Synthesis and GIAO NMR calculations for some new 4,5-dihydro-1H-1,2,4-triazol-5-one derivatives: comparison of theoretical and experimental 1H and 13C chemical shifts

Four novel 3-alkyl(aryl)-4-(4-methoxycarbonylbenzylidenamino)-4,5-dihydro-1H-1,2,4-triazol-5-ones (2) were synthesized by the reactions of 3-alkyl(aryl)-4-amino-4,5-dihydro-1H-1,2,4-triazol-5-ones (1) with methyl 4-formylbenzoate and characterized by elemental analyses and IR, 1H NMR, 13C NMR and UV spectral data. In addition, isotropic 1H and 13C nuclear magnetic shielding constants of 2 were obtained by the gauge-including-atomic-orbital (GIAO) method at the B3LYP density functional level. The geometry of each compound was optimized using the 6-311G basis set.     

Synthesis, Structure Characterization and Biological Activity of Adenine Salt of 12-Phosphotungstic Acid

IntroductionOwingtothegreatpotentialoftheapplicationsofpolyoxometalatesasdrugsagainsttumorsandviruses ,theircomplexeshaveattractedanincreasinginterestofbothinorganicchemistsandbiochemists[1,2 ] .Inthelastfewyears ,thenumberofreportsinthelitera tureaddressingtheuseofpolyoxometalatesasantivi ralandanti tumoragents[3— 5] mounteduprapidly .However ,many polyoxometalatestestedshowtheloweractivityinvivothanthatinvitro .Inordertoimprovetheefficacyofthedrugs ,itisconsideredtomodifythepolyoxoanionfram…     

新型1,2,4-三取代-1,2,3-三氮唑盐的合成

以邻溴苄醇(1)和水杨醛(2)为原料,经5步反应合成了一种分子内同时具有羟基和1,2,3-三氮唑环的新型类卡宾前体盐中间化合物(7),在三氟甲磺酸酐的催化下,分子内六元环化反应得到一种新型的1,2,4-三取代-1,2,3-三氮唑并三环体系类卡宾前体盐(8),其结构经1H NMR,13C NMR和MS(ESI)表征。     

4-(N-取代苯基)氨基喹唑啉类化合物的合成及抗磷酸化活性研究

以4-氯喹唑啉为起始原料, 经环化、氯化、取代三步反应, 合成了8个新的4-取代苯基氨基喹唑啉类化合物. 采用¹H NMR, ¹³C NMR, MS, IR及元素分析对目标化合物的结构进行了表征. 生物活性测试表明, 化合物1f在1 μmol• L^－1 浓度下对PC3细胞增殖抑制活性达到88.6%, 进一步研究表明该化合物具有较高的抑制细胞外信号调节激酶(ERK)磷酸化的活性.     

Synthesis,Bioactivity and Crystal Structure Analysis of 2-(Benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) Acetamide

A novel benzisothiazolin-3-one derivative, 2-(benzo[d]isothiazol-3-yloxy)-N-(3-cyano-1-(4-fluorophenyl)-1H-pyrazol-5-yl) acetamide(8), was synthesized from the initial compound benzo[d]isothiazol-3(2H)-one(BIT) 1 and 4-fluoroaniline 3. The structure of the target compound 8 was determined by elemental analyses, IR and 1H NMR. The single crystals of intermediate compound 6 and the target compound 8 were obtained and determined by X-ray diffraction analysis. The preliminary biological activity was also evaluated and the results showed the target compound exhibited a good anti-microbial activity.     

咪唑[1,5-a]吡啶鎓盐的合成、表征及生物活性测定

通过三组份串联反应合成一系列咪唑[1,5-a]吡啶鎓盐,利用1H NMR、13C NMR、MS以及X射线单晶衍射确定其结构,其中以二乙烯三胺与三乙烯四胺为原料获得预期外的结构。以青霉素作为对照,研究了化合物的抗菌性。结果表明,所合成的化合物对溶壁微球菌和乙型链球菌均有抗菌效果,化合物2的抗菌效果最好;含有杂原子O的化合物3对嗜麦芽单胞菌和肺炎克雷伯氏菌的抗菌能力优于青霉素;联苯桥联的刚性双齿咪唑[1,5-a]吡啶鎓(5)比乙基桥联的柔性双齿咪唑[1,5-a]吡啶鎓(4)的抗菌性更强;化合物6为单齿大π体系芳香环,其抗菌效果较好,而化合物7和8为双齿的大π体系芳香环,其抗菌效果较弱。     

苯基取代的苯并噻唑胺双苯甲酰胺衍生物的合成及生物活性

以取代苯甲酸和取代邻氨基苯甲酸为起始原料,设计合成了13个含取代苯并噻唑胺邻甲酰氨基苯甲酰胺类化合物,其结构经1H NMR、13C NMR、IR及元素分析确证。 初步生物活性测试结果表明,在500 mg/L目标化合物浓度下,对黄瓜花叶病毒有一定抑制作用。 采用MTT法进行化合物抑制PC3癌细胞体外活性测试,结果表明,所合成的化合物具有不同程度的抑制PC3癌细胞活性,其中化合物4f在10 μmol/L浓度下对PC3的抑制率为74.2%。     

N-(2-(取代苯并噻唑-2-氨基甲酰基)-取代苯基)-4-氟苯甲酰胺衍生物的合成及生物活性

以对氟苯甲酸和取代邻氨基苯甲酸为起始原料,设计并合成11个含氟基苯并噻唑基邻甲酰氨基苯甲酰胺类化合物,其结构经1 H NMR、13C NMR、IR及元素分析确证.初步生物活性测试结果表明,在500 mg/L浓度下部分化合物对烟草花叶病毒(TMV)有一定抑制作用.采用MTT法进行化合物抑制PC3及Bcap-37癌细胞体外活性测试,结果表明所合成的化合物具有不同程度的抑制PC3和Bcap-37癌细胞活性,其中化合物4d在10 μmol·L-1浓度下对PC3和及Bcap-37的抑制率分别为73.2％和68.1％.     

X-ray diffraction and solid-state NMR studies of a germanium binuclear complex

A compound formulated as (C4H12N2)[Ge2(pmida)2(OH)2] x 4 H2O (where pmida(4-) = N-(phosphonomethyl)iminodiacetate and C4H12N2(2+) = piperazinedium cation), containing the anionic [Ge2(pmida)2(OH)2]2- complex, has been synthesised by the hydrothermal approach and its structure determined by single-crystal X-ray diffraction analysis. Several high-resolution solid-state magic-angle spinning (MAS) NMR techniques, in particular two-dimensional 1H-X(13C,31P) heteronuclear correlation (HETCOR) and 1H-1H homonuclear correlation (HOMCOR) experiments incorporating a frequency-switched Lee-Goldburg (FS-LG) decoupling scheme, have been employed for the first time in such a material. Using these tools in tandem affords an excellent general approach to study the structure of other inorganic-organic hybrids. We assigned the NMR resonances with the help of C...H and P...H internuclear distances obtained through systematic statistical analyses of the crystallographic data. The compound was further characterised by powder X-ray diffraction techniques, IR and Raman spectroscopy, and by elemental and thermal analyses (thermogravimetric analysis and differential scanning calorimetry).     

Synthesis, spectroscopic characterization and biological analysis of a new palladium(II) complex with methionine sulfoxide

A new palladium(II) complex with methionine sulfoxide was synthesized and characterized by a set of chemical and spectroscopic techniques. Elemental and mass spectrometry analyses of the solid complex fit to the composition [Pd(C5H10NO3S)2].H2O. 13C NMR, [1H-15N] NMR and infrared spectra indicate coordination of the amino acid to Pd(II) through the carboxylate and amino groups in a square planar geometry. The complex is soluble in water. Biological activity was evaluated by cytotoxic analysis using HeLa cells. Determination of cell death was assessed using a tetrazolium salt colorimetric assay, which reflects the cells viability. After incubation for 48 h, 20% of cell death was achieved at a concentration of 200 micromol L-1 of the complex.     

邻苯二胺产品中针状未知化合物的结构鉴定

从邻苯二胺产品中分离出一种白色针状未知化合物,用液相色谱（ＨＰＬＣ）和气相色谱（ＧＣ）鉴定其纯度后,同时进行元素、红外光谱（ＩＲ）、紫外光谱（ＵＶ）、质谱（ＭＳ）、核磁共振（ＮＭＲ）氢谱及碳谱分析。根据分析的结果进行解析,最后确定未知针状不纯物中其主成分为２,１,３－苯并硫咪唑或２,１,３－硫二氮杂茚（Ｃ６Ｈ４Ｎ２Ｓ）（２,１,３－ｂｅｎｚｏｔｈ－ｉａｄｉａｚｏｌｅ）。     

1,2-双(四甲基环戊二烯基)四甲基二硅烷与六碳基钼的反应

1,2-双(四甲基环戊二烯基)四甲基二硅烷与正丁基锂作用生成(四甲基二硅撑)双(四甲基环戊二烯基负离子盐),后者随即与六碳基钼反应形成1,1'-(四甲基二硅撑)双(四甲基环戊二烯基铝负离子盐)-(Me₂SiSiMe₂)[Me₄CpMo(CO)₃-Li⁺]₂(I),I与冰醋酸作用,随即分别与CCl₄,NBS及I₂反应,生成相应的铝卤化合物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃X]₂[X=Cl(1),Br(2),I(3)].I与CH₃I反应,在钼原子上发生烃基化,得到产物(Me₂SiSiMe₂)[Me₄CpMo(CO)₃Me]₂(4);I与单质I₂直接反应,生成脱硅桥产物Me₄Cp(CO)>₃I(5).经元素分析、IR及¹HNMR表征了化合物1-5的结构。     

Synthesis and Characterization of New Binaphthyl‐Linked Phenanthroline‐, Bipyridine‐, or Pyridine‐Derived Ligands,and the Study of Their Cytotoxic Activity

In the present work, we describe the synthesis and characterization of five new versatile acyclic or macrocyclic ligands containing binaphthyl‐linked pyridine, bipyridine, or phenanthroline groups in their framework (see Schemes 1–4). The structures of the ligands were elucidated on the basis of elemental analyses, IR, ¹H‐NMR, ¹³C‐NMR, and FAB mass spectra. The cytotoxicity of these compounds was tested in vitro by using the tetrazolium salt reduction (MTT) assay on A549 (human lung carcinoma epithelial like) cells. All of the tested compounds induced time‐ and concentration‐dependent cytotoxic effect.     

Synthesis of novel biscalixarene-tube containing two kinds of calix[4]arene derivative units

A novel biscalixarene with two kinds of calix[4]arene derivative units connected by four bridging chains, was facilely＇ synthesized by ＂1 ＋ 1＂ condensation mode in high yield. The element analyses, ESI-MS, ^1H NMR and ^1H-^1H COSY spectrum showed that the calix[4]arene units of compound 4 were in cone conformations and compound 4 possessed biscalixarene-tube structure. 2007 Fa Fu Yang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.     

超分子自组装合成杯[4]芳烃黄原酸镍(Ⅱ)配合物

利用二维和三维的大环及笼状主体分子与金属离子直接进行自组装反应合成新型有机无机杂化分子是当前超分子领域的研究热点之一。这类分子不仅具有新奇的光、电、磁等特性，而且还可作为新型的主体分子在客体识别、催化、吸附与分离等方面有广阔的应用前景。杯芳烃是有机超分子领域广受     

Synthesis, growth and characterization of a new nonlinear optical material: 4-phenylpyridinium hydrogen squarate (4PHS)

A novel organic non-linear optical organic single crystal of 4-phenylpyridinium hydrogen squarate (4PHS) has been synthesized and successfully grown from aqueous solutions by slow evaporation solution growth method. In the present investigation the title compound has been synthesized by taking equimolar quantity of 4-phenylpyridine and squaric acid and mixed thoroughly using double distilled water as the solvent. The prepared concentrated solution was placed in an undisturbed condition, and then the solution was periodically inspected. The good quality single crystals have been harvested in a time span of 3 weeks. Then the grown crystal was characterized as single crystal XRD, differential thermal analysis, thermogravimetric analysis, FTIR, UV-vis-NIR, SHG, (1)H NMR and (13)C NMR analyses, respectively. The observed results from the characterization analyses show its suitability for NLO applications when compared with some of the existing organic crystals. The relative second harmonic generation of this grown crystal was found to be five times higher than that of KDP crystal. The UV cut-off wavelength and decomposition temperature of this grown crystal were also comparatively better. (1)H NMR and (13)C NMR spectroscopic studies were employed to elucidate the structure of the grown specimen.     

三羰基(五甲二硅基)环戊二烯基钼衍生物的合成和结构

通过三羰基(五甲二硅基)环戊二烯基钼负离子盐[η-Me~5Si~2C~5H~4Mo(CO)~3]^-Li^+的反应合成了标题化合物, 以元素分析、IR和1^H NMR谱表征了它们的结构, 并用X射线衍射测定了配合物[η-Me~5Si~2C~5H~4MoBr(CO)~3]和[η-Me~5Si~2C~5H~4Mo(CO)~3]~2的晶体结构。     

亚甲基蒽苯乙烯吡啶盐的合成、结构及双光子吸收性质

以氯化4-甲基-N-9-亚甲基蒽吡啶盐为原料,合成了一种新型的苯乙烯吡啶盐,通过红外、核磁共振氢谱、碳谱、电喷雾质谱、单晶X射线衍射等测试技术对化合物的结构进行了表征。单晶X射线衍射结果表明,该化合物属于单斜晶系,空间群为P21/c,晶胞参数a=1.255 7(1)nm,b=1.539(1)nm,c=2.220 2(8)nm,β=101.099(1)°,V=4.210 5(4)nm3,Z=4,Dc=1.159 g/cm3。用1 064 nm皮秒脉冲激光研究其三阶非线性光学特性,双光子吸收系数β=0.028 cm/GW,吸收截面为σ=8.68×10-48cm4.s.photon-1,表明目标化合物具有良好的三阶非线性光学性质。     

1H and 13C NMR assignments of three nitrogen containing compounds from the mangrove endophytic fungus (ZZF08)

A new natural product, named phomopsin A, 1-(meta-hydroxyphenyl)-4-hydroxy-3-isoquinolone (1), together with two known compounds cytochalasin H (2) and glucosylceramide (3), was isolated from the mangrove endophytic fungus Phomopsis sp. (ZZF08) obtained from the South China Sea coast. The structures were elucidated by 1D and 2D NMR experiments including COSY, HMQC, and HMBC. According to NMR and single-crystal X-ray diffraction, it was found that some assignments about (1)H and (13)C NMR data for cytochalasin H (2) were probably uncorrected in the previous reports. In our cytotoxicity assays, compound 1 showed moderate cytotoxicity toward KB cells with IC(50) at 28.0 microg ml(-1) and KBv200 cells with IC(50) at 16.8 microg ml(-1), and compound 2 exhibited strong cytotoxicity toward KB cells and KBv200 cells with IC(50) less than 1.25 microg ml(-1).     

The [2,5,12-C3B8H15]- anion, the first representative of the eleven-vertex hypho family of tricarbaboranes

In one synthetic step from the readily available 9-Me(2)SCH(2)-nido-7,8-C(2)B(9)H(11) (compound 1), the first representative of the eleven-vertex hypho family of tricarbaboranes, [2,5,12-C(3)B(8)H(15)][X] (X=[NMe4]+ or [PPh4]+) (compound 2), has been isolated in 32% yield and structurally characterised by single-crystal X-ray diffraction, multi-nuclear NMR spectroscopy, mass spectrometry, and computational methods. Both [NMe4]+ or [PPh4]+ salts of anion 2 were found to undergo degradative conversion to the [hypho-6,7-C(2)B(6)H(13)]- anion (anion 3) in alkaline medium. The [PPh4]+ salt of anion 2 converted quantitatively to the [6-CH3-arachno-5,10-C(2)B(8)H(12)]- anion (anion 4) if passed through a silica column or to the neutral 5-CH3-arachno-6,9-C(2)B(8)H(13) (compound 5) on treatment of its [NMe4]+ salt with dilute HCl. Moreover, the reaction of compound 2 with [RhCl2(C(5)Me(5))]2 afforded the eleven-vertex ruthenadicarbaborane [1-C(5)Me(5)-4-CH(3)-closo-1,2,3-RhC(2)B(8)H(9)] (compound 8). All these reactions resulted in an extrusion of one of the cluster carbon atoms into an exoskeletal position.