Synthesis and Characterization of Ferrocenyl Substituted Styryl Octasilsesquioxane

4-(2-Ferrocenylethenyl)-phenyl-POSS Fc-CH=CH-C6H6-(C5H9)7Si8O12 (FEPS, Fc: ferrocene), containing metal and C=C double bond, was firstly synthesized as a mixture of E/Z isomers by the Wittig reaction. The chemical structure of FEPS was characterized by FTIR, 1H-, 13Cand 29Si-NMR.     

二茂铁取代的笼型八聚(二甲基硅氧基)倍半硅氧烷的合成与表征

在Karstedt催化剂的催化作用下,通过把合成的笼型八聚(二甲基硅氧基)倍半硅氧烷与乙烯基二茂铁进行氧化硅烷化反应,合成了二茂铁取代的笼型八聚(二甲基硅氧基)倍半硅氧烷,产物经红外光谱、核磁共振氢谱与硅谱等进行了表征.     

Synthesis and Characterization of Acetone Hydrazones

1‐Isopropylidene‐2‐methylhydrazine ( 1 ), 1‐isopropylidene‐2‐hydroxyethylhydrazine ( 2 ) and 1‐isopropylidene‐2‐formylhydrazine ( 3 ) were synthesized by reaction of the corresponding hydrazine with an excess of acetone in the presence of a drying agent (anhydrous sodium sulfate or barium oxide). All compounds 1 – 3 were characterized by elemental analysis, coupled gas chromatography‐mass spectrometry (GC–MS), multinuclear NMR spectroscopy (¹H, ¹³C and ¹⁵N) and vibrational spectroscopy (infrared and Raman). Compounds 1 and 2 are liquid at room conditions and their density was measured by means of a picnometer, however, (at room conditions) compound 3 is a solid and its crystal density and structure were determined by low temperature X‐ray diffraction techniques (monoclinic, P2₁/n, Z = 4, a = 5.666(1) Å, b = 6.254(1) Å, c = 15.277(4) Å, β = 91.30(2)°, V = 541.2(2) ų). The structure of hydrazone 3 is discussed in detail and compared to that of monoformylhydrazine. Finally, the (gas phase) structure of compound 3 was optimized using DFT calculations (B3LYP/6‐31+G(d, p)) and its NBO charges are reported.     

Synthesis and Characterization of Benzenesulfonyl Hydrazones and Benzenesulfonamides

In the search for structural cyclic imide analogues of therapeutic interest, the syntheses and characterization of benzenesulfonyl hydrazones and benzenesulfonamides are described. The benzenesulfonyl chlorides (2) and (3) were obtained through the Diels–Alder reaction between N‐p‐chloro‐sulfonylfenylmaleimide (1) and furan or 2‐methylfuran. The reactions of (2) and (3) with hydrazine and amines afforded the hydrazides and sulfonamides, respectively. The sulfonylhydrazones were obtained through a condensation between the sulfonylhydrazides with different benzaldehydes.     

两种取代二茂铁基三甲基硅烷基氰醇醚的合成及晶体结构

通过两种取代的乙酰基二茂铁与三甲基氰硅烷的加成反应, 得到两种取代二茂铁基三甲基硅烷基氰醇醚的晶体: 1-(1-氰基-1-三甲基硅烷氧基乙烷基)二茂铁(1), 1,1'-二(1-氰基-1-三甲基硅烷氧基乙烷基)二茂铁(2), 用X射线单晶衍射、元素分析、红外光谱和核磁共振氢谱对分子结构进行了表征. 测试结果表明: 晶体1属正交晶系, Pbca空间群, a＝1.1995 nm, b＝1.2441 nm, c＝2.2183 nm, Z＝8, R₁＝0.0456, wR₂＝0.0880; 晶体2属正交晶系, Pna2(1)空间群, a＝2.0715 nm, b＝0.6440 nm, c＝1.8411 nm, Z＝4, R₁＝0.0485, wR₂＝0.0866. 晶体结构表明, 分子中都存在超共轭效应.     

Synthesis, Structural Characterization of Ferrocenyl Iminophosphines and Amidophosphines as Well as Their Application in the Suzuki Reaction

Ferrocenyliminophosphine 1 and 1,1'-bisferrocenyliminophosphine 2 were easily prepared from the condensation of formylferrocene or 1,1'-diformylferrocene with 2-(diphenylphosphino)aniline.The following reduction of imine group by LiAlH4 led to the formation of the corresponding ferrocenyl amidophosphines 3 and 4.The new ligands 2-4 were well characterized by IR,1H NMR,31P NMR spectra,elemental analysis,and ESI-MS.The catalytic activity of all the ligands with palladium compounds in the Suzuki reaction was evaluated.Ligand 1,in combination with Pd(OAc)2,was found to be the most effective for the Suzuki reaction of aryl bromides with phenylboronic acid.Typically,the use of 0.1%(molar fraction)of Pd(OAc)2/ligand 1 in the presence of two equivalents of K2CO3 as base in toluene at 110 ℃ provided good to excellent yields of the coupled products.     

Molecular Hybridization Strategy on the Design,Synthesis, and Structural Characterization of Ferrocene-N-acyl Hydrazones as Immunomodulatory Agents

Immunomodulatory agents are widely used for the treatment of immune-mediated diseases, but the range of side effects of the available drugs makes necessary the search for new immunomodulatory drugs. Here, we investigated the immunomodulatory activity of new ferrocenyl-N-acyl hydrazones derivatives (SintMed(141–156). The evaluated N-acyl hydrazones did not show cytotoxicity at the tested concentrations, presenting CC₅₀ values greater than 50 µM. In addition, all ferrocenyl-N-acyl hydrazones modulated nitrite production in immortalized macrophages, showing inhibition values between 14.4% and 74.2%. By presenting a better activity profile, the ferrocenyl-N-acyl hydrazones SintMed149 and SintMed150 also had their cytotoxicity and anti-inflammatory effect evaluated in cultures of peritoneal macrophages. The molecules were not cytotoxic at any of the concentrations tested in peritoneal macrophages and were able to significantly reduce (p < 0.05) the production of nitrite, TNF-α, and IL-1β. Interestingly, both molecules significantly reduced the production of IL-2 and IFN-γ in cultured splenocytes activated with concanavalin A. Moreover, SintMed150 did not show signs of acute toxicity in animals treated with 50 or 100 mg/kg. Finally, we observed that ferrocenyl-N-acyl hydrazone SintMed150 at 100 mg/kg reduced the migration of neutrophils (44.6%) in an acute peritonitis model and increased animal survival by 20% in an LPS-induced endotoxic shock model. These findings suggest that such compounds have therapeutic potential to be used to treat diseases of inflammatory origin.     

偶氮苯取代乙炔功能化合物的合成与表征

采用偶氮偶联和金属钯催化偶联反应法,合成了一系列非线性光学基团直接取代乙炔化合物,其结构经^1HNMR,IR,DSC及元素分析等表征。     

5-苯基-1H-3吡唑酰腙化合物的合成及其结构表征

采用"一锅法"合成了5-苯基-1H-3-吡唑甲酸乙酯,进而合成了9种5-苯基-1H-3-吡唑酰腙化合物,通过元素分析、红外光谱、核磁共振氢谱等测试技术对这9个化合物的结构进行了表征. 将5-苯基-1H-3-吡唑甲酸乙酯水解得到5-苯基-1H-3-吡唑甲酸,此化合物与Cu(AcO)2配位,得到一个铜的三核配合物晶体,该晶体属单斜晶系,空间群为C2/c,晶胞参数为a=2.576 7(3) nm,b=1.1 94 4(1) nm,c=1.412 7(2) nm,β=98.993(2)°,V=4.294 1(9) nm 3,Z=4,Dc=1.629 g/cm 3,R1=0.035 5,结果更进一步确定了吡唑环的结构.     

Synthesis and Characterization of New Unsymmetrically Substituted Phthalocyanines

Summary.  Unsymmetric metallophthalocyanines (M=Zn, Co, Ni) carrying alkylthio and acetyloxyethylthio groups on peripheral positions were prepared from 4,5-bis-alkylthio-phthalonitrile, 4,5-bis-(acetyloxyethylthio)-phthalonitrile, and the corresponding anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The extremely soluble compounds were characterized by their IR, ¹H NMR, and UV/Vis spectra. Their long wavelength absorption band was found to be bathochromically shifted; their solubility is superior to that of symmetrical phthalocyanines. Received July 27, 1999. Accepted (revised) September 30, 1999     

Synthesis and Characterization of Novel Mercapto-end Ferrocenyl Derivatives with Schiff Base Linkage

Novel ferrocenyl derivatives of p-(10-mercaptodecyloxy)benzal 4-ferrocenylaniline have been prepared and characterized by element analysis,HNMR,and FAB=MS,Cyclic voltammetry has been used to characterize the self-assembled monolayers formed from the compounds on the gold electrodes.     

Structural and Spectral Characterization of Two Charge-Transfer Salts Formed by Ferrocenyl and Polyoxometalate Units

Two charge-transfer (CT) salts based on the ferrocenyl cation CpFeCpCH₂N⁺(CH₃)₃ and Keggin-type anion [PW₁₂O₄₀]³⁻ or [SiMo₁₂O₄₀]⁴⁻ with the ratio of ferrocenyl:polyanion of 3:1 or 4:1, [CpFeCpCH₂N(CH₃)₃]₃[PW₁₂O₄₀] (1) and [CpFeCp-CH₂N⁺(CH₃)₃]₄[SiMo₁₂O₄₀] (2), were synthesized in high yields (68–71%) by traditional solution synthetic method and their structures were determined by X-ray diffraction analysis. The two salts both crystallize in triclinic space group P[`1] P\overline{1} and show the close interaction of the cyclopentadienyl ligand with the surface of the polyoxometalate. The UV–Vis diffuse reflectance spectra of 1 and 2 in the solid state indicate the presence of a new absorption band at λ _max = 550 and 630 nm, respectively, attributed to charge-transfer transitions between the ferrocenyl donors and the POM acceptors. The large difference of the shapes and positions of fluorescence emission bands of salts from the start materials also suggested the occurrence of a charge transfer process between the ferrocenyl cation and polyanion.     

Synthesis and Characterization of Organosilicon Substituted Fluorenyl Derivatives

Friedel‐Crafts cycloalkylation of biphenyl with 2,3‐dichlorobutyltrichlorosilane(Cl₃Si‐CH₂CHClCHClCH₃) at a temperature of 100°C in the presence of anhydrous aluminum chloride catalyst gave cyclized product, 9‐methyl‐9‐(2‐trichlorosilylethyl)fluorene 1a , in 33% yield. Methylation of 1a with nucleophilic reagent such as methyl magnesium chloride, gave 9‐methyl‐9‐(2‐trimethylsilylethyl)fluorene 2 while bromination of 2 with excess amount of bromine in DMF resulted in 2,7‐dibromo‐9‐methyl‐9‐(2‐trichlorosilyl)fluorene 3 in good yield. All the compounds were structurally identified by GC/MS, ¹H and ¹³C‐NMR spectroscopy.     

Synthesis and Characterization of New Unsymmetrically Substituted Phthalocyanines

 Unsymmetric metallophthalocyanines (M=Zn, Co, Ni) carrying alkylthio and acetyloxyethylthio groups on peripheral positions were prepared from 4,5-bis-alkylthio-phthalonitrile, 4,5-bis-(acetyloxyethylthio)-phthalonitrile, and the corresponding anhydrous metal salts Zn(CH₃COO)₂, NiCl₂, and CoCl₂. The extremely soluble compounds were characterized by their IR, ¹H NMR, and UV/Vis spectra. Their long wavelength absorption band was found to be bathochromically shifted; their solubility is superior to that of symmetrical phthalocyanines.     

Structural and Spectroscopic Properties of Benzoylpyridine-Based Hydrazones

Photochromic hydrazones are attracting the attention in the field of photochromic systems especially due to their P-type character. To understand the structural features and their correlation with the spectroscopic data, UV-Vis, vibrational and ellipsometry spectroscopic techniques are employed with the support of density functional theory (DFT) calculations to three hydrazone derivatives based on benzoylpyridine. Interestingly, analysis of the structure shows the presence of two distinct rotamers around the pyridine ring with different energy and the well-defined conjugation path that changes due to E to Z isomerization especially in the hydrazone −C=N−NH part of the skeleton. IR and Raman spectra are analyzed, showing a higher selectivity in the Z form; moreover, the comparison with the normal modes proves the effect of the reaction on the backbone structure. The experimental results are in good agreement with the theoretical predictions, especially in the case of the Raman spectrum. The molecular polarization also changes from E to Z forms as predicted by DFT calculations. Spectroscopic ellipsometry on thin films of TOPAS doped with 10 %wt of the dimethylamino hydrazone derivative is used to prove such change at the molecular level. A modulation of the refractive index is observed, and it is correlated with the concentration of the active moiety and the calculated electronic polarizabilities.     

Synthesis and Characterization of Niobium Substituted Hexagonal Tungsten Bronzes

Alkali metal tungsten bronzes, M_xWO₃, and its niobium substituted forms, M_xNb_yW_1‐yO₃, have been prepared with M = K and Rb and nominal compositions of x = 0.20, 0.25, 0.30 and 0.0 ≤ y ≤ 0.20 at temperatures between 600 and 900?C. The X‐ray powder patterns reveal that single phases of niobium substituted hexagonal tungsten bronze (HTB) can be prepared for x = 0.2, y ≤ 0.05 ; x = 0.25, y ≤ 0.125 and x = 0.3, y ≤ 0.15. Investigations of the optical reflectivity and the infrared absorption of Rb_0.3Nb_yW_1‐yO₃ indicate a decreasing concentration of free carrier with increasing niobium content.     

α-四(烷基苯氧基)酞菁配合物的合成与表征

以邻苯二甲酸酐为原料，经硝化、氨化、亲核取代和金属离子模扳等多步反应合成了两个系列共5个叔丁基取代苯氧基金属酞菁配合物，产物经元素分析，IR表征，测定了目标配合物的紫外可见吸收光谱、荧光光谱及在有机溶剂中的溶解性。结果发现：与无取代金属酞菁配合物相比，Q带最大吸收光谱波长红移；在710nm波激发下，目标配合物在环已烷等有机溶剂中均有荧光发射(最大发射波长在760nm左右)；在二氯甲烷、氯仿、环已烷、Py、苯、甲苯、乙基环已烷、乙基溶纤剂等中溶解性能良好。     

过渡金属离子置换钛酸(盐)纳米管的合成和表征

以掺杂(Mn、Cr、Cu)的锐钛矿相二氧化钛纳米粉体为前驱体, 采用水热法合成了过渡金属离子置换的钛酸(盐)纳米管, 并用扫描电镜(SEM)、透射电镜(TEM)、能谱元素分析(EDX)、粉末X射线衍射(XRD)、 荧光发射光谱(PL)和拉曼光谱(Raman)对产物进行了表征. 结果表明, 过渡金属离子置换的钛酸(盐)纳米管荧光发射强度随金属离子的置换都有不同程度的降低, 一般认为低电子空穴对复合率意味着高光量子效率. 期望置换后的钛酸(盐)纳米管有可能在催化领域得到应用.