Visible-light-induced deoxygenative C2-sulfonylation of quinoline N-oxides with sulfinic acids for the synthesis of 2-sulfonylquinoline via radical reactions

A simple and efficient method for the synthesis of 2-sulfonylquinoline from deoxygenative C2-sulfonylation of quinoline N-oxides with sulfinic acid induced by visible light is presented.This protocol shows a broad substrate scope,and desired products with various substituents can be formed in moderate to high yields at room temperature.

TsCl-promoted sulfonylation of quinoline N-oxides with sodium sulfinates in water

An eco-friendly protocol for the synthesis of various 2-sulfonyl quinolines/pyridines through sulfonylation of heteroaromatic N-oxides with sodium sulfinates in water at ambient temperature under metal-and oxidant-free conditions has been developed.The mild reaction conditions,high reaction efficiency,operational simplicity,short reaction time and remarkable functional-group compatibility make the developed protocol very attractive for the preparation of 2-sulfonyl N-heteroaromatic compounds.

Rh(Ⅲ)-catalyzed C8 arylation of quinoline N-oxides with arylboronic acids

Herein,we report the first Rh~Ⅲ-catalyzed regioselective C8 arylation of quinoline N-oxides with commercially available arylboronic acids as coupling partners.This procedure is simple,and the reaction shows perfect regioselectivity,a broad substrate scope,and isolated yields of up to 92%.We demonstrate the utility of the reaction by using it for late-stage functionalization of a fungicide.

Density Function Theory Study on Effects of Different Energetic Substituent Groups and Bridge Groups on Performance of Carbon-Linked Ditetrazole 2N-Oxides

Based on the parent tetrazole 2N-oxide, six series of novel carbon-linked ditetrazole 2N- oxides with different energetic substituent groups （-NH2, -Na, -NO2, NF2, -NHNO2） and energetic bridge groups （-CH2-, -CH2-CH2-, -NH-, -N=N-, -NH-NH-） were designed. The overall performance and the effects of different energetic substituent groups and energetic bridge groups on the performance were investigated by density functional theory and electrostatic potential methods. The results showed that most of designed compounds have oxygen balance around zero, high heats of formation, high density, high energy, and acceptable sensitivity, indicating that tetrazole N-oxide is a useful parent energetic compound employed for obtaining high energy compounds, even only combined with some very common energetic substituent groups and bridge groups. Comprehensively considering the effects on energy and sensitivity, the -NO2, -NF2, -NH- and-NH-NH- are appropriate substituent groups for combining tetrozale N-oxide to design new energetic compounds, while -NH2, -Na, -CH2-CH2-, and -N=N- are inappropriate.

Microbial Degradation of Quinoline: Kinetics Study With Burkholderia picekttii

Objective To investigate the kinetics of quinoline biodegradation by Burkholderia pickttii, a Gram negative rod-shaped aerobe, isolated in our laboratory. Methods HPLC (Hewlett-Packard model 5050 with an UV detector) was used for the analysis of quinoline concentration. GC/MS method was used to identify the intermediate metabolites of quinoline degradation. Results The biodegradation of quinoline was inhibited by quinoline at a high concentration, and the degradation process could be described by the Haldane model. The kinetic parameters based on Haldane substrate inhibition were evaluated. The values were v = 0.44 h-1,Ks=166.7 mg/L, Ki= 650 mg/L, respectively. The quinoline concentration to avoid substrate inhibition was inferred theoretically and determined to be 329 mg/L. Conclusion The biodegradation of quinoline conforms to the Haldane inhibition model and the main intermediate metabolite of quinoline biodegradation is 2-hydroxy-quinoline.

N-Oxides制备方法

综述了吡啶类衍生物、喹啉类衍生物等杂环含氮化合物,仲胺以及叔胺被氧化成为相应的氮氧化合物的方法。

Synthesis of 6-sulfamoyl-4-oxoquinoline-3-carboxylic acid derivatives as integrase antagonists with anti-HIV activity

A series of novel 6-sulfamoyl-4-oxoquinoline-3-carboxylic acids derivatives have been synthesized and screened for HIV integrase inhibition activity. Their structures were confirmed by ESI-MS, ^1H NMR and ^13C NMR. 2009 Li Ming Hu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Synthesis and Crystal Structure of 3,7,7-Trimethyl-1-phenyl-4-(3-nitrophenyl)-4,5,6,7,8,9-hexahydro-1H-pyrazolo[3,4-b]quinoline-5(6H)-one

The title compound (C25H24N4O3) has been prepared by the cyclocondensation of 5-amino-3-methyl-1-phenypyrazol, m-nitrobenaldehyde and dimedone in glycol under microwave irradiation without catalyst. The crystal structure was determined by single-crystal X-ray diffraction to be orthorhombic, space group Pbca with a = 16.3331(10), b = 13.8329(9), c = 19.4163(12) ?, V = 4386.8(5) ?3, Z = 8, Dc = 1.298 g/cm3, μ = 0.087 mm-1, F(000) = 1808, Mr = 428.48, the final R = 0.0519 and wR = 0.1019. X-ray analysis revealed that the pyridine ring is of boat conformation and the six-membered ring fused with it adopts twist boat conformation.② Corresponding author. Tu Shu-Jiang, born in 1957, professor, majoring in the synthesis of organic and heterocycle compounds. E-mail: laotu2001@ 263.net

Novel indole and quinoline alkaloids from Melodinus yunnanensis

6/7-Seco rearranged spiro-indolone alkaloids,meloyunines A(1)and B(2)and a monoterpenoid quinoline alkaloid meloyunine C(3)together with its possible intermediate 14,15-dehydromelohenine B(4),and their precursorΔ14-vincamenine(5)were isolated from Melodinus yunnanensis.All structures were elucidated based on NMR,FTIR,UV,and MS spectroscopic data.The isolation of monoterpenoid indole,quinoline,and its immediate from the same plant chemically supported the biosynthesis of quinoline from indole.Compound 2 was cytotoxic against several human cancer cell lines.

Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory

The pyrolysis mechanisms of quinoline and isoquinoline were investigated using the density functional theory of quantum chemistry,including eight reaction paths and a common tautomeric intermediate 1-indene imine.It is concluded that the conformational tautomerism of the intermediate decides the pyrolysis products(C6H6,HC≡C—C≡N,C6H5C≡N and HC≡CH)to be the same,and also decides the total disappearance rates of the reactants to be the same,for both original reactants quinoline and isoquinoline during the pyrolysis reaction.The results indicate that the intramolecular hydrogen migration is an important reaction step,which often appears in the paths of the pyrolysis mechanism.The activation energies of the rate determining steps are obtained.The calculated results are in good agreement with the experimental results.

A Novel Green Synthesis of Quinolines through Acid-catalyzed Friedlander Reaction in Ionic Liquids

Quinoline derivatives were efficiently prepared through acid-catalyzed Friedlander reaction in ionic liquid ([bmim][BF4]). It is shown that the proposed method is operationally simple and environmentally benign in that the reaction media and the catalyst can be recovered and be reused effectively for at least four times.

Bioremediation of Quinoline-contaminated Soil Using Bioaugmentation in Slurry-phase Reactor

Objective To investigate the possibility of using bioaugmentation as a strategy for remediating quinoline-contaminated soil. Methods Microorganisms were introduced to the soil to assess the feasibility of enhancing the removal of quinoline from quinoline-contaminated soil. Slurry-phase reactor was used to investigate the bioremediation of quinoline-contaminated soil. HPLC (Hewlett-Packard model 5050 with an UV detector) was used for analysis of quinoline concentration. Results The biodegradation rate of quinoline was increased through the introduction of Burkholderia pickettii. Quinoline, at a concentration of 1 mg/g soil, could be removed completely within 6 and 8 hours with and without combined effect of indigenous microbes, respectively. Although the indigenous microbes alone had no quinoline-degrading ability, they cooperated with the introduced quinoline-degrader to remove quinoline more quickly than the introduced microbes alone. Bioaugmentaion process was accelerated by the increase of inoculum size and bio-stimulation. The ratio of water to soil in slurry had no significant impact on bioremediation results. Conclusion Bioaugmetation is an effective way for bioremediation of quinoline-contaminated soil.

Preparation,Single-crystal Structure and Antibacterial Activity of N-((6-Bromine-2-methoxylquinoline-3-yl)benzyl)-3-morpho-line-N-(naphthalene-1-yl)propionamide

The halogenated hydrocarbon amination reaction between the original raw mate-rial N-（（6-bromine-2-methoxylquinoline-3-yl）benzyl）-3-chlorine-N-（naphthalene-1-yl）propionamide and morpholine produces the target molecule N-（（6-bromine-2-methoxylquinoline-3-yl）benzyl）-3-morpholine-N-（naphthalene-1-yl）propionamide （C34H32BrN3O3,Mr=610.54）,and its structure was characterized by 1H NMR,IR,H RMS and X-ray single-crystal diffraction.This crystal is of triclinic system,space group P1 with a=9.315（2）,b=10.3449（12）,c=15.901（3）,α=80.981（14）,β=76.996（17）,γ=74.917（13）°,V=1433.6（5）3,Z=2,Dc=1.414 g/cm3,F（000）= 632,μ（MoKα）=1.47 mm-1,the final R=0.0735 and wR=0.2457.In total,5585 independent reflections including 3727 observed ones with I 〉 2σ（I） were collected.The dihedral angle between naphthyl and substituted quinolyl and that between phenyl and substituted quinolyl are 61.2（1） and 108.2（1）°,respectively.Through C-H…O and C-H…N hydrogen bonds among molecules,the whole molecule is stacked into a three-dimensional structure.In addition,π-π stacking among adjacent naphthalene rings makes the molecule more stable,and the morpholine ring adopts a chair conformation.The target molecule exhibits good antibacterial activity.

Crystal Structure of 4-(4-chlorophenyl)-7,7-dimethyl-2,5- dioxo-1,2,3,4,5,6,7,8-octahydroquinoline

The crystal structure of the title compound (C17H18ClNO2) has been determined by single-crystal X-ray diffraction. The crystal is monoclinic with space group C2/c, a=23.677(5), b=9.5333(2), c=14.027(3)? b=98.06(3), V=313.5(1)?, Mr=303.77, Z=8, Dc=1.287g/cm3, l=0.71073, m(MoKa)=0.247mm-1, F(000)=1280. The structure was refined to R=0.0600, wR=0.1959 for 2020 reflections with I>2s(I). X-ray analysis reveals that the dihedral angle between plane 1 [C(1)~C(6)] and plane 2 [N(1), C(10), C(11), C(7)] is 78.8(1) , between plane 2 and plane 3 [C(10), C(11), C(12), C(13), C(15)] is 3.95(7) .

Syntheses of Tetrahydropyrrolizino[2,1-c]quinoline Derivatives

The three title compounds were prepared from 2-phenylaminomethyl-3H-1,2-dihydro-1-pyrrolizinols via an intramolecular Friedel-Crafts reaction. 2-Phenylaminomethyl-3H-1,2-dihydro-1-pyrrolizinols were prepared from 2-phenylaminomethyl-3H-1,2-dihydro-1-pyrrolizinones via reduction. The heterocyclic ring system of pyrrolizino[2,1-c]quinoline has not been found in literature.

Unsupported nanoporous palladium‐catalyzed chemoselective hydrogenation of quinolines:Heterolytic cleavage of H_2 molecule

An efficient and highly chemoselective heterogeneous catalyst system for quinoline hydrogenation was developed using unsupported nanoporous palladium(PdNPore).The PdNPore‐catalyzed chemoselective hydrogenation of quinoline proceeded smoothly under mild reaction conditions(low H2 pressure and temperature)to yield 1,2,3,4‐tetrahydroquinolines(py‐THQs)in satisfactory to excellent yields.Various synthetically useful functional groups,such as halogen,hydroxyl,formyl,ethoxycarbonyl,and aminocarbonyl groups,remained intact during the quinoline hydrogenation.No palladium was leached from PdNPore during the hydrogenation reaction.Moreover,the catalyst was easily recovered and reused without any loss of catalytic activity.The results of kinetic,deuterium‐hydrogen exchange,and deuterium‐labeling experiments indicated that the present hydrogenation involves heterolytic H2 splitting on the surface of the catalyst.

Measurable surface d charge of Pd as a descriptor for the selective hydrogenation activity of quinoline

Au Pd nanoalloys with tunable Pd concentrations have been synthesized and used as model catalysts. They have been directly imaged by high-angle annular dark-field scanning transmission electron microscopy and investigated by thorough analyses of their extended X-ray absorption fine structure, X-ray absorption near-edge structure, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The bimetallic nanoparticles are embedded in a carbonaceous matrix and have almost an identical structure at the atomic level and the same electronic properties as Au Pd bulk alloys with the same compositions. The d-electron increase at surface Pd sites is determined by the Pd concentration of the alloy. Similarly, their activation entropy and catalytic activity for the hydrogenation of quinoline is related to the Pd concentration, with Au50 Pd50 the most active of the alloys investigated. An almost 11 times higher activity was achieved compared to a pure Pd catalyst. The experimentally measurable surface d charge at the Pd sites in the Au Pd was found to linearly correlate with the activation entropy and catalytic activity for the hydrogenation of quinoline. The alloy structure is stable, showing negligible metal segregation, dissolution-redeposition and aggregation during the hydrogenation process which involves strong adsorption.

Charge effects on quinoline hydrodenitrogenation catalyzed by Ni-Mo-S active sites-A theoretical study by DFT calculation

The charge distribution on Ni-Mo-S active sites can affect hydrodenitrogenation(HDN)activity.In this study,a series of model Ni-Mo-S were developed with various charge distributions.For comparison,the charge distribution effects on quinoline HDN were studied.The results show that a lack of electrons and extra protons can both lower the orbital eigenvalue of the Ni-Mo-S,leading to stronger adsorption of nitrogen-containing compounds and inhibition of ammonia desorption.Electron deficiency will improve the generation of active hydrogen on the active sites but inhibit hydrogen transfer to the nitrogen compounds;extra protons can provide H^(+)to the nitrogen compounds,which will flexibly transfer between the nitrogen compound and active sites,thus improving the cleavage of the C-N bond.

Bioaugmentation: a new strategy for removal of recalcitrant compounds in wastewater—a case study of quinoline

To demonstrate the feasibility of using bioaugmentation to enhance biodegradation of quinoline, four strains capable of using quinoline as sole source of carbon, nitrogen and energy were isolated from different environmental samples by enrichment technique. Screening for quinoline degrader with the highest quinoline mineralizing rate was carried out in respirometer and one bacterium identified as \%Burkholderia pickettii W2\% was chosen as inoculum in bioaugmentation tests. Quinoline biodegradation experiment results showed that this bacterium degraded quinoline very quickly. 100, 200 and 500 mg/L quinoline can be transformed completely within 1, 2 and 7 hours respectively. A bioaugmentation procedure was proposed and laboratory experiments confirmed that bioaugmentation was an effective way to improve the performance of traditional wastewater treatment facilities for quinoline removal. The effect of inoculum size on bioaugmentation was also investigated in this paper.

Syntheses, Crystal Structures and Photoluminescence Properties of Cadmium(Ⅱ) and Nickel(Ⅱ) Complexes with 2-(2-Benzimidazolyl)quinoline

Two novel complexes, [Cd2（BMQU）2Cl4] （1） and [Ni（BMQU）2HPO4]·1.5H2O （2） （BMQU = 2-（2-benzimidazolyl）quinoline）, were synthesized by the hydrothermal method and characterized by elemental analysis, IR, and TG-DTG. The crystal structures were determined by single-crystal X-ray diffraction. Both 1 and 2 crystallize in the triclinic system, space group P . The data for 1： a = 0.8342（7）, b = 0.9226（9）, c = 1.0646（8） nm, α = 90.819（2）, β = 97.466（2）, γ = 98.280（2）°. The Cd（Ⅱ） is coordinated with three chlorine atoms and two nitrogen atoms of a BMQU molecule, generating a distorted square-pyramidal geometry. The dinuclear Cd（Ⅱ） complex is formed by two chlorine bridge bonds, and the one-dimensional chain structure is constructed with the hydrogen bond N-H…Cl and π-π stacking interaction. The data for 2： a = 1.2251（1）, b = 1.2451（1）, c = 1.2868（1） nm, α = 107.510（2）, β = 98.630（1）, γ = 109.921（2）°. The Ni（Ⅱ） is coordinated with four nitrogen atoms of two BMQU molecules and two oxygen atoms of a HPO42-, forming a distorted-octahedral geometry. The two-dimensional layer structure is formed by the hydrogen bonds and π-π stacking interaction between neighboring molecules. Complex 1 shows a strong blue fluorescence emission （λmax= 456 nm） at solid state.