2-羧甲氧基苯甲醛苯甲酰腙及其稀土配合物的合成、表征和抑菌活性

2-羧甲氧基苯甲醛苯甲酰腙及其稀土配合物的合成、表征和抑菌活性     

5-溴水杨醛硫代双酰腙及其Cu(Ⅱ)配合物的合成、表征及抑菌活性

5-溴水杨醛硫代双酰腙及其Cu(Ⅱ)配合物的合成、表征及抑菌活性     

5-溴水杨醛硫代双酰腙及其Cu(Ⅱ)配合物的合成、表征及抑菌活性

5-溴水杨醛硫代双酰腙及其Cu(Ⅱ)配合物的合成、表征及抑菌活性     

2-呋喃甲酰腙衍生物的合成、荧光性质及抑菌活性

以2-呋喃甲醛、苯甲酰肼及其衍生物为原料,合成了4个新型呋喃酰腙（4a~4d）,用溶剂挥发法获得了酰腙4a的单晶,并用X射线单晶衍射仪测定了晶体和分子结构。 通过元素分析、核磁共振、红外光谱、紫外光谱和荧光光谱等技术手段对酰腙（4a~4d）进行了表征。 结构分析表明,酰腙4a通过分子间氢键和分子间呋喃环错位面对面π…π作用力构成二维链式层状结构;荧光分析表明,酰腙4c拥有较强的荧光发射。 采用琼脂扩散法测试了酰腙（4a~4d）对大肠杆菌、金黄色葡萄球菌、绿脓杆菌的抑制活性,结果显示,酰腙4c对金黄色葡萄球菌有显著的抑制活性。     

2,4,6-三硝基苯腙的合成及其抑菌活性

三硝基氯苯与水合肼反应,直接合成了2,4,6-三硝基苯肼(2),2与醛、酮试剂反应合成了6个新的苯腙化合物,其结构经1H NMR,IR和元素分析表征。抑菌试验表明,部分目标产物具有良好的抑菌活性。     

5-溴-邻羟苯基芳基取代酰腙的合成、表征及抑菌活性研究

以水杨酸甲酯为原料,先经溴化反应制得5-溴水杨酸甲酯,再经肼解反应制得5-溴-2-羟基苯甲酰肼,再与取代芳香醛缩合反应,制得7种5-溴-2-羟基苯甲酰基取代芳醛腙,其中3种为新化合物。 化合物的结构经IR、¹H NMR、MS与元素分析测试技术表征确证。 抑菌测试表明,该类化合物对不同菌株的抑菌活性具有明显的选择性;在质量浓度为0.05%时,上述化合物对白色念珠菌、枯草芽孢杆菌的抑菌率高达100%,具有强抑菌活性,是一类极具潜力的抗真菌、抗革兰氏阳性菌的化合物。 5-溴-2-羟基苯基-3′,5′-二溴-2-羟基苯甲醛腙的抗菌活性接近广谱高效杀菌剂三氯生。 构效分析表明,化合物的抑菌活性与Ar环及其取代基性质有关,引入呋喃环、Ar环邻、对位引入-OH、-OCH₃等供电基容易导致化合物抑菌活性降低,Ar环的间位引入Cl、Br等卤素原子能够提高化合物的抑菌活性。     

2,5-噻吩双酰腙的合成

酰腙可提供氧、氮、硫等配位原子,与生物环境比较接近,且能与许多金属形成稳定的配合物[1 3]。1982年,Johnson及其合作者报道了芳香腙对DNA的合成具有奇特的抑制效果,并能抑制啮齿细胞链的增长;1988年,Mohan合成了7个含双吡啶环的芳香腙,这些配体都具有明显的抗肿瘤活性[4]。考虑到噻吩等杂环化合物在自然界中具有广泛的生物活性,故把杂环引入酰腙,我们合成了七个2,5 噻吩双酰腙,旨在为人们开发新药奠定一定的基础,合成路线如下:1　实验部分1 1　仪器与试剂意大利CarloErba1106型元素分析仪;美国NicoletESP360型傅立叶变换红外光谱…     

双核钒酰腙配合物的合成与表征

氧化还原性质;双核钒酰腙配合物的合成与表征     

5-溴-2-羟基苯甲酰基取代芳醛腙的合成、表征及抑菌活性

以水杨酸甲酯为原料,先经溴化反应制得5-溴水杨酸甲酯,再经肼解反应制得5-溴-2-羟基苯甲酰肼,再与取代芳香醛缩合反应,制得7种5-溴-2-羟基苯甲酰基取代芳醛腙,其中3种为新化合物. 化合物的结构经IR、1H NMR、MS与元素分析测试技术表征确证. 抑菌测试表明,该类化合物对不同菌株的抑菌活性具有明显的选择性;在质量浓度为0.05%时,上述化合物对白色念珠菌、枯草芽孢杆菌的抑菌率高达100%,具有强抑菌活性,是一类极具潜力的抗真菌、抗革兰氏阳性菌的化合物. 5-溴-2-羟基苯基-3′,5′-二溴-2-羟基苯甲醛腙的抗菌活性接近广谱高效杀菌剂三氯生. 构效分析表明,化合物的抑菌活性与Ar环及其取代基性质有关,引入呋喃环、Ar环邻、对位引入-OH、-OCH_3等供电基容易导致化合物抑菌活性降低,Ar环的间位引入Cl、Br等卤素原子能够提高化合物的抑菌活性.     

对苯双酰腙类化合物的合成与表征

以对苯二甲酸为起始原料,设计合成了5个新型的对苯双酰腙类化合物,其结构经1H NMR,MS和元素分析表征。     

First structural characterization of binary AsIII and SbIII azides

The highly explosive molecules As(N(3))(3) and Sb(N(3))(3) were obtained in pure form by the reactions of the corresponding fluorides with (CH(3))(3)SiN(3) in SO(2) and purification by sublimation. The crystal structures and (14)N NMR, infrared, and Raman spectra were determined, and the results compared to ab initio second-order perturbation theory calculations. Whereas Sb(N(3))(3) possesses a propeller-shaped, pyramidal structure with perfect C(3) symmetry, the As(N(3))(3) molecule is significantly distorted from C(3) symmetry due to crystal packing effects.     

Calcium-amidoborane-ammine complexes: thermal decomposition of model systems

Hydrocarbon-soluble model systems for the calcium-amidoborane-ammine complex Ca(NH(2)BH(3))(2)?(NH(3))(2) were prepared and structurally characterized. The following complexes were obtained by the reaction of RNH(2)BH(3) (R = H, Me, iPr, DIPP; DIPP = 2,6-diisopropylphenyl) with Ca(DIPP-nacnac)(NH(2))?(NH(3))(2) (DIPP-nacnac = DIPP-NC(Me)CHC(Me)N-DIPP): Ca(DIPP-nacnac)(NH(2)BH(3))?(NH(3))(2), Ca(DIPP-nacnac)(NH(2)BH(3))?(NH(3))(3), Ca(DIPP-nacnac)[NH(Me)BH(3)]?(NH(3))(2), Ca(DIPP-nacnac)[NH(iPr)BH(3)]?(NH(3))(2), and Ca(DIPP-nacnac)[NH(DIPP)BH(3)]?NH(3). The crystal structure of Ca(DIPP-nacnac)(NH(2)BH(3))?(NH(3)(3) showed a NH(2)BH(3)(-) unit that was fully embedded in a network of BH???HN interactions (range: 1.97(4)-2.39(4)??) that were mainly found between NH(3) ligands and BH(3) groups. In addition, there were N-H???C interactions between NH(3) ligands and the central carbon atom in the ligand. Solutions of these calcium-amidoborane-ammine complexes in benzene were heated stepwise to 60?°C and thermally decomposed. The following main conclusions can be drawn: 1)?Competing protonation of the DIPP-nacnac anion by NH(3) was observed; 2)?The NH(3) ligands were bound loosely to the Ca(2+) ions and were partially eliminated upon heating. Crystal structures of [Ca(DIPP-nacnac)(NH(2)BH(3))?(NH(3))](∞), Ca(DIPP-nacnac)(NH(2)BH(3))?(NH(3))?(THF), and [Ca(DIPP-nacnac){NH(iPr)BH(3)}](2) were obtained. 3)?Independent of the nature of the substituent R in NH(R)BH(3), the formation of H(2) was observed at around 50?°C. 4)?In all cases, the complex [Ca(DIPP-nacnac)(NH(2))](2) was formed as a major product of thermal decomposition, and its dimeric nature was confirmed by single-crystal analysis. We proposed that thermal decomposition of calcium-amidoborane-ammine complexes goes through an intermediate calcium-hydride-ammine complex which eliminates hydrogen and [Ca(DIPP-nacnac)(NH(2))](2). It is likely that the formation of metal amides is also an important reaction pathway for the decomposition of metal-amidoborane-ammine complexes in the solid state.     

3, 3-不对称二取代甲基氧杂丁环的合成

以2,2-二(溴甲基)-1,3-丙二醇(1)为原料合成了3-溴甲基-3-羟甲基氧杂丁环(2)、3-乙氧甲基-3-羟甲基氧杂丁环(3)、3-叠氮甲基-3-羟甲基氧杂丁环(4)、3-叠氮甲基-3-硝酸酯甲基氧杂丁环(5)、3-溴甲基-3-硝酸酯甲基氧杂丁环(6)及3-乙氧基甲基-3-硝酸酯甲基氧杂丁环(7)共六种3,3-不对称二取代甲基氧杂丁环化合物,其中6和7的合成未见文献报道。也提出了合成5的改进路线。     

Expanding the world of endohedral fullerenes--the Tm3N@C2n (39< or =n< or =43) clusterfullerene family

A new family of endohedral fullerenes, based on an encaged trithulium nitride (Tm(3)N) cluster, was synthesised, isolated and characterised by HPLC, mass spectrometry, and visible-NIR and FTIR spectroscopy. Tm(3)N clusterfullerenes with cages as small as C(76) and as large as C(88) were prepared and six of them were isolated. Tm(3)N@C(78) is a small clusterfullerene. The two isomers of Tm(3)N@C(80) (I and II) were the most abundant structures in the fullerene soot. Tm(3)N@C(82), Tm(3)N@C(84), and Tm(3)N@C(86) represent a new series of higher clusterfullerenes. All six isolated Tm(3)N clusterfullerenes were classified as large energy-gap structures with optical energy gaps between approximately 1.2 and approximately 1.75 eV. Tm(3)N@C(80) (I) and Tm(3)N@C(80) (II) were assigned to the C(80) cages C(80):7 (I(h)) and C(80):6 (D(5h)). For Tm(3)N@C(78), the analysis pointed to an elliptical carbon cage with C(78):1 (D(3)) or C(78):4 (D(3h)) being the probable structures.     

Coupling of CpCr(CO)3 and heterocyclic dithiadiazolyl radicals. synthetic, x-ray diffraction, dynamic NMR, EPR, CV, and DFT studies

The reaction of the 1,2,3,5-dithiadiazolyls (4-R-C(6)H(4)CN(2)S(2))(2) (R = Me, 2a; Cl, 2b; OMe, 2c; and CF3, 2d) and (3-NC-5-tBu-C(6)H(3)CN(2)S(2))(2) (2e) with [CpCr(CO)(3)](2) (Cp = eta(5)-C(5)H(5)) (1) at ambient temperature respectively yielded the complexes CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(4)R) (R = 4-Me, 3a; 4-Cl, 3b; 4-OMe, 3c; and 4-CF(3), 3d) and CpCr(CO)(2)(eta(2)-S(2)N(2)CC(6)H(3)-3-(CN)-5-(tBu)) (3e) in 35-72% yields. The complexes 3c and 3d were also synthesized via a salt metathesis method from the reaction of NaCpCr(CO)(3) (1B) and the 1,2,3,5-dithiadiazolium chlorides 4-R-C(60H(4)CN(2)S(2)Cl (R = OMe, 8c; CF(3), 8d) with much lower yields of 6 and 20%, respectively. The complexes were characterized spectroscopically and also by single-crystal X-ray diffraction analysis. Cyclic voltammetry experiments were conducted on 3a-e, EPR spectra were obtained of one-electron-reduced forms of 3a-e, and variable temperature 1H NMR studies were carried out on complex 3d. Hybrid DFT calculations were performed on the model system [CpCr(CO)(2)S(2)N(2)CH] and comparisons are made with the reported CpCr(CO)(2)(pi-allyl) complexes.     

Pt- (and Co-) Promoted Molybdena-Alumina Catalysts: Analysis of the Impregnation Steps

The equilibrium parameters for the adsorption of Mo(VI) on gamma-Al(2)O(3) and of Co(II) and Pt(IV) on MoO(3)/gamma-Al(2)O(3) were determined. The adsorption isotherms were performed from aqueous solutions of the corresponding precursors on two different alumina supports. According to the classification given by Giles, L-type-shaped, subgroup 2, adsorption curves were found for the system Mo on gamma-Al(2)O(3), L-type, subgroup 1, for the Pt on MoO(3)/gamma-Al(2)O(3), and S-type for Co on the MoO(3)/gamma-Al(2)O(3) system. Numerical calculations were carried out for all the isotherms to find the equilibrium parameters. These constants are being used to model the development of Pt, Co, and Mo profiles on MoO(3)/gamma-Al(2)O(3) or gamma-Al(2)O(3) extrudates, respectively, which belong to the new generation of noble-metal-MoO(3)/gamma-Al(2)O(3)-supported catalysts to be used in oil-refining processes. Copyright 2001 Academic Press.     

非对称取代卟啉锌、镉的生成反应动力学及动力学盐效应研究

本文报道应用停流方法对非对称取代卟啉［5-(4-乙酰氨基苯基)-10,15,20-三(4-甲基苯基)卟啉］(H₂T(p-CH₃)₃(p-NHCOCH₃)PP)与Zn(Ⅱ)、Cd(Ⅱ)在丙酮中的生成反应动力学进行了研究,提出了反应机理,并用非线性拟合和线性拟合的方法求得了生成反应各基元步骤的动力学参数,同时还探讨了温度,溶剂效应、动力学盐效应对反应体系的影响,并对锌、镉两种卟啉在生成机理及生成反应速率上的差异给予了解释。     

New acylated anthocyanins and other flavonoids from the red flowers of Clematis cultivars

Six new acylated cyanidin glycosides, cyanidin 3-O-beta-(2'-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-galactopyranoside (1), cyanidin 3-O-beta-(2'-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6'-malonylgalactopyranoside) (2), cyanidin 3-O-beta-(2'-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6'-succinylgalactopyranoside) (3), cyanidin 3-O-beta-(2'-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-galactopyranoside-3'- O-beta-glucuronopyranoside (4), cyanidin 3-O-beta-(2'-E-caffeoylglucopyranosyl)-(1 --> 2)-O-beta-(6'-malonylgalactopyranoside)-3'-O-beta-glucuronopyranoside (5), and cyanidin 3-O-beta-(2'-E-feruloylglucopyranosyl)-(1 --> 2)-O-beta-(6'-malonylgalactoside)-3' -O-beta-glucuronopyranoside (6), were isolated from the red flowers of two Clematis cultivars, 'Niobe'and 'Madame Julia Correvon'. The chemical structures of the isolated anthocyanins were determined by UV, LC-MS, HPLC, TLC, characterization of hydrolysates, and 1H and 13C NMR spectroscopy, including H-H COSY, C-H COSY, HMBC, HMQC and NOESY. The last three anthocyanins were widely distributed in 37 red flower Clematis cultivars. On the other hand, the first three compounds were found only in two cultivars. Five known flavonol glycosides, kaempferol 3-O-glucoside, kaempferol 3-O-rutinoside, quercetin 3-O-galactoside, quercetin 3-O-glucoside and quercetin 3-O-rutinoside, were isolated from the flowers of'Madame Julia Correvon'.     

Synthesis of (thia)Calixarene-based exTTF Derivatives and Their Electron Transfers Towards p-Chloranil and C60

Two novel (thia)calixarene-based exTTF derivatives(3a and 3b) were prepared by Mitsunobu reactions in toluene using diethyl azodicarboxylate(DEAD) and triphenylphosphine(PPh₃) system. The cyclic voltammograms of compounds 3a and 3b were provided, and two electron-irreversible waves with redox potentials were observed. Meanwhile, the intermolecular electron transfer(ET) properties of both compounds 3a and 3b towards p-chloranil(Q) and C₆₀ were investigated via UV-Vis and fluorescent spectroscopies, respectively. The results indicated that the introduced nonoxidable metal ions(Al³⁺, Pb²⁺, Sc³⁺) might promote the intermolecular ET from compounds 3a and 3b towards Q ensembles, whereas the effects of Sc³⁺ were the most impressive. Furthermore, the effects of the same metal ions(Al³⁺, Pb²⁺, Sc³⁺) added for compound 3b were greater than those for compound 3a. Additionally, the photoinduced intermolecular ET from compounds 3a and 3b towards C₆₀ was observed.     

新型他克林-吲哚杂二联体的微波促进Husigen[3+2]环加成反应合成及生物活性

以吲哚-3-丙酸和吲哚-3-丁酸为原料,分别与炔丙胺发生缩合反应得到3-(丙酰丙炔胺)吲哚(4a)和3-(丁酰丙炔胺)吲哚(4b),然后4a和4b分别与9-(叠氮基乙基氨基)-1,2,3,4-四氢吖啶类衍生物5a～5c在微波辐射下发生Husigen[3+2]环加成反应得到12个新型乙酰胆碱酯酶抑制剂——他克林-吲哚杂二联体,其结构经NMR,IR和HRMS表征.初步生物活性测试表明,目标化合物均具有较强的乙酰胆碱酯酶抑制能力,其中化合物2b和2d抑制鱼鳐乙酰胆碱酯酶的IC50值分别为1.6和2.0 nmol.L-1,是6T6BA(IC50=11.0 nmol.L-1,鱼鳐)的6.9和5.5倍.