One-pot synthesis of 2,5-bis(hydroxymethyl)furan from biomass derived 5-(chloromethyl)furfural in high yield

5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.

1,3-Bis(2-chloroethyl)-1-nitrosourea enhances the inhibitory effect of Resveratrol on 5-fluorouracil sensitive/resistant colon cancer cells

AIM:To study the mechanism of 5-fluorouracil(5-FU)resistance in colon cancer cells and to develop strategies for overcoming such resistance by combination treatment.METHODS:We established and characterized a 5-FU resistance(5-FU-R)cell line derived from continuous exposure(25μmol/L)to 5-FU for 20 wk in 5-FU sensitive HCT-116 cells.The proliferation and expression of different representative apoptosis and anti-apoptosis markers in 5-FU sensitive and 5-FU resistance cells were measured by the MTT assay and by Western blotting,respectively,after treatment with Resveratrol(Res)and/or 1,3-Bis(2-chloroethyl)-1-nitrosourea(BCNU).Apoptosis and cell cycle arrest was measured by 4',6'-diamidino-2-phenylindole hydrochloride staining and fluorescence-activated cell sorting analysis,respectively.The extent of DNA damage was measured by the Comet assay.We measured the visible changes in the DNA damage/repair cascade by Western blotting.RESULTS:The widely used chemotherapeutic agents BCNU and Res decreased the growth of 5-FU sensitive HCT-116 cells in a dose dependent manner.Combined application of BCNU and Res caused more apoptosis in5-FU sensitive cells in comparison to individual treatment.In addition,the combined application of BCNU and Res caused a significant decrease of major DNA base excision repair components in 5-FU sensitive cells.We established a 5-FU resistance cell line(5-FU-R)from 5-FU-sensitive HCT-116(mismatch repair deficient)cells that was not resistant to other chemotherapeutic agents(e.g.,BCNU,Res)except 5-FU.The 5-FU resistance of 5-FU-R cells was assessed by exposure to increasing concentrations of 5-FU followed by the MTT assay.There was no significant cell death noted in5-FU-R cells in comparison to 5-FU sensitive cells after5-FU treatment.This resistant cell line overexpressed anti-apoptotic[e.g.,AKT,nuclear factorκB,FLICE-like inhibitory protein),DNA repair(e.g.,DNA polymerase beta(POL-β),DNA polymerase eta(POLH),protein Flap endonuclease 1(FEN1),DNA damage-binding protein 2(DDB2)]and 5-FU-resistance proteins(thymidylate synthase)but under expressed pro-apoptotic proteins(e.g.,DAB2,CK1)in comparison to the parental cells.Increased genotoxicity and apoptosis were observed in resistant cells after combined application of BCNU and Res in comparison to untreated or parental cells.BCNU increased the sensitivity to Res of 5-FU resistant cells compared with parental cells.Fifty percent cell death were noted in parental cells when 18μmol/L of Res was associated with fixed concentration(20μmol/L)of BCNU,but a much lower concentration of Res(8μmol/L)was needed to achieve the same effect in 5-FU resistant cells.Interestingly,increased levels of adenomatous polyposis coli and decreased levels POL-β,POLH,FEN1 and DDB2 were noted after the same combined treatment in resistant cells.CONCLUSION:BCNU combined with Res exerts a synergistic effect that may prove useful for the treatment of colon cancer and to overcome drug resistance.

Preparation of 2,5-Bis(Aminomethyl)Furan by Direct Reductive Amination of 2,5-Diformylfuran over Nickel-Raney Catalysts

The direct reductive amination of 2,5-diformylfuran (DFF) with ammonia to 2,5-bis(aminomethyl)furan (BAF) was demonstrated, for the first time, over the commercial type Nickel-Raney and acid treated Nickel-Raney catalysts. The effects of reaction parameters such as reaction medium, temperature and hydrogen pressure were described. The acid treated Nickel-Raney catalyst exhibited the highest BAF yield in the THF-water mixed reaction medium. The relatively higher Ni0 species composition and larger surface area of the acid treated Nickel-Raney catalyst with specific reaction conditions contributed greatly to the BAF formation. The oligomeric species, such as furanic imine trimers and tetramers confirmed by MALDI-MS analysis were presented as the intermediates of DFF reductive amination.

Synthesis and Crystal Structure of 2,6-Bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophenyl)pyrazine

The title compound,2,6-bis（2-pyridinylmethyl）-3,5-bis（2-hydroxyl-5-chlorophe nyl）-pyrazine（C26H12Cl2N4O2C2H8O2,Mr=551.41）,has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C（2） and C（3） are substituted by 2-pyridinyl,whereas those on C（1） and C（4） are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433（12）,b=32.003（4）,c=10.5209（18）,β=111.199（2）°,V=2807.5（7）3,Z=4,Dc=1.305 mg/m3,F（000）=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17～25.01o by using a phi and omega scan mode,of which 4923 were unique（Rint=0.0692） and 2872 observed reflections with Ⅰ 〉2σ（Ⅰ） were used in the structure solution and refinement.

Synthesis and Crystal Structure of 3,3'-Bis(5-(N-(4-hydroxylphenyl)imidomethyl)- pyrrol-2-yl)pentane·2CH_3OH

3,3＇-Bis（5-（N-（4-hydroxylphenyl）imidomethyl）pyrrol-2-yl）pentane 1 has been synthesized and characterized. The crystal of its methanol complex, 1·（CH3OH）2, belongs to the orthorhombic system, space group Pccn with a = 18.094（2）, b = 11.6890（16）, c = 13.3629（19） , V = 2826.3（7） 3, Z = 8, C14.5H18N2O2, Mr = 252.31, Dc = 1.186 g/cm3, F（000） = 1080 and μ（MoKα） = 0.080 mm-1. The final R = 0.0662 and wR = 0.1801 for 1908 observed reflections with I 2σ（I）, and R = 0.0800 and wR = 0.1948 for all reflections. In the solid state, bridged by included methanol molecules, the molecules of compound 1 form interpenetrated grid structure through N–H···O and O–H···O hydrogen bonds.

Catalytic Kinetic on the Thermal Decomposition of Ammonium Perchlorate with a New Energetic Complex Based on 3,5-Bis(3-pyridyl)-1H-1,2,4-triazole

A new energetic complex,[Co（3,3？-Hbpt）（Htm）]·H_2O（1,3,3？-Hbpt = 3,5-bis（3-pyridyl）-1H-1,2,4-triazole and H_3tm = trimesic acid）,has been synthesized by hydrothermal reactions and characterized by single-crystal X-ray diffraction,elementary analysis,IR spectroscopy,thermogravimetric analysis and X-ray powder diffraction. Single-crystal X-ray diffraction indicates that the complex belongs to triclinic system,space group P 1 with a = 10.0911（1）,b = 10.2573（1）,c = 10.6393（1） ？,α = 103.793（2）,β = 101.041（2）,γ = 107.918（3）o,V = 974.9（2） ？~3,Z = 2,D_c = 1.732 g·cm-3,μ = 0.941 mm^（-1）,M_r = 508.31,F（000） = 518,the final R = 0.0523 and wR = 0.0935 with I 〉 2σ（I）. In the title complex,Co（Ⅱ） ions are connected by Htm2-anions generating 1D ladder-like chains which are linked by 3,3？-Hbpt to form 1D cages. In addition,the thermal decomposition of ammonium perchlorate（AP） with complex 1 was explored by differential scanning calorimetry（DSC）. AP is completely decomposed in a shorter time in the presence of complex 1,and the decomposition heat of the mixture is 2.531 kJ·g^（-1）,significantly higher than that of pure AP. By Kissinger＇s method,the ratio of Ea/ln（A） is 11.05 for the mixture,which indicates that complex 1 shows good catalytic activity toward the AP decomposition.

Synthesis,Crystal Structure,and Magnetic Property of One 3D Nickel Coordination Polymer Based on 2-Hydroxy-5-(3',5'-terephthalic acid)Pyridine and 1,4-Bis(1-imdazoly)benzene

One novel nickel coordination polymer, {[Ni（OTP）（bib）1.5（H2O）]·2H2O}n（1, H2 OTP = 2-hydroxy-5-（3＇,5＇-terephthalic acid） pyridine, bib = 1,4-bis（1-imdazoly）benzene）, has been synthesized and characterized by elemental analysis（EA）, IR, powder X-ray diffraction（PXRD）, and thermogravimetric（TG） analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860（5）, b = 13.8246（6）, c = 19.0140（8） A, β = 104.3870（1）°, V = 3128.2（2） A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F（000） = 1444 and μ（Mo Kα） = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ（I） and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni（OTP）]n chain and the 2D [Ni2（bib）3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.

One-Pot Synthesis of N-Boc-2, 5-bis(trimethylsilyl)pyrrolidine

N-Boc-2, 5-bis(trimethylsilyl)pyrrolidine 4 was synthesized from the reaction of N-Boc-pyrrolidine 1 with trimethylsilyl chloride (TMSCl) at optional temperature in one-pot in good yield.

Synthesis and Crystal Structure of 2,5-Bis(morpholino)-3,4-bis(p-chlorophenyl)thiophene

The title compound 2,5-bis(morpholino)-3,4-bis(p-chlorophenyl) thiophene 2 was obtained by the reaction of -thio-p-chlorobenzoyl thioformmorpholine 1 with trimethyl phosphite in refluxing xylene. The crystal is of triclinic, space group P?with unit cell constants: a = 6.0740(1), b = 10.3250(1), c = 19.779(2) , ?= 76.740(1), = 87.110(1), = 74.920(1), C24H24Cl2N2O2S, Mr = 475.41, Z = 2, V = 1165.7(3) ?, Dc = 1.354 g/cm3, (MoK) = 0.71073, = 0.392 mm-1, F(000) = 496, the final R = 0.0324 and wR = 0.0819 for 3102 observed reflections (I > 2(I)). X-ray analysis reveals that the two morpholinyl groups are located at the -position of thiophene, and the two p-chlorophenyl groups at the -position. Therefore, the title compound is a new symmetric thiophene derivative.

Synthesis of 1, 4-Bis[3-N-propionyl-2-aryl-1, 3, 4- oxadiazoline-5-yl]phenylenes

1, 4-Bis[3-N-propionyl-2-aryl-1, 3, 4-oxadiazoline-5-yl]phenylenes 4 were synthesized by cyclization of corresponding hydrazones 3 with propionic anhydride.

Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide

Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.

A One-dimensional Cobalt Coordination Polymer Based on Biphenyl-2,3,3',5'-tetracarboxylic Acid and N-donor Ancillary Ligands: Crystal Structure and Magnetic Property

Hydrothermal reactions of biphenyl-2,3,3A,5A-tetracarboxylic acid（H4bptc） with cobalt salt in the presence of 1,4-bis（2-pyridylmethyl）piperazin（bpmp） afforded one novel coordination polymer, namely, [Co（H2bptc）（bpmp）0.5（H2O）]n（1）. Its structure was established by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR spectra and TG analysis. Complex 1 crystallizes in monoclinic, space group P21/c with a = 11.4839（11）, b = 16.6690（16）, c = 11.5559（11） A, V = 2201.8（4） A3, Mr = 539.35, Dc = 1.627 g/cm^3, μ（MoK α） = 0.841 mm-1, F（000） = 1108, Z = 4, the final R = 0.0309 and w R = 0.0705 for 4090 observed reflections（I 2σ（I））. Complex 1 displays a one-dimensional（1D） chain bridged by bpmp. Two carboxylic groups of H4 bptc ligand adopt μ01-η1：η1 and μ1-η1：η coordination modes to bridge adjacent Co（Ⅱ） ions together with bpmp ligand to give alternately arranged left- and right-handed helical chains. In addition, variable-temperature magnetic susceptibility measurements indicate that complex 1 shows weak antiferromagnetic interactions between the adjacent Co（Ⅱ） ions.

Synthesis and Crystal Structure of One New Coordination Polymer: [Ni(qptc)_(0.5)(bpp)( H_2O)]_n

Solvothermal reaction of aromatic terphenyl-2,5,2＇,5＇-tetracarboxylic acid （H4qptc） ligand and the transitional metal cation of Nin in the presence of 1,3-bi（4-pyri- dyl）propane （bpp） affords one new coordination polymer, [Ni（qptc）0.5（bpp）（H2O）], （1）. The structure has been determined by single-crystal X-ray diffraction analysis and further characterized by elemental analysis, IR, TGA, and magnetism. The qptc4- acts as a H-shaped ligand linking the NiⅡ centers together to form a 2D polymeric [Ni（qptc）0.5], layer consisting of alternately arranged left- and right-handed helical chains. Each 2D polymeric [Ni（qptc）0.5], layer is further linked through the bridging bpp ligands, thus resulting in a unique （3,4）- connected network with the （62.8）（62. 84） topology. The crystal of 1 crystallizes in monoclinic, space group C2/c with a = 16.088（5）, b = 14.913（5）, c = 18.849（6） A, β= 100.982（4）, V= 4439（2） A3, Z= 8, C24H21N2NiO5, Mr = 476.14, Dc = 1.425 g/cm3, F（000） = 1976 and μ（MoKa） = 0.912 mm-1. The final R = 0.0584 and wR = 0.1131 for 3894 observed reflections with Ⅰ 〉 20（I） and R = 0.1224 and wR = 0.1279 for all data.

SYNTHESIS OF THE RING—AND SIDE—CHAIN—^(14)C—LABELED 1,2—BIS—(4—MORPHOLINOMETHYL—3,5—DIOXOPIPERAZIN—1—YL) PROPANE

The ring-and side-chain-14C-labeled probimane, 1,2-bis （4-morpholinomethy1-3,5-dioxopiperazin-1-yl） propane were synthesized from acetic acid-1-14C in 4 steps and from 14C-formaldehyde in 1 step respectively. The radiochemical yeild for the ring labeling was 28.1%; for the side-chain labeling was 18.5%.

Determination of Trace Manganese (Ⅱ) by Its Catalytic De-colourizing Reaction On the Aerial Oxidation of 1.5-his (2-hydroxy-5-chlorophenyl)-3-cyanoformazan and Its Kinetic Reaction Mechanism

A kinetie method is described for the determination of trace amounts of mangancsc (Ⅱ)based on its catalylic effect on the aerial oxidation of 1.5-bis (2-hydroxy-5-chlorophenyl)-3-cyanofrmazan. The reaction is followed spectrophotometrically by measurin the rate of change in absorbance at 580nm. The calibration curve (rate constant vs. manganese concentration) is linearin the range of 10~200ng in 25ml solutions. Kinetic parameters of the reaction are reported. Thereare few Interferences.

沉淀法制备Bi2O3的晶相转变过程及其光催化性能

以硝酸铋为原料,氨水为沉淀剂,通过液相沉淀法制得前驱体Bi(OH)_3,并将Bi(OH)_3分别在不同温度和时间下焙烧。利用X射线衍射(XRD)、拉曼光谱、热重(TG)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)及紫外-可见漫反射光谱(UV-Vis DRS)详细研究了Bi(OH)_3转变为Bi2O3的过程及相变过程中粒子形貌、大小、光吸收性质等。结果表明,前驱体Bi(OH)_3经过焙烧之后,发生了如下的转变过程:Bi(OH)_3→Bi_5O_7NO_3→β-Bi_2O_3/Bi_5O_7NO_3→β-Bi_2O_3/Bi_5O_7NO_3/α-Bi_2O_3→α-Bi_2O_3,而且转变过程伴随着粒子长大。在上述转变过程中,与Bi_5O_7NO_3向β-Bi_2O_3转变的过程相比,从β-Bi_2O_3到α-Bi_2O_3相变过程更为迅速。此外,以光催化降解罗丹明B(RhB)为模型反应,考察了不同晶相的Bi_2O_3光催化活性,结果表明Bi_5O_7NO_3和β-Bi_2O_3材料具有优异的光催化性能,而α-Bi_2O_3具有较低的光催化活性。

Synthesis of bis(amino)furans from biomass based 5-hydroxymethyl furfural

In this study we report a new reaction pathway in which the hydroxyl and the aldehyde groups of 5-hydroxymethyl furfural were aminated respectively. Hydroxyl group was aminated via Ritter reaction followed by direct reductive amination of aldehyde group. For the Ritter reaction of 5-hydroxymethyl furfural, mixture of trifluoromethane sulfonic acid and phosphoric anhydride showed good performance and the intermediate N-acyl-5-aminomethyl furfural with the highest yield of 89.1 wt% was obtained.Optimization of direct reductive amination of 2,5-bis（aminomethyl） furan was conducted and a yield of45.7 wt% was achieved. This study presents a simple way for preparing bis（amino）furans from renewable biomass based 5-hydroxymethyl furfural, which enriches the biorefinery concept from biomass.

A Zn(Ⅱ) Coordination Polymer Based on a Flexible Polycarboxylate Ligand 5-(4-Hydroxypyridinium-1-ylmethyl)-isophthalic Acid: Synthesis, Structure, and Property

A Zn（Ⅱ） supramolecular coordination polymer, {[Zn2（L）2（m-bix）（H20）]6H2O}n（1）, with an interesting 1D→2D polythreading array from a flexible and angular organic aromaticpolycarboxylate ligand 5-（4-hydroxypyridinium-l-ylmethyl）isophthalic acid （H2L）, and N-donorligand 1,3-bis（imidazol-l-ylmethyl）benzene （m-bix）, has been obtained under hydrothermalconditions and characterized by elemental analysis, powder X-ray diffraction （PXRD）, IR, thermalgravimetric analyses （TGA） and single-crystal X-ray diffraction. In 1, the Zn（Ⅱ） center has twocoordination geometries. One exhibits a trigonal bipyramidal coordination sphere, and the other isa tetrahedral geometry; L2- has two different coordination modes, with one connecting three Zn（Ⅱ）ions through two monodentate carboxylate groups and the monodentate hydroxyl group, and theother bridging two Zn（Ⅱ） ions through two carboxylate groups. The L2- anions connect the Zn（Ⅱ）centers forming an infinite 1D tubular structure. These 1D tubes are interconnected by the m-bixspacers to form a 2D framework. Such 2D layers are further assembled into a 3D supramolecularnetwork via hydrogen bonds. Meanwhile, the luminescent property of 1 has also been investigatedin detail.

Synthesis and Crystal Structure of a Cadmium(Ⅱ) Coordination Polymer:[Cd_2Cl_4(bpme)]_n·n(2H_2O)

A novel coordination polymer, [Cd2Cl4（bpme）]n·n（H2O） （1, bpme=2,5-bis（be-nzoimidazol-2-yl）pyrazine）, has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal of the complex belongs to the triclinic system, space group P , with a=7.0737（9）, b=8.7886（11）, c=9.4561（12） , α=105.3580（10）, β=94.981（2）, γ=96.879（2）°, V=558.46（12） 3, Mr=714.97, Z=1, F（000）=346, Dc=2.126 g/cm3, μ=2.412 mm-1, T=296（2） K, S=1.057, R=0.0533 and wR=0.1480. According to the structural analysis, the Cd（Ⅱ） ion adopts a slightly distorted six-coordinated octahedral geometry. The Cd（Ⅱ） atoms are bridged by four Cl atoms along the a direction, forming infinite straight chains which are further constructed to generate 2D network layer structures through the μ4-N bpme ligand in the b direction, and such 2D network layer structures finally form a novel three-dimensional infinite supramolecular framework through weak π-π stacking between two network layers and hydrogen bonds.

A New Co(Ⅱ)Coordination Compound Constructed by Tripyridyltriazole and Pyromellitic Acid:Synthesis,Crystal Structure and Antifungal Activity

A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470（8）, b = 10.2879（9）, c = 10.2951（11） ？, α = 109.398（2）, β = 97.6590（10）, γ = 95.3260（10）°, V = 1003.60（16） ？3, Z = 1, Dc = 1.565 g/cm^3, μ = 0.508 mm%^-1, Mr = 945.73, F（000） = 485, the final R = 0.0562 and w R = 0.0783 with I 〉 2σ（I）. Two L223 as chelating ligands link one Co（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.