Cycloaddition dipolaire [3+2] à partir d'hétérocycles aromatiques N-aminés

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Visible-light-induced selective photocatalytic oxidation of benzylamine into imine over supported Ag/AgI photocatalysts

Titanate nanotubes (TNT) supported AgI nanoparticles were prepared by a two-step method: the deposition of Ag2O on titanate nanotubes from AgNO3 solution and the subsequent I-adsorption process from NaI solution. It is found that the supported AgI samples exhibited excellent photoactivity for the selective oxidation of benzylamine to the corresponding imine under visible light illumination and the photocatalyst can be used for many times without apparent activity loss. X-ray diffraction studies, transmission electron microscopy, diffuse reflectance UV-Vis spectroscopy and nitrogen adsorption measurements were used for the characterization of the as-prepared and recycled AgI samples. It is found that under visible light irradiation, AgI partially decomposed to produce Ag/AgI nanostructure and thus stabilized. The photoactivity of supported Ag/AgI for the selective oxidation of benzylamine was studied in terms of the light intensity, wavelength, temperature and substituent. It is proposed that the formation of plasmonic Ag nanoparticles should be responsible for the high activity and selectivity.

Design of redox/radical sensing molecules via Nitrile Imine-Mediated Tetrazole-ene Cycloaddition (NITEC)

The current study introduces a novel synthetic avenue for the preparation of profluorescent nitroxides via nitrile imine-mediated tetrazole-ene cycloaddition (NITEC). The photoinduced cycloaddition was performed under metal-free, mild conditions allowing the preparation of a library of the nitroxide functionalized pyrazolines and corresponding methoxyamines. High reaction rates and full conversion were observed, with the presence of the nitroxide having no significant impact on the cycloaddition performance. The formed products were investigated with respect to their photophysical properties in order to quantify their “switch on/off” behavior. The fluorescence quenching performance is strongly dependent on the distance between the chromophore and the free radical spin as demonstrated theoretically and experimentally. Highest levels of fluorescence quenching were achieved for pyrazolines with the nitroxide directly fused to the chromophore. Importantly, the pyrazoline profluorescent nitroxides were shown to efficiently act as sensors for redox/radical processes.

Metal chelates in vinyl polymerization: Bulk polymerization of acrylonitrile initiated by Cu(II)-imine complexes

This article deals with the kinetics and mechanism of acrylonitrile (AN) polymerization initiated by Cu(II)-4-anilino 3-pentene 2-one[Cu(II)ANIPO], Cu(II)-4-p-toluedeno 3-pentene 2-one [Cu(II)TPO], and Cu(II)-4-p-nitroanilino 3-pentene 2-one [Cu(II)NAPO] in bulk at 60°C. The polymerization is free radical in nature. The exponent of initiator(I) is 0.5. The initiation step is a complex formation between the chelate and monomer and subsequent decomposition of the intermediate complex giving rise to free radical and Cu(I). This is substantiated by ultraviolet (UV) and electron spin resonance (ESR) studies. The activation energies and kinetic and chain transfer constants have also been evaluated.

Metal Chelates in Vinyl Polymerization: Kinetics and Mechanism of Acrylonitrile Polymerization Initiated by Cu(I1) Imine Complexes

The free radical polymerization of acrylonitrile (AN) initiated by Cu(I1) 4-anilino 3-pentene 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(I1) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCld), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were 22 at two different temperatures and in different solvents. The square-root dependence of R, on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formatign was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.

Mode of Coordination and Chemical Reactivity of Alpha-Imine Hydrasone Ligands

Interaction of nickel(I1) and copper(I1) complexes of 4,9-dimethy1-5,8-diazadodeca-4,8diene-2,1 ldione, Ni(baen) and 4,6,9-trimethyl-5, 8diazadodeca-4,8-diene-2,ll-dione, Ni(bapn), with arene diazonium chlorides in buffered solutions of methanol yielded metal derivatives of glyoxaliminearylhydrazones. This typical electrophilic addition at the 3-carbon of the complex occurs owing to the pseudo aromatic behaviour of the chelate ring. A mechanism which predicts the attack of the diazonium cation through the coordination shell of the metal is well documented from the available experimental evidences. The chemical reactivity of a few complexes with a single residual non-substituted y-carbon is reasonably manifested by their reaction with phenyl isocyanate.

Metal chelates in vinyl polymerization: Kinetics and mechanism of acrylonitrile polymerization initiated by Cu(II) imine complexes

The free radical polymerization of acrylonitrile (AN) initiated by Cu(II) 4-anilino 2-one [Cu(II) ANIPO] Cu(II), 4-p-toluedeno 3-pentene 2-one [Cu(II) TPO], and Cu(II) 4-p-nitroanilino 3-pentene 2-one [Cu(II) NAPO] was studied in benzene at 50 and 60°C and in carbon tetrachloride (CCl4), dimethyl sulfoxide (DMSO), and methanol (MeOH) at 60°C. Although the polymerization proceeded in a heterogeneous phase, it followed the kinetics of a homogeneous process. The monomer exponents were 2 at two different temperatures and in different solvents. The square-root dependence of Rp on initiator concentration and higher monomer exponents accounted for a 1:2 complex formation between the chelate and monomer. The complex formation was shown by ultraviolet (UV) study. The activation energies, kinetics, and chain transfer constants were also evaluated.

Linkage isomerism in nickel(II) I-isonitroso-imine ligand complexes

I-isonitroso-imine ligand complexes of nickel(II), namely, bis(isonitrosomethylacetoacetate-imino)Ni(II), Ni(IMI)(IMI); bis(isonitrosobenzoylacetoneimino)Ni(II), Ni(IBI)(IBI) and bis(isonitrosoacetoacetanilideimino)Ni(II), Ni(IANI)(IANI), have been prepared and characterized. On the basis of their spectroscopic and magnetic properties, these complexes are suggested to have a square-planar stereochemistry around the metal ion with both nitrogen (ligand denoted without prime) and oxygen (ligand denoted with prime) coordinated isonitroso groups. The i.r. and NMR spectra of these and other similar complexes are discussed.

Heterojunctions between amorphous and crystalline niobium oxide with enhanced photoactivity for selective aerobic oxidation of benzylamine to imine under visible light

The formation of heterojunctions between two crystals with different band gap structures, acting as a tunnel for the unidirectional transfer of photo-generated charges, is an efficient strategy to enhance photocatalytic performance in semiconductor photocatalysts. The heterojunctions may also promote the photoactivity in the visible-light-response of any surface complex catalysts by influencing the transfer of photo-generated electrons. Herein, Nb2O5 microfibers, with a high surface area of interfaces between an amorphous phase and crystalline phase, were designed and synthesised by the calcination of hydrogen-form niobate while controlling the crystallization The photoactivity of these microfibers towards selective aerobic oxidation reactions was investigated. As predicted, the Nb2O5 microfibres containing heterojunctions exhibited the highest photoactivity. This could be due to the band gap difference between the amorphous phase and the crystalline phase, which shortened the charge mobile distance and improved the efficiency.

Poly propyl ether imine (PETIM) dendrimer: A novel non-toxic dendrimer for sustained drug delivery

In the present study, an attempt was made to study the acute and sub-acute toxicity profile of G3-COOH Poly (propyl ether imine) PETIM] dendrimer and its use as a carrier for sustained delivery of model drug ketoprofen. Drug-dendrimer complex was prepared and characterized by FTIR, solubility and in vitro drug release study. PETIM dendrimer was found to have significantly less toxicity in A541 cells compared to Poly amido amine (PAMAM) dendrimer. Further, acute and 28 days sub-acute toxicity measurement in mice showed no mortality, hematological, biochemical or histopathological changes up to 80 mg/kg dose of PETIM dendrimer. The results of study demonstrated that G3-COOH PETIM dendrimer can be used as a safe and efficient vehicle for sustained drug delivery. (C) 2010 Elsevier Masson SAS. All rights reserved.

Studies on ß-arylhydrazone-imine nickel(II) complexes—Examples of metal template syntheses

ß-arylhydrazone-imine ligand complexes of nickel(II), namely, 4,10-dimethyl-5,9-diazatrideca-4,9-diene-2,12-dione-3,11-diphenylhydrazonato nickel(II), Ni(acacpn)(N2Ph-R)2 and 1,11-diphenyl-3,9-dimethyl-4,8-diazaun-deca-3,8-diene,1,11-dione-2,10-diphenyl hydrazonato nickel(II), Ni (beacpn) (N2Ph-R)2, [R = H, o-CH3p-CH3] have been prepared by metal template reactions and characterized. Both the azomethine nitrogens and α-nitrogens of bis-hydrazone form the coordination sites of the square-planar geometry around the nickel(II) ion. Loss of CO from the molecule and subsequently an interesting methyl group migration to the nucleus of the chelate ring have been observed in the mass spectrum. Structures are proposed based on the spectral and magnetic properties.