Hydrogenation of schiff bases with group 6 metal carbonyls and sodium methoxide as catalyst precursors

Summary Schiff bases are hydrogenated to secondary amines by H₂ in the presence of [M(CO)₆](M=Cr, Mo or W) and NaOMe in methanol solution at 60–160 °C andca. 100 bar H₂ pressure. The reaction is significantly slower in the absence of NaOMe. In a stoichiometric reaction, [HCr(CO)₅]^– hydrogenatesN- benzylidene-aniline at 75 °C toN-benzylaniline forming [Cr₂(CO)₁₀]^2–.     

Uracil ring opening in the reaction of 5-formyl-2′-deoxyuridine with primary alkyl amines

Treatment of 5-formyl-2′-deoxyuridine (f⁵dU) with stoichiometric amounts of strongly nucleophilic, non-hindered primary alkyl amines led to fast and quantitative formation of the corresponding Schiff bases. In the presence of excess amines, novel nucleosides with ring opened pyrimidine bases were formed as a result of the Michael addition of a second amine to the pre-formed imines. In the reaction of f⁵dU with aromatic amines, the formation of Schiff base derivatives was slower and even under prolonged treatment with an excess of amine the uracil ring remained intact.     

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.     

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.     

Some aminophosphinocarboxylic acids and their derivatives

The addition of Schiff bases of α-aminoacid esters to vinylphosphoryl compounds was studied as a method for the synthesis of phosphinothricin and its analogues. The reaction was found to proceed smoothly in DMSO in the presence of strong nitrogen bases and under the conditions of phase transfer catalysis. The Claisen condensation of β-phosphorylated propionitrile with diethyl oxalate was studied; phosphorylated derivatives of hydroxycitraconic acid nitrile were prepared on hydrolysis; transformation of such a derivative into a cyclic imide as well as into trimethylsilyl esters of these acids and their Z → E transformation were investigated. Cyclization reactions between α,ω-dibromoalkanes and phosphoryl compounds containing an active methylene group affording cyclopropane and other cyclic derivatives were studied. The cyclopropane ring is cleaved by amines to give aminophosphinocarboxylic acids.     

Thermodynamic quantities for the acid dissociation of alkylammonium ions in water over a wide temperature range

Enthalpies of protonation in aqueous solution have been determined from calorimetric measurements between 0 and 100°C for methylpentylamine, butyldimethylamine, and quinuclidine; between 0 and 125°C for di-iso-propylamine; and between 0 and 75°C for 1-azacycloheptane. Values ofpK_a at 25°C have been determined from pH measurements using a glass electrode for di-iso-propyl-, methylpentyl-, and butyldimethylamine. The calorimetric results are used together with values ofpK_a at 25°C to derive expressions which allow the calculation of accuratepK_a values over a large temperature range. The heat capacity and entropy changes for the protonation of aqueous alkylamines found in the present and in previous studies are discussed in terms of differences in hydrophobic solvation of the alkyl groups in the neutral amines and the ions.     

Synthesis of di‐nitrogen Schiff base complexes of methyltrioxorhenium(VII) and their application in epoxidation with aqueous hydrogen peroxide as oxidant

Several di‐nitrogen Schiff bases were synthesized through the condensation of 2‐pyridinecarboxaldehyde with primary amines. The Schiff bases as ligands coordinated with methyltrioxorhenium (MTO) smoothly to afford the correspondent complexes which were characterized by IR, ¹H NMR, ¹³C NMR, MS and elemental analysis. One of the complexes was analyzed by X‐ray crystallography as well. The results revealed that the complexes display distorted octahedral geometry in the solid state with a trans‐position of Schiff base. Catalytic results indicated that the complexes as catalysts increased the selectivity of epoxides remarkably compared with MTO in the epoxidation of alkenes with 30% hydrogen peroxide as oxidant and the increasing rate depended on the structure of the Schiff base ligands of the complexes. The results indicated that the stronger the donating ability of the ligand, the higher selectivity of epoxides the complex gave in the epoxidation of alkenes with 30% hydrogen peroxide as oxidant. Copyright © 2010 John Wiley & Sons, Ltd.     

Deuterium isotope effects on 15N chemical shifts of double Schiff bases in the solid state and solution

The proton transfer equilibrium in a series of double Schiff base derivatives of trans‐1,2‐diaminocyclohexane in solution and the solid state was studied by means of ¹⁵N NMR spectroscopy and analysis of the deuterium isotope effect on the chemical shifts Δ¹⁵N(D). The presence of a proton transfer equilibrium in the N‐2‐hydroxynaphthylidene moieties of the Schiff bases studied in the solid state at room temperature was evidenced. The results confirmed the interrelation of the two hydrogen bonds in double Schiff base derivatives of trans‐1,2‐diaminocyclohexane. Copyright © 2003 John Wiley & Sons, Ltd.     

Chiral Silver Amides as Effective Catalysts for Enantioselective [3+2] Cycloaddition Reactions

Asymmetric [3+2] cycloaddition of α‐aminoester Schiff bases with substituted olefins is one of the most efficient methods for the preparation of chiral pyrrolidine derivatives in optically pure form. In spite of its potential utility, applicable substrates for this method have been limited to Schiff bases that bear relatively acidic α‐hydrogen atoms. Here we report a chiral silver amide complex for asymmetric [3+2] cycloaddition reactions. A silver complex prepared from silver bis(trimethylsilyl)amide (AgHMDS) and (R)‐DTBM‐SEGPHOS worked well in asymmetric [3+2] cycloaddition reactions of α‐aminoester Schiff bases with several olefins to afford the corresponding pyrrolidine derivatives in high yields with remarkable exo‐ and enantioselectivities. Furthermore, α‐aminophosphonate Schiff bases, which have less acidic α‐hydrogen atoms, also reacted with olefins with high exo‐ and enantioselectivities. The stereoselectivities of the [3+2] cycloadditions with maleate and fumarate suggested that the reaction proceeded by means of a concerted mechanism. An NMR spectroscopic study indicated that complexation of AgHMDS with the bisphosphine ligand was not complete, and that free AgHMDS, which did not show any significant catalytic activity, existed in the catalyst solution. This means that significant ligand acceleration occurred in the current reaction system.     

Synthesis of Novel Symmetric Porphyrin Schiff Base Dimers by Solid–Liquid Reaction Methodology

A new convenient solid–liquid condensation reaction procedure for the synthesis of novel asymmetric and symmetric meso‐tetraarylporphyrin and metalloporphyrin Schiff bases is reported. The condensation reaction between β‐formyl porphyrin or metalloporphyrins and aromatic amines was carried out at solid–liquid interface by using neutral alumina powder as a solid support for β‐formyl porphyrin or metalloporphyrins and absolute ethanol as the carrier solvent for aromatic amines. Six different asymmetric porphyrin/metalloporphyrin Schiff bases were synthesized via solid–liquid interface reaction methodology. The same solid–liquid synthetic methodology was applied for the synthesis of six novel symmetric Schiff base porphyrin/metalloporphyrin dimers. The comparison of UV–visible spectra of porphyrin Schiff base monomers and dimers revealed that some degree of electronic perturbation has occurred upon dimerization as the Soret bands of the monomers underwent peak broadening along with red shifts. Column chromatography and crystallization were used to purify the compounds. Fourier transform infrared, UV–visible, elemental analysis, ¹H NMR, and mass spectrometry were used to characterize the newly synthesized compounds.     

Synthesis and antibacterial activity of Schiff bases of 5-substituted isatins

Based on the existing reports on the bioactive isatin derivatives, a number of Schiff bases were synthesized by reacting 5-substituted isatins with bioactive amines/hydrazides and their structures were confirmed using spectroscopic methods such as NMR, IR and mass spectrometry. Furthermore, Nbenzylation of isatin followed by the Schiff base formation furnished a new series of compounds(11a–13c) which allowed the analysis of the effect of isatin N-substitution on the bioactivity of the resulting compounds. The antibacterial activity of the synthesized derivatives was evaluated using a microtiter plate method on a series of gram positive and gram negative bacterial strains. Compounds 2d, 3b, 5c and 6a were among the most potent derivatives against Pseudomonas aeruginosa(MIC = 6.25 μg/m L).Analysis of the structure–activity relationship showed that the incorporation of(thio)urea-based Schiff bases lead to more potent derivatives with a broader spectrum of antibacterial activity. In addition,highly lipophilic compounds such as 11a–12c did not show any measurable antibacterial activity, which implies that an optimal lipophilicity might be an important requirement for the antibacterial activity of the studied isatins. Finally, the finding that hydantoin derivatives of N-benzylisatins(13a–13c) still exhibit some antibacterial activity prompted us to consider exploring the bioactivity of more diverse derivatives of isatin-aminohydantoin Schiff bases(compounds 1a–1d) in our future studies.     

cis-Dioxo(N-salicylidene-2-aminophenolato)(imidazole)-molybdenum(VI) complexes

Summary cis-Dioxo(N-salicylidene-2-aminophenolato) (imidazole)-molybdenum(VI) complexes, [MoO₂(Sap)(Im)], (Im = imidazole or its derivatives, sap = salicylidene-2-aminophenolate) are prepared by the ligand substitution of [MoO₂(Sap)(EtOH)] with a unidentate imidazole ligand. All complexes are red or yellow, diamagnetic, non-electrolytes and possess an octahedral stereochemistry. The i.r. spectra shows two bands attributable tocis-MoO₂ stretches in addition to the vibrations of the Schiff base ligand and the imidazole derivatives. Thermal degradation of the complexes result in successive loss of imidazole ligand followed by the Schiff base, with ultimate formation of MoO₃ atca. 500 °C.     

Synthesis,spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

New metal based triazoles (1–12) have been synthesized by the interaction of novel Schiff base ligands (L¹–L³) with the Co(II), Ni(II), Cu(II) and Zn(II) metal ions. The Schiff base ligands and their all metal(II) complexes have been thoroughly characterized using various physical, analytical and spectroscopic techniques. In vitro bacterial and fungal inhibition studies were carried out to examine the antibacterial and antifungal profile of the Schiff bases in comparison to their metal(II) complexes against two Gram‐positive, four Gram‐negative and six fungal strains. The bioactivity data showed the metal(II) complexes to have more potent antibacterial and antifungal activity than their uncomplexed parent Schiff bases against one or more bacterial and fungal species. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermodynamic quantities for the solution and protonation of four C6-amines in water over a wide temperature range

The enthalpies of solution ofn-hexyl- and cyclohexylamine have been determined at temperatures up to 125°C, of di-n-propylamine up to 100°C, and of triethylamine up to 75°C from reaction-solution calorimetric experiments. Quadratic polynomials were found to give good representations of the experimental values, implying a linear variation with temperature of the heatcapacity changes. The enthalpies of protonation of the aqueous amines have been determined in the same temperature range. Linear expressions give satisfactory representations of the protonation enthalpies of the hexylamines and dipropylamine, whereas a quadratic expression is required to represent the triethylamine values. The calorimetric results are used together with reported pK _a values at 25°C to calculate the dissociation constants of the corresponding ammonium ions between 0 and 200°C. At 0°C triethylamine was found to be the weakest base, the relative base strengths being triethyln-hexyl相似文献   

Metallosurfactant Schiff base cobalt(III) coordination complexes. Synthesis,characterization, determination of CMC values and biological activities

Twelve surfactant Schiff base ligands were synthesized from salicylaldehyde and its chloro-, bromo- and methoxy- derivatives by condensation with long-chain aliphatic primary amines, and a number of mixed ligand cobalt(III) surfactant Schiff base coordination complexes of the type [Co(trien)A]²⁺ were synthesized from the corresponding dihalogeno complexes by ligand substitution. The Schiff bases and their complexes were characterized by physico-chemical and spectroscopic methods. The complexes form foams in aqueous solution upon shaking. The critical micelle concentration (CMC) values of the complexes in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303–323 K) served for the evaluation of the thermodynamics of micellization ( \Updelta G_\textm⁰ \Updelta G_{\text{m}}^{0} , \Updelta H_\textm⁰ \Updelta H_{\text{m}}^{0} , \Updelta S_\textm⁰ \Updelta S_{\text{m}}^{0} ). The complexes were tested for its antimicrobial activity.     

Synthesis and evaluation of novel O-functionalized aminated chitosan derivatives as antibacterial,antioxidant and anticorrosion for 316L stainless steel in simulated body fluid

Chitosan’s Schiff base derivatives are taking the attention of scientists as a promising biomaterial for various applications. In this study, O-functionalized aminated chitosan (O-F-Am-Ch) was coupled with 4,4-dimethyl amino-benzaldehyde and N-methyl-2-pyrrolidone to produce Schiff bases (I) and (II), respectively. The chemical and physical properties of the new derivatives were investigated by Fourier transform infrared (FT-IR) that show a significant band for C=C between 1400 and 1600 cm⁻¹, thermal gravimetric analysis (TGA), which demonstrate an increase in the thermal stability of new derivatives than O-F-Am-Ch and scanning electron microscope (SEM) that indicates a slight increase in the rough structure of the surface. In addition, 2,2′-Azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) and 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assays that examined the antioxidant properties of the new Schiff bases. The biocidal activity against four different bacterial strains [two gram-negative (Pseudomonas aeruginosa and Escherichia coli) and two gram-positive (Bacillus cereus and Staphylococcus aureus)] demonstrates significant improvement of the inhibition activity compare to O-F-Am-Ch with more activity against Gram-negative bacteria than that against gram-positive bacteria.As an implanted alloy, 316L stainless steel is used as a temporary biomaterial in different countries without any pretreatment. Our study focused on further improving the alloy features by investigating the protection efficiency of O-F-Am-Ch and the synthesized Schiff bases for the 316L stainless steel surface against corrosion in simulated body fluid (SBF). The corrosion inhibition of these compounds was investigated using two electrochemical methods (potentiodynamic polarization technique and electrochemical impedance spectroscopy). The results suggested the formation of self-assembled monolayers (SAMs) of the compounds under investigation. Furthermore, they demonstrated a considerable dose-dependent inhibiting corrosion of 316L stainless steel in SBF, whereas the inhibition efficiency exceeds 77% at 1000 ppm for the Schiff bases II. In conclusion, the tested derivatives show promising properties to refine stainless steel for implant applications.     

Synthesis,potentiometric and antimicrobial activity studies on 2-pyridinilidene-DL-amino acids and their complexes

To investigate the relationship between antimicrobial activities and the formation constants of Cu^II, Ni^II and Co^II complexes with three Schiff bases, which were obtained by the condensation of 2-pyridinecarboxyaldehyde with DL-alanine, DL-valine and DL-phenylalanine, have been synthesized. Schiff bases and the complexes have been characterized on the basis of elemental analyses, magnetic moments (at ca. 25 °C), molar conductivity, thermal analyses and spectral (i.r., u.v., n.m.r.) studies. The i.r. spectra show that the ligands act in a monovalent bidentate fashion, depending on the metal salt used and the reaction pH = 9, 8 and 7 medium, for Cu^II, Ni^II and Co^II, respectively. Square-planar, tetrahedral and octahedral structures are proposed for Cu^II, Ni^II and Co^II, respectively. The protonation constants of the Schiff bases and stability constants of their ML-type complexes have been calculated potentiometrically in aqueous solution at 25 ± 0.1 °C and at 0.1 M KCl ionic strength. Antimicrobial activities of the Schiff bases and the complexes were evaluated for three bacteria (Bacillus subtillis, Staphylococcus aureus, and Escherichia coli) and a yeast (Candida albicans). The structure–activity correlation in Schiff bases and their metal(II) complexes are discussed, based on the effect of their stability contants.     

Lead Aerosol Collection Studies Using Solid Sorbent Packed Sampling Tubes

Abstract

The use of packed-bed solid sorbent tubes was investigated for the collection and concentration of lead and lead compound aerosols utilizing a lead metal laboratory test atmosphere and lead containing automobile exhaust. Four different sorbents were tested: alumina (100–150 mesh), silica gel (80–200 mesh), Chromosorb 102 (60–80 mesh), and Tenax-GC (80–100 mesh). The following average collection efficiencies were observed for the first portion of each sorbent in the tube (200 mg of sorbent) when sampling automobile exhaust: 95.8 ± 5.7 % for alumina, 98.5 ± 3.2 % for silica gel, 98.0 ± 3.7 % for Chromosorb 102, and 99.2 ± 2.6 % for Tenax-GC. Using the lead metal test aerosol, the average efficiencies were 99.2 ± 1.0, 99.2 ± 1.1, 99.9 ± 0.1, and 100.0 ± 0.0 % for the alumina, silica gel, Chromosorb 102, and Tenax-GC, respectively. Consideration of percent collection efficiency, blank values, and elution efficiency of lead from the sorbent indicated that Tenax-GC provided the best results.     

Oligonucleosides with a Nucleobase‐Including Backbone,Part 4, A Convergent Synthesis of Ethynediyl‐Linked Adenosine Tetramers

Deprotection of the tetramer 24 , obtained by coupling the iodinated dimer 18 with the alkyne 23 gave the 8′,5‐ethynediyl‐linked adenosine‐derived tetramer 27 (Scheme 3). As direct iodination of C(5′)‐ethynylated adenosine derivatives failed, we prepared 18 via the 8‐amino derivative 17 that was available by coupling the imine 15 with the iodide 7 ; 15 , in its turn, was obtained from the 8‐chloro derivative 12 via the 4‐methoxybenzylamine 14 (Scheme 2). This method for the introduction of the 8‐iodo substituent was worked out with the N‐benzoyladenosine 1 that was transformed into the azide 2 by lithiation and treatment with tosyl azide (Scheme 1). Reduction of 2 led to the amine 3 that was transformed into 7 . 1,3‐Dipolar cycloaddition of 3 and (trimethylsilyl)acetylene gave 6 . The 8‐substituted derivatives 4a – d were prepared similarly to 2 , but could not be transformed into 7 . The known chloride 8 was transformed into the iodide 11 via the amines 9 and 10 . The amines 3 , 10 , and 16 form more or less completely persistent intramolecular C(8)N−H⋅⋅⋅O(5′) H‐bonds, while the dimeric amine 17 forms a ca. 50% persistent H‐bond. There is no UV evidence for a base‐base interaction in the protected and deprotected dimers and tetramers.