双金属层状配位聚合物{[ML][FeⅡFeⅡ(Ox)3]·H2O}∞的合成和波谱表征

合成和表征了两种新的Schiff碱配合物[ZnL(ClO4)@4H2O(A)和CdL(ClO4)@3H2O(B)],其中L=2-{[2-(Aminomethyl-amino)-ethylimino]-methyl}-phenol.A(或B)、FeSO4@7H2O和K3[Fe(ox)3]@3H2O进一步反应,生成了配位聚合物{[ML][FeⅡFeⅢ(ox)3]@H2O}∞,其中M=Zn2+(C)或Cd2+(D).红外光谱和Mossbauer谱测定结果表明,C和D具有二维层状结构,其阴离子层由[FeⅡFeⅢ(ox)3]-单元构成.     

二(三)丁基锡烯基(炔基)膦酸酯的合成与表征

合成了12个新的二(三)丁基锡烯基(炔基)膦酸酯[(n-C4H9)nSn]n-1O2P(0)R,并用元素分析,红外光谱,核磁共振氢谱和TG-DTA对其组成和结构进行了表征,初步生物活性测试表明,有些化合物具有较强的杀螨和杀菌活性。     

1,3-双(偶氮介晶基)-1,1,3,3-四甲基二硅氧烷的 合成、2D NMR结构分析和液晶性能

合成了2个(CH3(C6H4)N2(C6H3A)COO(C6H4)OCH2-Si(CH3)2)2O化合物,其中A = H为1,A = CH3为2。经IR、1H NMR和元素分析表征,并用2D NMR1H-1H COSY记录了2个化合物中不同取代基苯环上所有质子的化学位移和相关-自旋偶合常数,对谱线的归属作了指认。通过偏光显微镜和DSC分析,1具有液晶性能,而2没有液晶性能。同时,用AM1方法计算了它们的电子结构,讨论了它们的结构与性能之间的关系。     

钨钼杂多酸及其盐与二甲基甲酰胺加合物的制备和性质研究

合成了10种钨钼杂多酸及其盐与DMF的加合物,用IR光谱、Raman光谱、UV光谱、¹HNMR、TG-DTA和X射线衍射方法研究了加合物的性质。加合物中配体DMF以C=O键的氧作为配位原子,与杂多酸中的质子或杂多酸盐中的金属阳离子配合成键。IR光谱中ν_c-o的位移可作为配位键成键强度的判据。     

2-取代苯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑衍生物的合成及生物活性研究

合成了10个2-取代苯基-5-(3,4,5-三甲氧基苯基)-1,3,4-噁二唑衍生物. 并经过元素分析, IR, ¹H NMR, ¹³C NMR对其结构进行了确认. 初步生物活性测试表明, 部分化合物具有一定抗癌活性.     

Studies on the Syntheses and Biological Activities of 3-Aryl-6-(1,1'-biphenyl-4-yl)-7H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines

IntroductionAmongst various heterocycles 3 ,6 -disubstituted- 7H- 1 ,2 ,4- triazolo[3 ,4- b][1 ,3 ,4]thiadiazines have received considerable attentionduring the lasttwo decades as potentially biologicalactive agents[1,2 ] . A literature survey indicated thatthis kind of N - bridged heterocycles displayed awide spectrum of biological properties,such asantimicrobial[3] ,antibacterial,antifungal[4 ] ,antiinflammatory[5] ,diuretic[6 ] ,anthelmintic,andanalgesic[7] . They can also be used as the p…     

Rotationally resolved infrared spectroscopy of adamantane

We present the first rotationally resolved spectra of adamantane (C(10)H(16)) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm(-1)range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry (T(d) point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν(30), ν(28), ν(27), ν(26), ν(25), ν(24), and ν(23). The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10(-3) cm(-1).     

稀土硝酸盐与1,1,1-三(4′-二苯胺甲酰基-2′-氧杂丁基)丙烷配合物的合成及谱学性质

三角架型配体由于其独特的配位方式而具有许多优良的物理和化学性质 ,如能稳定高氧化态的过渡金属离子[1 3] ,用作优良的电极活性物质[4] ,具有生物活性[5] 等 .因此近十余年来对该类配合物的研究一直是配位化学研究领域的一个重要部分 .但到目前为止 ,对具有三角架结构的三酰胺型开链冠醚的研究却很少 ,且主要集中于研究它与过渡金属和碱金属离子的相互作用及其性质[4,5] ,有关该类配体与稀土离子的配位形式及性质的研究则更少[6] .为了进一步研究该类配体与稀土离子的配位能力及所形成配合物的性质 ,我们参照文献 [5]方法 ,合成出配体 1 ,…     

三苯基锡芳氧乙酸酯的合成和表征

三苯基锡芳氧乙酸酯的合成和表征刘宝殿，包明，张景萍（东北师范大学化学系、东北师范大学分析测试中心，长春，１３００２４）关键词芳氧乙酸，三苯基锡芳氧乙酸酯，合成，生物活性三苯基醋酸锡和三苯基氢氧化锡是防治甜菜褐斑病的有效药剂［１］．芳氧乙酸及其酯也具有...     

Synthesis and evaluation of in vitro antibacterial activity of novel 2,5-disubstituted-1,3,4-thiadiazoles from fatty acids

A series of new 1-(alkenoyl/hydroxyalkenoyl)-4-benzoyl-thiosemicarbazides 2a-d and 2-benzamide-5-alkenyl/hydroxyalk-enyl-1,3,4-thiadiazoles 3a-d were synthesized from fatty acid hydrazides. Structure of all these compounds was confirmed by IR, 1H NMR, 13C NMR, mass spectra and elemental analysis. The bioassay results indicate that some compounds 2,c, 2d, 3c and 3d have good antibacterial activity.     

芳基-8-喹啉氧基汞化合物的合成与波谱性质研究

本文合成了一系列共13种芳基-8-喹啉氧基汞化合物,其中12种为新化合物, 经IR,^1H NMR和元素分析鉴定了其组成与结构,紫外光谱研究表明分子中存在有N→Hg分子内配位.提出了溶剂效应对紫外光谱性质和N→Hg分子内配位影响的机理. 核磁共振氢谱表明取代基仅影响汞-苯环质子的化学位移,说明共轭效应未通过分子内配位贯穿于整个分子.^1^9^9Hg化学位移值与Hammett-Brown常数σ^+间存在有良好的线性关系     

两个异亚硝基乙酰丙酮-n-芳基亚胺Pd(Ⅱ)配合物的合成、谱学性质和PdCl(C6H5一IAI)(C6H5NH2)的晶体结构

合成了两个异亚硝基乙酰丙酮-n-芳基亚胺的Pd(Ⅱ)配合物,PdCl(C6H5一IAI)(C6H5NH2)(1)和PdCl(P-CH3C6H4－IAI)(P-CH3C6HtNH2)(2),并测定了配合物1的晶体结构.配合物1晶体属正交晶系,空间群为Pca2l,晶胞参数a一1.858 7(4)nm,b＝0.938 0(2)nm,c一2.123 7(4)nm,2=8,F(000)一1 760,μ＝1.160 mm-1,R1＝O.027 二齿Schiff碱配体的异亚硝基(肟基)的N原子和亚胺的N原子,苯胺基N原子和CL-离子与Pd(Ⅱ)配位,形成PdN3Cl平面正方形配位构型.红外和喇曼光谱表明,形成配合物后νC=O和νc=N 移向低频,而vN-.o则移向高频.电子光谱说明存在π-π*和d-π*跃迁     

Conformational studies by nuclear magnetic resonance—IV: Restricted rotation in vinylogous thioamides

Enamino -thial and -thiones R¹C(S)CH?CHNR (R¹ = H or alkyl; R² = Me or Et) have been shown by NMR spectra to exist in two rotational forms, s-cis and s-trans, the populations of the latter being approximately the same as in the case of the parent oxa analogues. An increase of the order of 2 to 4 Kcal/mole in the heights of C? C and C? N rotation barriers (ΔG*) was found on comparing the title compounds with their oxa analogues. IR spectra failed as a tool to establish the rotational equilibrium. IR absorption bands of the ν_{C? C}, ν_{C? H} (in the NMe₂ group) and γ_HC?CH vibrations have been found, but the ν_C?S band could not be assigned unambiguously. Anomalies concerning the frequency and intensity of the ν_C?C band are discussed.     

内式及外式-5,5-二取代-3-氧代-4-氧杂三环[5,2,1,02,6]-8-癸烯类化合物的合成

由于许多降冰片烷衍生物及内酯类化合物都是很好的香原料,可用于调制化妆品或食用香精。为了探讨结构与香气的关系,并寻找新型的香原料,我们将上述两部分骨架-降冰片烷环系及内酯环系结合在一起,合成了具有如下结构的化合物16个。     

新型查尔酮类化合物的合成及其生物活性研究

以3,5-二羟基苯甲酸为原料, 分别经酯化、甲氧甲基保护或甲基化、酰肼化、氧化、醛酮缩合、脱保护基、O-法呢基化或O-异戊烯基化等步骤, 以5.6%～46%的总收率合成了8个未见文献报道的查尔酮类化合物1a～1h, 产物通过¹H NMR, ¹³C NMR, IR, MS进行了结构确证. 对所合成的目标化合物在3个标准活性筛选模型中进行了生物活性试验, 结果表明化合物1b在组织蛋白酶B (CAT-B)模型、化合物1e在细胞分离周期基因25表达的蛋白磷酸酶(CDC25)模型中表现出良好的活性.     

N′-(取代嘧啶-2-基)-N-菊酰硫脲的合成与生物活性研究

采用活性基团拼接法, 将第一菊酸构型中的最高活性组分(＋)-反式菊酸以及二氯菊酸引入到含取代嘧啶环的酰基硫脲结构中, 合成了5个未见文献报道的N′-(取代嘧啶-2-基)-N-(＋)-反式菊酰硫脲衍生物(3a～3e)和3个均未见文献报道的N′-(取代嘧啶-2-基)-N-二氯菊酰硫脲(3f～3h), 结构经元素分析、IR和¹H NMR得到确证. 初步的生物活性测试结果表明: 大部分化合物具有较好的杀菌活性, 有的化合物兼具除草和杀菌活性, 有的化合物兼具杀虫和杀菌活性.     

Visualization and quantification of the anisotropic effect of C=C double bonds on 1H NMR spectra of highly congested hydrocarbons-indirect estimates of steric strain

The anisotropic effect of the olefinic C=C double bond has been calculated by employing the NICS ( nucleus independent chemical shift) concept and visualized as an anisotropic cone by a through space NMR shielding grid. Sign and size of this spatial effect on (1)H chemical shifts of protons in norbornene, exo- and endo-2-methylnorbornenes, and in three highly congested tetracyclic norbornene analogs have been compared with the experimental (1)H NMR spectra as far as published. (1)H NMR spectra have also been calculated at the HF/6-31G* level of theory to get a full, comparable set of proton chemical shifts. Differences between delta( (1)H)/ppm and the calculated anisotropic effect of the CC double bond are discussed in terms of the steric compression that occurs in the compounds studied.     

N-取代芳环-4-氨基喹唑啉类化合物的合成及生物活性研究

以4-氯喹唑啉和芳香胺反应,合成了三个新的N-取代苯环或杂环4-氨基喹唑啉类化合物.三个新化合物经1HNMR,IR及元素分析证明其结构.生物活性测试表明,三个新化合物均有一定的抑菌效果.     

Manganese alkane complexes: an IR and NMR spectroscopic investigation

Manganese propane and manganese butane complexes derived from CpMn(CO)(3) were generated photochemically at 130-136 K with the alkane as solvent and characterized by FTIR spectroscopy and by (1)H NMR spectroscopy with in situ laser photolysis. Time-resolved IR spectroscopic measurements were performed at room temperature with the same laser wavelength. The ν(CO) bands in the IR spectra of the photoproducts in propane are shifted to low frequency with respect to CpMn(CO)(3), consistent with formation of CpMn(CO)(2)(propane). The (1)H NMR spectra conform to the criteria for alkane complexes: a high-field resonance for the η(2)-CH protons that shifts substantially on partial deuteration of the alkane and exhibits a coupling constant J(C-H) on (13)C-labeling of ca. 120 Hz. The NMR spectrum of each system exhibits two diagnostic product resonances in the high-field region for the η(2)-CH protons, corresponding to CpMn(CO)(2)(η(2)-C1-H-alkane) and CpMn(CO)(2)(η(2)-C2-H-alkane) isomers. Partial deuteration of the alkane at C1 results in characteristic strong isotopic perturbation of equilibrium of the η(2)-CH resonance of CpMn(CO)(2)(η(2)-C1-H-alkane). With propane-(13)C(1), the η(2)-CH resonance of CpMn(CO)(2)(η(2)-C1-H-alkane) isomer exhibits (13)C satellites with J(C-H) = 119 Hz. The corresponding resonance of CpMn(CO)(2)(η(2)-C2-H-alkane) is identified by use of propane-2,2-d(2). The lifetimes of the (η(2)-C1-H-alkane) isomers of the manganese complexes were determined by NMR spectroscopy as 22 ± 2 min at 134 K (propane) and 5.5 min at 136 K (butane). The corresponding spectra and lifetimes of the CpRe(CO)(2)(alkane) complexes were measured for reference (CpRe(CO)(2)(propane) lifetime ca. 60 min at 161 K; CpRe(CO)(2)(butane) 13 min at 171 K). The lifetimes determined by IR spectroscopy were similar to those determined by NMR spectroscopy, thereby supporting the assignments. These measurements extend the range of alkane complexes characterized by NMR spectroscopy from rhenium and rhodium derivatives to include less stable manganese derivatives.     

3－芳基－6－三氯甲基－1，2，4－三唑并[3,4-b]-1,3,4-噻二唑的合成与波谱表征

首次报道3－芳基－4－氨基－5－巯基－1，2，4－三唑与三氯乙酸在三氯氧磷 存在下关环，合成了3－芳基－6－三氯甲基－1，2，4－三唑并[3,4-b]－1，3，4 －噻二唑，标题化合物结构经元素分析、红外光谱、核磁共振氢谱、碳谱与质谱确 证。