Polymeric Schiff Bases. III. Some Prototype Exchange Reactions of Schiff Bases

The amine moiety in Schiff bases can be exchanged quantitatively by another amine to yield new Schiff bases if the volatility of the replacing amine is lower than the derived amine, thereby allowing the latter to distilled from the reaction mass. This amine exchange was shown to be quantitative also for diamines and di-Schiff bases. Similarly, quantitative conversions were found for aldehydes and acetal exchanges with Schiff bases for both monofunctional and difunctional reactants. The bis exchange, involving two complementary Schiff bases, was quantitative also when the reactants were so selected that one of the new derived Schiff bases could be removed by distillation. The bis exchange was demonstrated with mono and di-Schiff bases.

Mechanisms are suggested for these Schiff base exchange reactions: attempts to isolate the proposed intermediates physically were unsuccessful; however spectroscopic evidence indicates the formation of intermediate compounds.

The Schiff base exchanges involving polyfunctional reactants are of interest in the synthesis of polymers.     

The Preparation, Characterization and Biological Activity of Palladium(II) and Platinum(II) Complexes of Tridentate NNS Ligands Derived from S-methyl- and S-benzyldithiocarbazates and the X-ray Crystal Structure of the [Pd(mpasme)Cl] Complex

New complexes of general formula, [M(NNS)Cl] (M = Pd^II, Pt^II; NNS = anionic forms of the 6-methyl-2-formylpyridine Schiff bases of S-methyl- and S-benzyldithiocarbazates) have been prepared and characterized by a variety of physico-chemical techniques. Based on conductance and spectral evidence, a square-planar structure is assigned to these complexes. The crystal and molecular structure of the [Pd(mpasme)Cl] complex (mpasme=anionic form of the 6-methyl-2-formylpyridine Schiff base of S-methyldithiocarbazate) has been determined by X-ray diffraction. The complex has a distorted square-planar geometry with the ligand coordinated to the palladium(II) ion via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the fourth coordination position around the palladium(II) ion is occupied by the chloride ligand. The distortion from a regular square-planar geometry is ascribed to the restricted bite angle of the ligand. Both the Schiff bases exhibit strong cytotoxicity against the human ovarian cancer (Caov-3) cell lines, the S-methyl derivative being two times more active than the S-benzyl derivative. The [Pt(mpasme)Cl] complex is moderately active but the palladium(II) complex is weakly active against this cancer. None of the complexes of Hmpsbz are active against Caov-3. The Schiff base, Hmpasme exhibits moderate activity against the bacteria, MRSA, P. aeruginosa and S. typhimurium but is inactive against B. subtilis. Coordination of the ligand with palladium(II) substantially reduces its activity. The Schiff base, Hmpasbz and its palladium(II) and platinum(II) complexes are inactive against these bacteria. The Schiff bases and their palladium(II) and platinum (II) complexes are inactive against the pathogenic fungi, C. albican, Aspergillus ochraceous and Saccharomyces cerevisiae.     

SYNTHESIS, CHARACTERIZATION AND SELECTIVITY STUDIES OF POLY(ACRYLAMIDE) INCORPORATING SCHIFF BASES

Three novel polymers incorporating Schiff bases,derived from condensation reactions of poly(acrylamide) with 5- chloro-2-hydroxybenzaldehyde,5-bromo-2-hydroxybenzaldehyde and 5-methyl-2-hydroxybenzaldehyde,have been synthesized,and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been prepared.The ~1H-NMR signals of the—CH=N—and—NH_2 groups have been utilized to determine the relative abundances of Schiff base and acrylamide groups in the polymers containing Schiff bases.Poly(acrylamide) incorporating Schiff bases a...     

Spectral,magnetic, biological,and thermal studies of metal(II) complexes of some unsymmetrical Schiff bases

New nickel(II) and copper(II) complexes with unsymmetrical Schiff bases derived from aromatic 2-hydroxy aldehydes were synthesized and characterized by elemental analyses, melting points, ¹H-NMR, magnetic susceptibility, thermogravimetric analysis, differential scanning calorimetry (DSC), infrared (IR), and electronic spectral measurements. Comparison of IR spectra of the Schiff bases and their metal complexes indicated that the Schiff bases are tetradentate, coordinated via the two azomethine nitrogens and the two phenolic oxygens. Magnetic moments and electronic spectral data confirm square-planar geometry for the complexes. Thermal studies reveal a general decomposition pattern, whereby the complexes decomposed partially in a single step due to loss of part of the organic moiety. A single endothermic profile, corresponding to melting point, was observed from the DSC of all complexes, except those whose ligand contained the nitro group, which decomposed exothermally without melting. The Schiff bases and their complexes were screened in vitro against 10 human pathogenic bacteria. The metal(II) complexes exhibited higher antibacterial activity than their corresponding Schiff bases.     

Chemical release control—Schiff bases of perfume aldehydes and aminostyrenes

Schiff bases of p- and m-aminostyrenes with perfume aldehydes such as citral, cinnamaldehyde, piperonal, vanillin, and ethyl vanillin were synthesized in ethanol in more than 50% yield. Water-soluble copolymers of these Schiff bases with N-vinyl-2-pyrrolidone or with N,N-dimethylacrylamide were obtained. The hydrolytic behavior of Schiff base monomers and copolymers to liberate perfume aldehydes was structure dependent, thereby affording chemical release control.     

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.     

Polymeric arylsulfonylmethyl isocyanide,a novel polymer reagent

p-Vinylphenylsulfonylmethyl isocyanide (1M) was synthesized starting with sodium p-styrenesulfinate via p-vinylphenylsulfonylmethylformamide (4M). Free-radical polymerization of 1M provided cross-linked insoluble polymers (1), whereas 4M provided soluble polymers, which could be converted to soluble polymer 1. Conversions of carbonyl compounds to nitriles and Schiff bases to 1,5-disubstituted imidazoles with both soluble and cross-linked polymers 1 as reagents proceeded almost as efficiently as with their low molecular weight analog. Reusability of polymer 1 was fairly good.     

Oxotitanium(IV) complexes of some bis‐unsymmetric Schiff bases: Synthesis,structural elucidation and biomedical applications

A number of oxotitanium(IV) complexes of the type TiOL with bis‐unsymmetric dibasic tetradentate Schiff base (LH₂) containing ONNO donor atoms have been synthesized. Mono‐Schiff base (OPD‐HNP) was prepared by the condensation of 1:3 molar ratio of 2‐hydroxy‐1‐naphthaldehyde (HNP) with o‐phenylenediamine (OPD). Dibasic unsymmetric tetradentate diamine Schiff bases were prepared by the reaction of OPD‐HNP with 2‐hydroxyacetophenone, 2‐hydroxypropeophenone, benzoylacetone, acetylacetone and ethylacetoacetate. Further, titanylacetylacetonate was reacted with these ligands to obtain their metal complexes. On the basis of analytical and physiochemical data, the formation of complexes as TiOL was suggested having square pyramidal geometry. Quantum mechanical approach also confirmed this geometry. The assessment of the synthesized ligands and their complexes showed that some behave as good inhibitors of mycelial growth against selected phytopathogic fungi but weak inhibitors against some selected bacteria. A few of them also showed antioxidant properties.     

Synthesis and antitumor activity evaluation of some schiff bases derived from 2‐aminothiazole derivatives

A novel series of thiazolyl Schiff bases have been designed and synthesized. These new compounds were obtained by the reactions of 4‐phenyl‐5‐(1H‐1,2,4‐triazol‐1‐yl) thiazol‐2‐amine and substituted aromatic aldehydes and were characterized on the basis of ¹H NMR and elemental analysis. The newly synthesized compounds were screened for their antitumor activity against human cancer cell lines, namely HL‐60 (leukemia), BGC‐823 (stomach), and HEP‐2 (larynx cancer). © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:55–59, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20256     

Systematic studies on mechanochemical synthesis: Schiff bases from solid aromatic primary amines and aldehydes

A versatile and robust mechanochemical route to Aldehyde–Schiff base conversions has been established for a broad range of aldehydes via a simple cogrinding in mortar with a pestle under a solvent‐free, as well as solvent‐assisted, environment. The extent of amines reactivity under these conditions has also been explored, along with an examination of the possible connection between reactivity and electronic substituent effects. Results obtained demonstrated that the solvent‐free mechanochemical conversion of p‐toluidine and aromatic aldehydes to the corresponding Schiff bases proceeded more smoothly than the corresponding synthesis with 4‐aminobenzonitrile. The present approach not only provides good to excellent yields but also eliminates the disadvantages of the traditional synthesis of Schiff bases, such as the use of hazardous solvents, more or less demand of expensive catalysts, and looking for optimization on reaction conditions.     

Catalytic and antimicrobial activities of new ruthenium(II) unsymmetrical Schiff base complexes

Hexa-coordinated ruthenium(II) complexes of the type [Ru(CO)(PPh₃)(Z)(L)] [Z = PPh₃, pyridine (py) or piperidine (pip); L = anion of the Schiff base] have been prepared by reacting [RuHCl(CO)(PPh₃)₂(Z)] with tridentate Schiff bases derived by condensing anthranilic acid with acetylacetone, salicylaldehyde, o-vanillin and o-hydroxyacetophenone. The complexes were characterised by analytical and spectral (i.r., electronic, ¹H- and ³¹P-n.m.r.) data, and were found to be effective catalysts for oxidising primary alcohols to aldehydes in the presence of N-methylmorpholine-N-oxide (NMO) as co-oxidant. The Schiff bases and their ruthenium(II) complexes show growth inhibitory activity against pathogenic fungi Aspergillus flavus, Fusarium oxysporium and Rhizoctonia solani.     

Green and Catalyst-Free One-Pot Synthesis of Anthranilamide Schiff Bases: An Approach Toward Sirtinol

A novel and simple method for the green one-pot synthesis of anthranilamide Schiff bases is described. The reported Schiff bases are obtained via the reaction of isatoic anhydride, amines, and aromatic aldehydes in water at room temperature, without using any catalysts. No cyclization toward 2,3-dihydro-4(1H)-quinazolinones occurred in this method and anthranilamide Schiff bases were produced exclusively. This approach offers a green method to prepare the medicinally important Schiff base sirtinol and other bioactive anthranilamide Schiff bases.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

二茂铁席夫碱的合成及细胞毒活性

为了研究二茂铁席夫碱对癌细胞毒性,以二茂铁甲醛或乙酰基二茂铁与3-取代-4-氨基-1,2,4-三唑-5-硫酮或酰肼缩合,得到6个新型的含二茂铁基的缩胺类席夫碱和4个酰腙类席夫碱.利用1H NMR,IR,MS谱和元素分析对化合物结构进行了表征.体外细胞测试结果表明,所有化合物对Hela (宫颈癌细胞)均有一定的抑制生长活性,而且杂环缩胺类席夫碱2的细胞毒活性要强于酰腙类席夫碱4.     

Syntheses,Structures and Anticancer Activity of NNO‐Tridentate Schiff Base Copper(II) Complexes

A series of heteroleptic copper(II) complexes [Cu( ^R QYMP )(Py]] ( 1a ‐ 4d ) supported on NNO‐tridentate Schiff base ( ^R QYMP ‐H) and bipyridine (Py=bpy, a ; phen, b ; dpq, c ; dppz, d ) co‐ligands have been synthesized and characterized. X‐ray crystal structural studies of complexes 1b , 2c , 3d and 4a displays that these complexes are mononuclear with a distorted square pyramidal geometry around the copper center. Cytotoxicity results indicate that all of these complexes have much higher activity against HeLa, SCC15, BCC and Ca9‐22 cancer cell lines as compared to cisplatin. Further, copper complex bearing suitable bulky group Schiff base ligands with dppz co‐ligand could be considered in designing efficient metalbased anticancer agents.     

Diorganotin(IV) complexes of biologically potent 4(3H)-quinazolinone derived Schiff bases: synthesis, spectroscopic characterization, DNA interaction studies and antimicrobial activity

Four Schiff base ligands and their corresponding organotin(IV) complexes have been synthesized and characterized by elemental analyses, IR, (1)H NMR, MS and thermal studies. The Schiff bases are obtained by the condensation of 3-amino-2-methyl-4(3H)-quinazolinone with different substituted aldehydes. The elemental analysis data suggest the stoichiometry to be 1:1 ratio formation. Infrared spectral data agreed with the coordination to the central metal ion through imine nitrogen, lactam oxygen and deprotonated phenolic oxygen atoms. All the synthesized compounds have been evaluated for antimicrobial activity against selected species of microorganisms. In addition, DNA binding/cleavage capacity of the compounds was analyzed by absorption spectroscopy, viscosity measurements and gel electrophoresis methods.     

Synthesis,characterization, and antioxidant activity of heterocyclic Schiff bases

Schiff base derivatives have gained great importance due to revealing a great number of biological properties. Schiff bases were synthesized by treatment of 4-amino-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one ( 1 ) with various aldehydes in methanol at reflux. In addition, diamine was reacted with an aldehyde to yield the corresponding Schiff bases. The structures of synthesized Schiff bases were elucidated by spectroscopic methods such as microanalysis, ¹H-NMR, ¹³C-NMR, and FTIR. Antioxidant activities of synthesized Schiff bases were carried out using different antioxidant assays such as 1,1-diphenyl-2-picryl-hydrazyl free radical (DPPH^•) scavenging, 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) radical scavenging, and reducing power activity. (E)-4-((1H-indol-3-yl)methyleneamino)-1,5-dimethyl-2-phenyl-1H-pyrazol-3(2H)-one ( 3 ), (E)-1,5-dimethyl-4-((2-methyl-1H-indol-3-yl)methyleneamino)-2-phenyl-1H-pyrazol-3(2H)-one ( 5 ), (E)-1,5-dimethyl-2-phenyl-4-(thiophen-2-ylmethyleneamino)-1H-pyrazol-3(2H)-one ( 7 ), (E)-1,5-dimethyl-2-phenyl-4-(quinolin-2-ylmethyleneamino)-1H-pyrazol-3(2H)-one ( 9 ), (1S,2S,N1,N2)-N1,N2-bis((1H-indol-3-yl)methylene)cyclohexane-1,2-diamine ( 11 ), and (1S,2S,N1,N2)-N1,N2-bis((2-methyl-1H-indol-3-yl)methylene)cyclohexane-1,2-diamine ( 12 ) were synthesized in high yields. Compound 5 displayed a good ABTS^•+ activity. Compound 3 revealed the outstanding activity in all assays. Compound 7 has the best-reducing power ability in comparison to other synthesized compounds. Although compounds 5, 11, 12 are new, compounds 3, 7, 9 are known. Due to revealing a good antioxidant activity, the synthesized compounds ( 3, 5, 7 ) have the potential to be used as synthetic antioxidant agents.     

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.     

Applying Cu(II) complexes assisted by water-soluble porphyrin to DNA binding and selective anticancer activities

Cancer is one of the killers endangering human health and its treatment has always been a focus of the medical community. For anticancer drugs, water-soluble porphyrin and Schiff bases have always been of interest. We report here three Cu(II)-based complexes functionalized by water-soluble cationic porphyrin and hydrazine Schiff base, which were prepared and evaluated for their biological activity. The three Cu(II) complexes all exhibited potent binding affinity to calf thymus DNA, the strongest interaction being between CuP2 and DNA. We studied the cytotoxicity of the complexes and ligands against different types of cancer cells (A549, H-1975, HepG2 and T47D), results showing the ligands are less cytotoxic; therefore, the anticancer activity of the complexes is improved by complexation. Furthermore, the cytotoxicity of ligands and complexes was also evaluated against the normal cell line Hs 578Bst, complexes showing more negligible cytotoxicity than ligand. Moreover, the cellular uptake of these Cu(II) complexes was investigated using the extraction method and results suggested that CuP2 exhibits the best cellular uptake towards H-1975 cells. Interestingly, fluorescence microscopy experiments and flow cytometric analysis (cell cycle) were used to further investigate the potent anticancer activities.     

Nitrile elimination and hydrogen rearrangement upon electron impact in schiff base peptide esters

A series of Schiff base peptide esters were examined by gas chromatography mass spectrometry. Electron impact induced elimination of aryl nitriles (ArCN) from Schiff bases , where R, R′ …are amino acid sidechains formed from aromatic aldehydes and peptide esters was shown to be associated with formation of C-terminal peptide fragments. Schiff base derivatives prepared from benzaldehyde and α-deuterobenzaldehyde with several peptide esters indicated that aryl nitrile elimination was accompanied by H(D) transfer to the α-C of the N-terminal amino acid residue. Of the many Schiff base peptide esters of different aldehydes studied, HCN elimination of the type observed in some nonpeptide Schiff bases could only be found among N-methyl pyrrolemethylidene derivatives.     

Design,synthesis, and antilung adenocarcinoma activity research of novel paeonol Schiff base derivatives containing a 1,2,3-triazole moiety

A new series of paeonol Schiff base derivatives containing a 1,2,3-triazole moiety were synthesized using the copper(I) catalyzed azide-alkynecycloaddition (CuAAC) reaction and evaluated for their cytotoxicity in vitro against human cervical carcinoma HeLa cells, human lung cancer A549 cells, and human liver cancer HepG2 cells. Unfortunately, all the tested compounds showed poor activities toward the human cervical carcinoma HeLa cells and human liver cancer HepG2 cells. However, compounds (E)-2-(1-(((1-[2-fluorophenyl]-1H-1,2,3-triazol-4-yl)methyl)imino)ethyl)-5-methoxyphenol ( 4c ) and (E)-2-(1-(((1-[3- chlorophenyl]-1H-1,2,3-triazol-4-yl)methyl)imino)ethyl)-5-methoxyphenol ( 4i ) exhibited inhibitory activities toward human lung cancer A549 cells (IC₅₀ = 45.1 μM for 4c and 78.9 μM for 4i ) compared with that of paeonol, which indicated that such paeonol Schiff base derivatives containing a 1,2,3-triazole moiety could be further modified to obtain good cytotoxicity in vitro against human lung cancer A549 cells.