Synthesis, Crystal Structure and Property of a Series of Supramolecular Polymers Based on Novel 3,5-Dimethyl- 2,6-bis(3-(pyrid-2-yl)-1,2,4-triazolyl)pyridine Ligand

Solvothermal reactions of 3,5-dimethyl-2,6-bis（3-（pyrid-2-yl）-1,2,4-triazolyl） pyridine （L）, 1,4-benzendicarboxylic acid （H2bdc）, and transitional metal cations of M11 （M = Mn, Co, Cd） in the presence of oxalic acid （H2ox） afford three novel supramolecular polymers （CPs）, namely, {[M2（ox）（L）2][bdc][M2（Hox）2（OH）（H2O）4]·3H2O}n （M = Mn for 1, Co for 2, Cd for 3）. Single-crystal X-ray diffraction analysis reveals that complexes 1-3 are isostructural and the 3D supramolecular structure was connected through non-covalent interactions. With the help of H2ox, the L ligands cheated with center atoms forming a butterfly [M2（ox）（L）2]2＋ building block. The bdc2- ligand linked with the unprecedented [M2（Hox）2（OH）2（H2O）4] units through strong O-H...O hydrogen bonds forming a zigzag chain, which are further connected through π-π interactions between L and bdc2- ligands to form a 3D supramolecular structure. Moreover, elemental analyses, IR, thermogravimetric, PXRD and luminescence have been investigated.

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.

Synthesis and Structure of [Cu_2(μ-NO_2)(aepy)_4](ClO_4)_3 (aepy = 2-(2-Aminoethyl)pyridine)

The title compound [Cu2(m-NO2)(aepy)4](ClO4)3 (Cu2C28H40N9Cl3O14, Mr = 960.12, aepy = 2-(2-aminoethyl)pyridine) was synthesized and its crystal structure was determined by X-ray diffraction method. It crystallizes in monoclinic, space group C2/c with cell parameters: a = 21.958(3), b = 12.205(2), c = 15.180(3) ? b = 106.06(1), V = 3909.5(12) ?, Z = 4, Dc = 1.631 g/cm3, F(000) = 1968 and m(MoKa) = 1.368 mm-1. The structure was solved by direct methods and refined by full-matrix least-squares techniques. The final R = 0.0734 and wR = 0.1954 for 1606 observed reflections with I ≥2.0s(I). The crystal structure revealed that the [Cu2(m-NO2)(aepy)4]3+ cation consists of two square-based pyramidal copper (Ⅱ) atoms bridged by one nitrate anion. The distance between the two copper atoms (Cu(1)…Cu(1A)) is 5.373 (2) ?

A New Diiminopyridyl Cobalt Complex [CoCl_2L](L=2,6-Bis(N,N'-bis(2,6-diisopropyl-4-(2,3-dimethyoxylbenzoylamide)phenylimino))pyridine)

The reaction of CoCl2·6H2O with 2,6-bis（N,N＇-bis（2,6-diisopropyl-4-（2,3-dimethy-oxyl-benzoylamide）phenylimino））pyridine（L） afforded the complex [CoCl2L],which was fully characterized by elemental analysis,UV-vis,IR spectroscopy,fluorescence,and X-ray diffraction analysis.The compound is of triclinic system,space group P1 with a = 13.058（3）,b = 13.798（3）,c = 16.695（3） ,α = 98.191（3）,β = 102.792（3）,γ = 101.820（3）°,V = 2815.0（9） 3,Z = 2,F（000） = 1122,μ = 0.45 mm-1,R = 0.061 and wR = 0.1349 for 9842 observed reflections（Ⅰ 〉 2σ（Ⅰ））.The Co（Ⅱ） center adopts a distorted square-pyramidal coordination geometry.The extended structure shows a one-dimensional zigzag double chain linked by hydrogen bonds and π-π stacking interactions.

A Novel Degradation Pathway of Zn(dmid)(phen)_2 in Pyridine

The light-oxidation degradation processes of Zn(dmid)(phen)_2 ( dmid = 4,5-dimercapto-l, 3-dithiole-2-one, phen = 1,10-phenanthroaline) in pyridine solvent has beenmonitored. It has been found under the light, dmid^(2-) of Zn(dmid)-(phen)_2 in pyridine solutioncould generate NCS~ and NCS^-replaces dmid^(2-) to form Zn(NCS)_2 (phen)_2 simultaneously. Thecrystal structure of Zn(NCS)_2 (phen)_2 has been determined. In the crystal of Zn(NCS)_2 (phen)_2,two NCS~ ligands are arranged in syn-configuration, and there is strong pi-pi interaction betweenthe two adjacent parallel phen.

Synthesis, Reactions and Characterization of 1,1’-(1,4-Phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(ethan-1-one)

Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.

N-甲基-2-吡啶乙胺二盐酸盐的合成

通过实验确定了以2-羟乙基吡啶为原料经2-乙烯基吡啶合成N-甲基-2-吡啶乙胺二盐酸盐的方法,总结明确了合成工艺控制点,解决了中间体纯度重现性差、不稳定等问题,保证了中间体和成品质量。以2-羟乙基吡啶计总收率为14%,质量符合药用标准,易于生产,有利于实现更高的经济意义。

2-羟乙基吡啶的常压合成研究

研究了以2-甲基吡啶和多聚甲醛常压催化合成2-羟乙基吡啶的方法。从反应类型和机理出发,分析了在反应过程中不同性质的催化剂的影响;然后根据推论,采用酸碱两类催化剂,并对其催化效果分析比较,发现碱性催化剂三乙胺,更有利于2-羟乙基吡啶合成;探讨了催化剂量、反应比例、反应时间等影响因素,得出了适宜的反应条件:n(2-甲基吡啶)∶n(甲醛)=5∶1,在三乙胺催化下,反应时间40 h,反应收率85.2%,产物纯度可达99.0%,水分低于1.0%。

气相色谱法测定2-羟乙基吡啶合成液主要成分的方法

利用气相色谱校正面积归一法测定2-羟乙基吡啶合成液的主要成分,使用GC9790气相色谱仪对合成液进行分离与定量。4种待测物质甲醛、2-甲基吡啶、2-乙烯基吡啶、2-羟乙基吡啶的绝对质量校正因子的线性关系良好。实验数据表明该方法变异系数均小于5%,回收率为97%～102%。

脱水反应生成2-乙烯基吡啶的研究

研究了以2-羟乙基吡啶经脱水生成2-乙烯基吡啶的方法。采用酸碱两类脱水剂,对其反应效果分析比较,发现碱性脱水剂氢氧化钾,更有利于2-乙烯基吡啶合成;探讨了脱水剂用量、反应温度、反应时间等影响因素,得出了适宜的反应条件:n(2-羟乙基吡啶):n(氢氧化钾)=5:2,在100℃温度条件下,反应时间2 h,反应收率80.2%,产物纯度可达98.1%,水分低于1%。

2-乙烯基吡啶的合成研究

研究了以2-羟乙基吡啶为原料,经脱水反应合成2-乙烯基吡啶的实验方法。探讨了反应过程中催化剂、反应温度、反应时间等影响因素,得出了适宜的反应条件：在固体氢氧化钾催化下,n（氢氧化钾）∶n（2-羟乙基吡啶）=0.2∶1,反应时间1~1.5 h,反应温度100℃,收率达到85%以上,产品纯度大于98%。反应过程催化剂采用循环套用的方法,减少了原料消耗,降低了生产成本,具有较强额实际生产意义。

2-羟乙基吡啶的合成技术

采用三乙胺作为催化剂,常压合成2-羟乙基吡啶,考查了催化剂种类、三乙胺用量、物料配比、温度、回流时间对反应收率的影响,得出优化的反应条件:三乙胺作为催化剂,摩尔量为0.06 mol时,2-甲基吡啶与多聚甲醛摩尔比为3∶1时,阶段升温反应,110℃回流反应20 h,反应收率达到85.3%。

N-(2-Phenoxy)ethyl imidazo[1,2-a]pyridine-3-carboxamides containing various amine moieties:Design,synthesis and antitubercular activity

Seven 2,6-disubstituted N-(2-phenoxy)ethyl imidazo[1,2-a]pyridine-3-carboxamide series containing various amine moieties were designed and synthesized as new anti-TB agents.Many of them show excellent in vitro activity against both drug-sensitive MTB strain H37Rv and two MDR-MTB clinical isolates(MIC:<0.002-0.030 μg/mL).Compounds 2f,5e and 5g display acceptable safety and pharmacokinetic profiles,opening a new direction for further development.

One Novel Tetranuclear Copper Cluster by 2-(1H-Pyrazol-3-yl)pyridine:Synthesis, Structure and Properties

A novel tetranuclear copper cluster[Cu4(μ-L)6Cl2]was constructed by 2-(1H-pyrazol-3-yl)pyridine(HL)under hydrothermal conditions,and structurally concluded by single-crystal X-ray diffractions,elemental analyses and IR spectra.The title complex 1 was of triclinic system,space group■,C24H18ClCu2 N9,Mr=595.01,a=9.6497(13),b=11.4133(7),c=13.0919(15)?,α=99.166(7),β=108.707(11),γ=111.974(9)°,V=1200.7(2)?3,Z=2,Dc=1.997 g/cm^3,F(000)=706,μ(MoKα)=3.203 nm-1,Rint=0.0404,R=0.0536 and wR=0.1490 for4890 observed reflections with I>2σ(I).In this structure,complex 1 was the unimolecule with unprecedented tetranuclear cluster,which was expanded into a 2D network by wide-ranging C-H…Cl intermolecular hydrogen bonds and further exhibited a 3D supramolecular architecture based onπ-πstacking interactions.In addition,the complex was thermally stable up to 300℃and the solid state fluorescent property of 1 was examined and compared with the ligand.

三棱的化学成分研究

目的:研究三棱Sparganium stoloniferumBuch.-Ham.的化学成分。方法:采用硅胶柱层析,Sephadex LH-20,ODS C-18,重结晶等方法,根据理化性质和光谱鉴定化合物的结构。结果:从三棱中得到8个化合物,分别为棕榈酸(1),5-羟甲基糠醛(2),6,7,10-三羟基-8-十八烯酸(3),棕榈酸单甘油酯(4),5-Hydroxy-2-(hydroxymethyl)pyridine(5),β-谷甾醇(β-sitosterol)(6),β-胡萝卜苷(daucosterol)(7),Betulinic acid(8)。结论:化合物5,8为首次从该植物中分离得到。

气相色谱内标法测定2-甲基吡啶和2-羟乙基吡啶的含量

利用气相色谱内标法测定2-甲基吡啶和2-羟乙基吡啶的含量,以吡啶作为内标物,乙醇作溶剂,使用FFAP毛细管色谱柱和FID检测器,对缩合油进行分离与定量。2-甲基吡啶的线性相关系数为0.9995,标准偏差为0.30,变异系数为0.61%,平均回收率为99.76%;2-羟乙基吡啶的线性相关系数为0.9994,标准偏差为0.31,变异系数为1.35%,平均回收率为99.22%。

天然活性化合物羟基白藜芦醇中间体的制备研究

白藜芦醇（Resveratrol,3,4＇,5-trihydroxy-trans-stil-bene）即反式3,4＇,5-三羟基茋,广泛存在于虎杖、葡萄、花生等多种植物中。白藜芦醇作为一种重要的植物抗毒素,具有多种医疗保健生理活性作用,如抗菌、抗氧化、抗癌、抗血小板凝聚、抗艾滋病活性等[1～5]。被誉为继紫杉醇后的第二大抗癌药物。