New Heterocyclic Phosphorus Ylides: Synthesis,Crystal Structure,and Theoretical Calculation of Alkyl Substituted 3-(4-Benzoyl-1,5-diphenyl-2,3-dihydro-1H-pyrazol-3-yl)-3-oxo-2-(triphenylphosphoranylidene) Propanoates

Novel alkyl substituted 3-(4-benzoyl-1,5-diphenyl-2,3-dihydro-1H-pyrazol-3-yl)-3-oxo-2-(triphenylphosphoranylidene) propanoates (3) were synthesized from 4-benzoyl-1,5-diphenyl-1H-pyrazole-3-carbonylchloride (1) and alkyl (triphenylphosphoranylidene) acetates (2a–b). The synthesized compounds were characterized by elemental analysis, spectroscopic studies (3a–b), and single crystal X-ray diffraction (3a). The mechanism of the reaction between (1) and (2a) was studied by AM1, and the geometrical parameters of the studied molecules were also carried out in B3LYP methods with the standard 6–31G (d,p) basis set. NBO analysis were studied for 1 and 2a B3LYP methods with the standard 6–31G (d,p) basis set.     

Characteristic features of intra- and intermolecular interactions in crystals of pyrrole-2-carbaldehyde isonicotinoylhydrazone and its hydrate

Pyrrole-2-carbaldehyde isonicotinoylhydrazone (1) and its hydrate [1·H₂O] (2) were studied by single-crystal X-ray diffraction analysis. The introduction of the pyrrole substituent into N"-substituted isonicotinic hydrazide (INH) causes the intramolecular redistribution of the electron density compared to those in INHs studied earlier, which increases the basicity of the hydrazone nitrogen atom (N") involved in intermolecular hydrogen bonding. This effect has not been observed in the structures of N"-substituted INHs and benzhydrazides studied previously. Intermolecular hydrogen bonds play a decisive role in the formation of the crystal structures of 1 and 2.     

Shape Selectivity in Enol Thioether Synthesis Catalyzed by Zeolites

The competitive reaction catalyzed by solid acid catalyst between two cyclohexanones (1a) and (1b) with thiophenol (2) has been studied. No selectivity was observed with the lamellar montmorillonite in contrast with microporous aluminosilicates (zeolites) where shape selectivity was observed, in particularly when the zeolites were saturated by thiophenol (2) before a competitive reaction.     

Simple and Dendritic Cyclam Derivatives. Photophysical Properties,Effect of Protonation and Zn2+ Coordination,Preliminary Screening as Inhibitors of Tumour Cell Growth

We have synthesized two novel dendrimers (BG1 and BG2) consisting of a 1,4,8,11-tetraazacyclotetradecane (cyclam, 1) core with appended four dimethoxybenzene and eight benzyl units (BG1) and twelve dimethoxybenzene and sixteen benzyl units (BG2). The absorption and luminescence spectra of these compounds and the changes taking place upon protonation and Zn²⁺ coordination of their cyclam core have been investigated in acetonitrile-dichloromethane 1:1 v/v solution. For comparison purposes, the absorption and luminescence spectra of 1,4,8,11-tetrabenzyl-cyclam (2), and dendrons BD1 and BD2, model compounds of the branches of BG1 and BG2 respectively, have also been studied. BD1, BD2, BG1, and BG2 exhibit the absorption and emission spectra of their 1,3-dimethoxybenzene unit, but in the two dendrimers the emission intensity is quenched by the cyclam amine groups and increases upon protonation and metal coordination. In order to test if these cyclam derivatives have an antitumour effect, we have studied their action on proliferation in the human neuroblastoma TS12 cell line. Screening experiments have shown that cell proliferation was (i) strongly reduced by the tetrabenzyl substituted cyclam 2, and (ii) unaffected by cyclam and the benzo dendrimers BG1 and BG2. Antitumour screening experiments have also been performed on the tetranaphthyl substituted cyclam 3 and the naphtho-dendrimer NG2, whose photophysical properties have been previously studied. Cell proliferation came out to be moderately reduced by 3, whereas dendrimer NG2 had no effect, similar to dendrimers BG1 and BG2.     

Regularities in the stabilization by hemoglobin of binuclear iron complexes [Fe<Subscript>2</Subscript>(μ-N—C—SR)<Subscript>2</Subscript>(NO)<Subscript>4</Subscript>] containing benzimidazolylthiol and benzothiazolylthiol ligands

The NO-donor ability of new binuclear tetranitrosyl complexes of the μ-N—C—S type, namely, bis(5-methylbenzimidazol-2-ylthio)- (1), bis(benzimidazol-2-ylthio)- (2), and bis(benzothiazol-2-ylthio)(tetranitrosyl)diiron (3), was studied in aqueous solutions by spectrophotometry. All kinetic regularities obtained for complexes 1–3 are well described in terms of formalism of pseudo-first-order reactions. The apparent first-order reaction rate constants for NO evolution by the complexes to solution were determined. Complexes 1–3 are good donors of NO. The structures of the complexes and the effect of their stabilization by hemoglobin were compared. The stabilization effect is explained by different basicities of the sulfur-containing ligands in the complexes studied.     

磺酸咔咯及其镓(Ⅲ)配合物与DNA的相互作用和光核酸酶活性

本文用紫外-可见光谱、荧光光谱、圆二色光谱和粘度法研究了2,17-二(磺酸钠基)-5,10,15-三(五氟苯基)咔咯(1)及其镓配合物(1-Ga)与小牛胸腺DNA(ct-DNA)的相互作用。结果表明1和1-Ga通过外部结合的方式与ct-DNA相互作用,且结合能力1-Ga比1大。琼脂糖凝胶电泳实验显示1和1-Ga均具较好的光核酸酶活性,1-Ga光断裂DNA效果比1好,其光断裂机理与羟基自由基的产生有关。     

Indium(III) complexes containing bithiazole derivatives,chloride, methanol,and dimethyl sulfoxide: X‐ray studies,spectroscopic characterization,and thermal analyses

[In(dm4bt)Cl₃(MeOH)]?·?0.5dm4bt (1) (dm4bt is 2,2′‐dimethyl‐4,4′‐bithiazole) and [In(4bt)Cl₃(MeOH)] (2) (4bt is 4,4′‐bithiazole) were prepared from the reaction of 4,4′‐bithiazole and 2,2′‐dimethyl‐4,4′‐bithiazole with InCl₃?·?4H₂O in methanol, respectively. [In(4bt)Cl₃(DMSO)] (3) was also prepared from recrystallization of 2 in DMSO. These complexes were characterized by IR, UV‐Vis, ¹H NMR, ¹³C{¹H} NMR, and luminescence spectroscopy and their structures were studied by single‐crystal X‐ray crystallography. The thermal stabilities of 1 and 3 were studied by thermogravimetric and differential thermal analyses.     

Studies on fluorescent species of spiro-indolinonaphthooxazines and their fluorescence spectra

Photophysical behavior of spiro[1,3,3-trimethylindolino-2,3′-naphtho[2,1-b]-1,4-oxazine] (SP1) and spiro[1,3,3,2′-tetramethylindolino-2,3′-naphtho[2,1-b]-1,4-oxazine] (SP2) were studied. The fluorescent species and their spectra of SP1 and SP2 in polar solvents (acetonitrile and methanol) and non-polar solvent (cyclohexane) were investigated. The fluorescence decay in polar solvents was studied by picosecond time-correlated single photon counting. In most cases, fluorescence decay obeyed triexponential decay kinetics. The major fluorescent species is an excited intermediate which has similar conformation as its precursor (¹ SP ^*) formed after the bond cleavage between spirocarbon and oxygen in oxazine ring. The effects of molecular structure and solvent polarity on fluorescence spectra and fluorescence decay lifetime were studied.     

Detection of relative dimer and rotamer concentrations of diacetamide in different solvents by FT-IR spectroscopy and DFT calculations

The relative rotamer, dimer and tautomer concentrations of diacetamide have been studied by means of infrared spectroscopy, with the recorded spectra being analyzed employing results from density functional theory calculations. It is observed that the cis–trans monomeric form of diacetamide (1) is found to be the most stable isomer in all studied solvents, with trans–trans diacetamide (2) being found to be 20% of total diacetamide in methanol. While the dimer form of diacetamide (3) is present only in carbontetrachloride (about 34% of the total), its tautomeric forms (4, 5) are not favorable in any of the studied solvents.     

含氨基酸单元的手性主体的合成及手性识别研究

以L-丙氨酸和2,7-二萘酚为原料通过简单的方法合成了二种带有荧光基团萘的手性阴离子主体(1和2), 用红外光谱、质谱、元素分析、核磁共振氢谱及碳谱表征了它们的结构. 用荧光光谱及核磁共振氢谱研究了主体与二苯甲酰酒石酸阴离子的相互作用, 结果表明1, 2与D-或L-二苯甲酰酒石酸阴离子均形成1∶1的配合物, 主体1展现出良好的对二苯甲酰酒石酸阴离子对映选择性识别能力.     

Peculiarities of thermal decomposition of inorganic and organometallic compounds of GeIV and GeII. Thermolysis of (acac)2GeX2 (X = Cl,N3) and (CO)5MGeCl2(thf) (M = Cr,Mo, W)

Thermal decomposition of the complexes (acac)₂Ge(N₃)₂ (1), (acac)₂GeCl₂ (2), and (CO)₅M=GeCl₂(THF) (M = Cr (3), Mo (4), W (5)) was studied by differential scanning calorimetry and thermogravimetry. The phase compositions of the products of thermolysis of compounds 1—3 and 5 were determined by X-ray phase analysis. Possible schemes of thermal decomposition of these compounds were proposed. The heat capacities of complexes 3—5 were studied in the temperature range 113—313 K. The structures of complexes 1 and 5 were established by X-ray diffraction analysis.     

Syntheses,structures and properties of two Cu complexes with 4-(1H-imidazol-4-ylmethyl)aminophthalic acid

Two temperature-dependent copper(II) complexes {[Cu(HL)][Cu(HL)(H₂O)]} _n (1) and {[Cu(HL)]·H₂O} _n (2) [H₃L = 4-(1H-imidazol-4-ylmethyl)aminophthalic acid] have been synthesised under hydrothermal conditions. X-ray diffraction analysis reveals that complex 1 displays two crystallographic independent units, 1D chain and binuclear unit, respectively. The 1D chains and binuclear molecules are staggered arrangements along the c-axis in an (…ABAB…) fashion. When increasing the reaction temperature, complex 2 was obtained with only 1D chains structure. In addition, the magnetic property of complex 2 was studied, which indicates antiferromagnetic interactions between the neighbouring Cu(II) centres. The electrochemical and electrocatalytic properties of complex 2 have also been studied by modified glassy carbon electrode of 2.     

The preparation and reactivity of metal-containing monomers. 54. Thermolysis of the acrylamide monomer [Co(CH2=CHCONH2)4(H2O)2](NO3)2

The kinetics and pathways of thermolysis of the Co(II) complex with acrylamide, [Co(CH₂=CHCONH₂)₄(H₂O)₂](NO₃)₂ (1) were studied. The rate of gas evolution is satisfactorily approximated by a first-order equation of autocatalysis. The composition of gaseous and solid products of thermolysis of 1 was studied by IR spectroscopy, mass spectrometry, and electronic microscopy. Thermal transformations of acrylamide complex 1 include three macro stages: dehydration, polymerization of the dehydrated monomer, and thermooxidative destruction of the resulting polymer.     

New silica hybrids elaborated by sol-gel process from bifunctional thiadiazole and 1,2,4-triazole precursors

New hybrid materials were synthesized from an inorganic precursor, (tetraethoxysilane: TEOS) and bifunctional organic precursors through the sol-gel process. Indeed, monolithic and transparent hybrid gels were obtained by the reaction of tetraethoxysilicate (TEOS) with 1,2,4-thiadiazole-3,5-diamine (1), 5-amino-1,3,4-thiadiazole-2-thiol (2), and 1H-1,2,4-triazole-3-thiol (3) in ethanol as solvent, using chloric acid (HCl 10^?1M) as catalyst. It is shown that TEOS has been cross-linked with bi-functional heterocyclic compounds: (1), (2) and (3) leading to the formation of transparent and colorous gels. The characterization was realized by infrared, ²⁹Si and ¹³C CP MAS NMR. The xerogels morphology and texture were studied by scanning electron microscopy (SEM) and Brunauer – Emmet – Teller method (BET). The obtained results show that organic adducts (1), (2) and (3) react with TEOS leading to gels in which Si–N and Si–S bridges were formed. According to N₂-physisorption results, xerogels are mesoporous with specific surface area varied from 105 to 312 m²g^?1 and their isotherms are classified as type IV. The optic and magnetic properties of hybrids were studied respectively by UV-Vis spectroscopy and RPE. This study showed that all materials are paramagnetic semiconductors.     

Two lanthanide luminescent coordination compounds based on 3,5-pyrazoledicarboxylate and oxalic acid

Two isostructural 3-D complexes [Ln(pdc)(ox)_0.5(H₂O)₂]?H₂O (Ln = Tb(1), Eu(2); pdc = 3,5-pyrazoledicarboxylate; ox = oxalate) have been synthesized under hydrothermal conditions. Both are characterized by single crystal X-ray diffraction, elemental analysis, and IR. Compounds 1 and 2 possess a 3-D framework with 1-D rectangular channels built from 2-D, brick-like networks, and pdc ligands. The photoluminescence and lifetimes of 1 and 2 in the solid state have been studied.     

Synthesis,characterization and crystal structure determination of iron(III) complexes containing 4,4′-dimethyl-2,2′-bipyridine,dimethyl sulfoxide and chloride, [Fe(dmbipy)Cl4][dmbipyH] and [Fe(dmbipy)Cl3(DMSO)]

[Fe(dmbipy)Cl₄][dmbipyH], 1 (dmbipy is 4,4′-dimethyl-2,2′-bipyridine), was prepared from reaction of FeCl₃ · 6H₂O with 4,4′-dimethyl-2,2′-bipyridine in 0.1 molar aqueous HCl. Treatment of 1 with dimethyl sulfoxide in methanol produced [Fe(dmbipy)Cl₃(DMSO)], 2 (DMSO is dimethyl sulfoxide). Both complexes were characterized by IR, UV-vis, and ¹H-NMR spectroscopies and their structures were studied by single crystal diffraction. Compounds 1 and 2 are high-spin with spin multiplicity of six.     

Role of the C3-substituted derivatives of cinchonidine in the enantioselective hydrogenation of ethyl pyruvate on Pt-alumina catalyst in AcOH

Summary The enantioselective hydrogenation of ethyl pyruvate (EtPy) was studied on Pt-alumina catalysts modified by C3-substituted cinchonidines (NC, A, B, C1, C2in Fig. 1) and for comparison by DHCDand MeO-DHCDin AcOH. The effect of the C3-substituent on the reaction rate and the enantioselectivity were examined. Using the Engelhard 4759 catalyst under mild experimental conditions (room temperature, hydrogen pressure 1 bar) such as DHCDthe (R)-ethyl lactate formed in excess (e.e.max: 79-91%)</o:p>     

Acetato and formato copper(II) paddle-wheel complexes with nitrogen ligands

Compounds Cu(AcO)₂(pydz) (1), Cu(HCOO)₂(pymd)_1/2 (2), Cu(AcO)₂(pymd)_1/2 (3), and Cu(AcO)₂(4,4′-bipy)_1/2 (4) were obtained by reactions of Cu(AcO)₂?H₂O and Cu(HCOO)₂ ? 4H₂O with pyridazine, pyrimidine, or 4,4′-bipyridine. In all the studied structures, the paddle-wheel units [Cu₂[µ-RCOO)₄] are present. Coppers show a square pyramidal coordination determined by four oxygens in the equatorial positions and a nitrogen in the axial position. Compound 1 consists of centrosymmetric dimeric molecules. Compounds 2 and 3 instead consist of zig-zag chains of [Cu₂[µ-RCOO)₄] units linked by bridging pyrimidine molecules. The chains run in the (1 0 1) and (1 1 ?2) directions in 2 and 3, respectively. By crystallization of a solution of 4 in chloroform, Cu(AcO)₂(4,4′-bipy)_1/2 ? 1/2CHCl₃ (5) was obtained. It consists of monodimensional chains of [Cu₂(µ-CH₃COO)₄] units linked by bridging 4,4′-bipy molecules. The chains, of two different types, run parallel to the b-axis in the crystal. Two chlorines of each CHCl₃ molecule are close to two oxygens of two parallel chains. The packing can be described as sheets parallel to the (1 0 ?1) plane. Magnetic properties and electron paramagnetic resonance spectra have been studied.     

ETHYLENESULFONANILIDE

Abstract

The preparation and the chemistry of ethane-1,2-disulfonyl chloride, has been previously studied and described by Kohler.¹ In his work Kohler claimed the isolation of an “anhydrophenyltaurine” 2 (a four-membered ring β-sultam) from the reaction in the cold of ethane-1,2-disulfonylchloride (1) with excess aniline in ether.     

Syntheses and characterization of three mercury(II) complexes, [Hg(phen)2(SCN)2], [Hg(2,2′-bipy)2(SCN)2] and [Hg(phen)2(NO3)2], thermal and fluorescence studies

Mercury(II) complexes of 1,10-phenanthroline (phen) and 2,2′-bipyridine (bipy), [Hg(phen)₂(SCN)₂] (1), [Hg(2,2′-bipy)₂(SCN)₂] (2) and [Hg(phen)₂(NO₃)₂] (3) have been synthesized and characterized by elemental analysis, IR, ¹H NMR and ¹³C NMR spectroscopy. The thermal stability of 1–3 were studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The structure of 1 has been confirmed by X-ray crystallography. The complex is a monomer and the Hg atom has an unsymmetrical six-coordinate geometry, formed by four nitrogen atoms of the two phen ligands and two sulfur atoms of the two thiocyanate anions. Solid-state luminescent spectra of phen, 2,2′-bipy and 1–3 indicate emission with the maximum intensity at ca 467 nm upon excitation at 295 nm.