity of Schiff bases had a great influence on their antibacterial activity. Of these Schiff bases, the greater their hydrophilicity, the higher their antibacterial activity. The antibacterial structure-activity relationship (SAR) of Schiff base derivatives was also briefly discussed.     

New Schiff base complexes of tetrachlorouranium

Summary Tetrachlorouranium complexes containing a Schiff base ligand, p-XC₆H₄NH=CHC₆H₄OH(L), derived from p-XC₆H₄NH₂ and salicylaldehyde, have been prepared. Atris complex was obtained when X=NO₂ andbis complexes for the other p-substituted Schiff bases when X=Cl, Br, OH and Me.     

A structural study of 4‐aminoantipyrine and six of its Schiff base derivatives

Six derivatives of 4‐amino‐1,5‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐3‐one (4‐aminoantipyrine), C₁₁H₁₃N₃O, (I), have been synthesized and structurally characterized to investigate the changes in the observed hydrogen‐bonding motifs compared to the original 4‐aminoantipyrine. The derivatives were synthesized from the reactions of 4‐aminoantipyrine with various aldehyde‐, ketone‐ and ester‐containing molecules, producing (Z)‐methyl 3‐[(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)amino]but‐2‐enoate, C₁₆H₁₉N₃O₃, (II), (Z)‐ethyl 3‐[(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)amino]but‐2‐enoate, C₁₇H₂₁N₃O₃, (III), ethyl 2‐[(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)amino]cyclohex‐1‐enecarboxylate, C₂₀H₂₅N₃O₃, (IV), (Z)‐ethyl 3‐[(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)amino]‐3‐phenylacrylate, C₂₂H₂₃N₃O₃, (V), 2‐cyano‐N‐(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)acetamide, C₁₄H₁₄N₄O₂, (VI), and (E)‐methyl 4‐{[(1,5‐dimethyl‐3‐oxo‐2‐phenyl‐2,3‐dihydro‐1H‐pyrazol‐4‐yl)amino]methyl}benzoate, C₂₀H₁₉N₃O₃, (VII). The asymmetric units of all these compounds have one molecule on a general position. The hydrogen bonding in (I) forms chains of molecules via intermolecular N—H...O hydrogen bonds around a crystallographic sixfold screw axis. In contrast, the formation of enamines for all derived compounds except (VII) favours the formation of a six‐membered intramolecular N—H...O hydrogen‐bonded ring in (II)–(V) and an intermolecular N—H...O hydrogen bond in (VI), whereas there is an intramolecular C—H...O hydrogen bond in the structure of imine (VII). All the reported compounds, except for (II), feature π–π interactions, while C—H...π interactions are observed in (II), C—H...O interactions are observed in (I), (III), (V) and (VI), and a C—O...π interaction is observed in (II).