Photoredox-neutral ring-opening pyridylation of cyclic oximes via phosphoranyl radical-mediated N-O/C-C bond cleavages and sequential radical-radical coupling

A novel photoredox-neutral ring-opening pyridylation of non-prefunctionalized cyclic oximes has been accomplished through phosphoranyl radical-mediated N-O/C-C bond cleavages followed by radicalradical coupling.This mild acid-,base-,and oxidant-free protocol provides highly site-selective and efficient access to distally pyridylated alkylnitriles,which could be scale-up synthesized and readily converted into skeletally diverse compounds.Notably,the oxidized ground-state photocatalyst generated via the SET oxidation of the highly reducing excited-state photocatalyst by cyanopyridines might initiate the following phosphoranyl radical-mediated deoxygenative process.

甲基亚硝胺基吡啶基丁酮致癌作用研究进展

甲基亚硝胺吡啶基丁酮(4-(methylnit-rosamino)-1-(3-pyridyl)-1-butanonoe,NNK)是一种香烟特异性亚硝胺,它是烟碱与硝酸钠在PH2-7, 温度20℃时进行亚硝化而产生的一种亚硝胺酮。1978年Hoffman等首次报道香烟中有NNK,并对NNK的活化代谢进行了研究。在过去的十几年中有关NNK的研究有较多报道。实验表明,NNK是香烟的主要致癌物之一,它在香烟中含量较高,且致癌性较强,可诱发动物肺癌,鼻咽癌等肿瘤。近年来,在NNK致癌机制等方面有了更进一步的认识,NNK对人的致癌作用也开始引人注目,本文就NNK的研究资料。

Synthesis and Biological Activities of α-Amino Acylamines Derivatives Containing Furan and Pyridine Ring

In order to find better herbicidal activity and fungicidal activity of a-amino acid derivatives, we introduced furan rings and pyridyl groups to seven different a-amino acids to form a series of 14 novel a-amino acylamines derivatives via dicyclohexylcarbodiimide/4-dimethylaminopyridine（DCC/DMAP） coupling method. The structures of all the compounds prepared were confirmed by IR, LC/MS, IH NMR, and elemental analysis. The herbicidal and fungicidal results show that some compounds containing glycine and valine substrate have good activities.

PREPARATION OF POLYMER MICROSPHERES WITH PYRIDYL GROUP AND THEIR STABILIZED GOLD METALLIC COLLOIDS

Narrow disperse poly（ethyleneglycol dimethacrylate-co-4-vinylpyridine） （poly（EGDMA-co-4-VPy）） microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate （EGDMA） and 4-vinylpyridine （4-VPy） with 2,2＇-azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile. The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm, which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles. The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.

Crystal Structure and Electronic Structure of a Luminescent Compound 2-(2-Pyridyl) Benzimidazole

The crystal structure of 2-(2-pyridyl) benzimidazole was determined by single- crystal X-ray diffraction at 193(2) K. It crystallizes in orthorhombic system, space group Pbca with unit cell constants a = 10.6204(7), b = 10.1407(4), c = 18.6327(8) , Z = 8, V = 2006.7(2) 3, Dc = 1.292 g/cm3, F(000) = 816 and m(MoK) = 0.081 mm-1. The structure was refined to R = 0.0317 and wR = 0.0454 for 795 observed reflections with I > 2s(I). In the solid state, it has an emission maximum at 369 nm, while in solution (DMSO), the maximum excitation is at 372 nm. Quantum chemistry calculation was performed by the method of density functional theory. Theoretical results show that atom N is the reactive site when coordinating with a metal, and the electronic structure of the title compound presents excellent carrier transport properties.

New thermally stable polyesters based on 2,5-pyridinedicarbonyl dichloride and aromatic diols:Synthesis and characterization

Six new thermally stable polyesters （4a-f） were synthesized through the solution polycondensation reaction of 2,5-pyridine dicarbonyldichloride （2） with six aromatic diols in N,N＇-dimethyl acetamide （DMAc） solution and in the presence of pyridine as a base. The polycondensation reactions produce a series of new polyesters （4a-f） in high yields, and inherent viscosity between 0.30 and 0.55 dL/g. The resulting polyesters were characterized by elemental analysis, viscosity measurements, thermal gravimetric analysis （TGA and DTG）, solubility test, Fourier transform infrared （FT-IR） spectroscopy and gel permeation chromatography （GPC）. C 2009 Khalil Faghihi. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Synthesis and characterization of new polyesters based on 2,5-bis[(4-chloro carboxyanilino)carbonyl]pyridine and aromatic diols

Six new polyesters 7a-f were synthesized through the solution polycondensation reaction of diacid chloride 5 with six aromatic diols 6a-f in N,N-dimethyl acetamide(DMAc) as solvent in the presence of pyridine as base.The polycondensation reaction produced a series of novel polyester containing pyridyl moiety in the main chain in high yields with inherent viscosities between 0.35 and 0.54 dL/g.The resulted polymers were fully characterized by means of FT-IR spectroscopy,elemental analyses,inherent viscosity ...

Dication-accelerated anion transport inside micropores for the rapid decontamination of pertechnetate

Over 70%of the treated contaminated water at the Fukushima Daiichi Nuclear Power Station contains radionuclides beyond the regulatory standard for discharge that need to be re-purified.Technetium-99(^(99)Tc),mainly in the form of pertechnetate Tc(VII)O_(4)^(-),is one of the main sources of long-term radiotoxicity that jeopardizes the environment and human health.Herein,we used a series of dicationic pyridinium(DCP)derivative groups(–Py^(+)C_(n)H_(2n)N^(+)Me_(3),n=2,3,and 5)to modify commercial Reillex 425 resins containing tertiary pyridyl groups to improve the adsorption performance of rhenium(Re,an analog of radioactive Tc)and Tc.As the quaternary pyridinium and ammonium sites in one DCP group can adsorb ReO_(4)^(-) simultaneously,DCP-modified Reillex 425(Reillex-Cn)exhibited high maximum adsorption capacities for Re under neutral conditions.Adsorption capacities reached 344.8,416.7,and 588.2 mg g^(-)1 for Reillex 425-C2,Reillex 425-C3,and Reillex 425-C5,respectively.Intraparticle diffusion of ReO_(4)^(-)/TcO_(4)^(-) in Reillex 425-Cn was verified to be the rate-limiting step of adsorption.However,adsorption can be adjusted by the length of the alkyl spacers between the two positively charged N sites in DCP.–Py^(+)C_(2)H_(4)N^(+)Me_(3) significantly enhanced intraparticle diffusion compared to–Py^(+)C_(5)H_(10)N^(+)Me_(3).The two positive sites in–Py^(+)C_(2)H_(4)N^(+)Me_(3) would be laterally distributed,leading to a smaller steric hindrance for ReO_(4)–/TcO_(4)^(-) transport inside the microporous channels.Meanwhile,the longer alkyl spacers in–Py^(+)C_(5)H_(10)N^(+)Me_(3) formed hydrophobic microphases,repulsing the hydrated ReO_(4)–/TcO_(4)^(-) anions.Thus,the adsorptions of both ReO_(4)^(-) and TcO_(4)^(-) on Reillex 425-C2 were faster than those on Reillex 425-C5.Moreover,Reillex 425-Cn exhibited an exothermic nature,good selectivity,excellent reusability,and strong salinity tolerance.This study provides a simple strategy to enhance the Tc removal performance of adsorbents containing abundant micropores,which implies enormous environmental and economic benefits.

LANTHANIDE COMPLEXES OF ACETYLACETONATE-MESO-TETRA-(4-PYRIDYL)PORPHYRIN

New tanthanide comptexes of acetylacetonate-meso-tetra- (4-pyridyt)porphyrin(LnTpypacac,Ln=Dy,Ho,Yb,Lu,H_2Tpyp= tetra-(4-pyridyl)-porphyrin,Hacac=acetylacetone)were prepared by reaction of Ln(acac)_3·3H_2O with H_2Tpyp and were characterized by elemental analyses,ultra-viotet spectra,infrared spectra and thermal analyses.

THE SEPARATIONS OF ENANTIOMERS OF α—SUBSTITUTED-(2—PYRIDYL)—METHYLAMINES ON A CHIRASIL-VAL CAPILLARY COLUMN

Enantiomers of a-substituted-(2-pyridyl)-methylarfdnes uere separated on SC -7 gas chromatograph with a 20m×0.25mm Chirasil-Val capIlary column,Carrier gas was nitro- gen or hydrogen.The resolution factors(ri.s) were 1.02 to 1.06.Enantiomers of pyridyl anines were separated to and near to base line.

IN VIVO-I:VITRO TRANSFORMATION SYSTEM OF RAT TRACHEAL EPITHELIAL CELLS

An in vivo-in vitro transformation system was establi-shed in primary rat tracheal epithelial cells(RTE) whichwere cultured in serum-free F12 medium with the additionof growth factors.Carcinogens were given in vivo by subcu-taneous injection or intratracheal instillation.About 7days after carcinogen exposure,RTE cells were cultured inserum-free medium and then selected in serum-containingmedium.Transformed colonies were counted 5-6 weeks afterthe plating of RTE cells.

Synthesis, Crystal Structure, and Catalytic Performance of 2,6-Bis[1-(2,4,6-trimethylphenylimino)ethyl]pyridine Nickel(Ⅱ) Complex

A novel nickel（II）-complex Ni[L]Cl2-CH3CN（1） containing the tridentate ligand 2,6-bis[1-（2,4,6- trimethylphenylimino）ethyl]pyridine（L） has been synthesized. The crystal structure of complex 1 was determined by single crystal X-ray diffraction analysis. The catalytic activity of complex 1 for the polymerization of ethylene was studied under activation with methylaluminoxane（MAO）.

VINYL POLYMERIZATION OF NORBORNENE CATALYZED BY [2-(2-BENZIMIDAZOLYL)-6-((1-ARYLIMINOETHYL)PYRIDYL)]NICKEL CHLORIDE/MAO SYSTEM

The catalytic system of[2-(2-benzimidazolyl)-6-((1-aryliminoethyl)pyridyl)]nickel chloride/MAO(methylalu- minoxane)was found to be good active for vinyl polymerization of norbornene and provided polymers with relative narrow molecular distributions.Various reaction parameters,such as the ratios of nickel precursor to MAO or monomer norbornene, and the nature of the ligands in complexes were carefully investigated to realize their effects on the catalytic activities, polymer molecular weight and molecular we...

A homopolymolybdate-supported plate-like 2D cobalt network constructed from a new pyrazole-amide-pyridyl ligand: highly electrochemical activity in both capacitive performance and the detection of Cr(Ⅵ)

By employing a new semi-rigid pyrazole-amide-derived bis(pyridyl)ligand[N,N'-bis(4-picolylamine)-1-hydropyrazole(4-dpap)],a new homopolymolybdate-based two-dimensional(2D)plate-like complex[Co(4-dpap)(H_(2)O)(β-Mo_(8)O_(2)6)1/2](1)has been prepared under solvothermal condition and structurally characterized.Theβ-Mo_(8)anions are fi xed between the 2D metal–organic networks[Co(4-dpap)(H_(2)O)]n 2n+via hydrogen-bonding interaction.Complex 1 possesses satisfactory specifi c capacitance of 1512.4 F·g^(−1)(current density:1 A·g^(−1))and good cycling stability(90.8%after 1000 cycles).Moreover,1 represents a promising amperometric sensor for measurement of Cr(Ⅵ)with low detection limit(0.042μmol·L^(−1))and high durability.The insertion ofβ-Mo_(8)anions between the unique 2D metal−organic networks improves the active area of polyoxometalates,which further promotes electrochemical performance.

Rh(Ⅱ)-catalyzed intermolecular carboamination of pyridines via double Csp^(2)-H bond activations

We disclose the development of the Rh-catalyzed amine-directed remote 5,6-carboamination protocol of pyridines via dual Csp^(2)-H functionalizations.A variety of readily available 2-aminopyridines and 1,2,3-triazoles are allowed for coupling cyclization to access polyfunctionalized azaindoles.Mechanistic studies including DFT calculations unveil that relay carbenoidelectrophilic addition to pyridines and the sequential pyridyl Csp^(2)-H amination are involved in this transformation.The postsynthetic utility of this methodology is showcased by versatile and site-selective modification of azaindoles.

Peculiarities of Ethylene Polymerization Reactions with Bis(imino)pyridyl Complexes of CoCl_(2) and FeCl_(2)

The article describes ethylene polymerization reactions with transition metal catalysts based on complexes of CoCl_(2) and FeCl_(2) with an N,N,N-tridentate ligand 2,6-bis[1-(2,6-dimethylphenylimino)ethyl]pyridine. The complexes are converted into polymerization catalysts by reacting them either with polymethylalumoxane (MAO) or with a combination of Al(C2H5)2Cl and Mg(C4H9)2 at an [Al]:[Mg] ratio of ~3. Both MAO-activated complexes readily polymerize ethylene at 35 ℃ with the formation of linear, low molecular weight polymers with a narrow molecular weight distribution. The same complexes, when activated with the Al(C2H5)2Cl-Mg(C4H9)2 combination, form multi-center catalysts and generate polyethylenes with a broad molecular weight distribution.

Metal-free synthesis of pyridyl conjugated microporous polymers with tunable bandgaps for efficient visible-light-driven hydrogen evolution

Conjugated microporous polymers(CMPs) with tunable bandgaps have attracted increasing attention for photocatalytic hydrogen evolution. However, the synthesis of CMPs usually needs expensive metal-based catalysts. Herein, we report a metal-free synthetic route to fabricate pyridyl conjugated microporous polymers(PCMPs) via a condensed polymerization between aldehyde and aryl ketone monomers. The PCMPs show widely tunable specific surface areas(347–418 m^(2)/g), which were controlled via changing the used monomers. The PCMPs synthesized using monomers of dialdehyde and diacetylbenzene(diacetylpyridine) in the presence of pyridine exhibited the highest visible-light driven hydrogen evolution rate(9.56 μmol/h). These novel designed PCMPs provide wide adaptability to current materials designed for high-performance photocatalysts in different applications.

Synthesis and Biological Activities of Substituted Triazolethione Schiff Base

Six novel Schiff bases have been synthesized by the condensation reaction of 4-amino-5-（4-pyridyl）-2,4-dihydro-1,2,4-triazole-3-thione with various benzaldehydes. The sfructures of the compounds have been confirmed by ^1H NMR, IR and elemental analysis. The preliminary bioassay indicated that the title compounds possessed good fungicidal activities to several vegetable pathogens.