Synthesis and characterization of bis-cyclopropanated 1,3,5-tricarbonyl compounds. A combined synthetic, spectroscopic and theoretical study

Bis-cyclopropanated 1,3,5-tricarbonyl compounds were prepared by a sequence of Claisen condensations and cyclopropanations. The optimization of the conditions proved to be very important to suppress retro-Claisen reactions. The conformation of these molecules was studied by experimental and computational methods. The syn/syn;syn/syn conformation is present for all derivatives. It is exclusively present in the case of the derivative containing a phenyl group located at the terminal carbon atom. In most cases, equilibria with other conformers are found.     

Reversible valence equilibrium reactions in main group compounds. A theoretical study

The potential energy surface for the intramolecular reaction of singlet state RR'E=ERR' (E = C, Si, Ge, Sn, and Pb) has been explored using density functional theory. All the stationary points, including the unsymmetrical reactant (R'R(2)E-ER'), the transition state, the symmetric product (R'RE=ERR'), and the monomer (R'RE) were completely optimized at the B3LYP/LANL2DZdp level of theory. Our theoretical findings suggest the following: (1) Both double-bonded RR'C=CRR' and RR'Si=SiRR' species are true minima on their potential energy surfaces and should be the only compounds existing at all temperatures. (2) The germanium system will occur either in the dimeric R(2)R'Ge-GeR' and RR'Ge=GeRR' structures or the monomeric RR'Ge structure, depending on the temperature. (3) If the size of the substituent (R) is small, then the unsymmetrical single-bonded R(2)R'Sn-SnR' molecule can exist at low temperatures. At room temperature, the unsymmetrical R(2)R'Sn-SnR' species can exist in equilibrium with its RR'Sn monomer. (4) The unsymmetrical R(3)Pb-PbR compound may be kinetically stable at low temperatures. On the other hand, it is predicted that both the unsymmetrical R(3)Pb-PbR and the symmetric R(2)Pb=PbR(2) species will spontaneously dissociate into R(2)Pb monomers at room temperature. Our theoretical results are in good agreement with available experimental observations (J. Am. Chem. Soc. 2003, 125, 7520), and the results obtained allow a number of predictions to be made.     

Synthesis,structural and spectroscopic study of aromatic thioester compounds

Eight novel thioesters were obtained and characterized by elemental analysis, mass spectrometry, infrared and NMR spectroscopy. The data were analyzed on the basis of the relevant resonance structures. The X-ray single crystal structure of o-methoxythiophenyl 4-methylbenzoate is reported.     

Melt-polymerizable bisimido-bisphthalonitriles containing silicon,fluoro, and ether groups: Synthesis,characterization, and NMR study

Various melt-polymerizable bisimido-bisphthalonitrile polymer precursors were synthesized by the reaction of 4-aminophthalonitrile (4-APN) with bis(3,4-dicarboxyphenyl) dimethylsilane dianhydride (SIDA), 4,4′-hexafluoroisopropylidene diphthalic anhydride (6FDA), bis(3,4-dicarboxyphenyl)ether dianhydride (ODPA), and 3,3′, 4,4′-tetracarboxylichenzophen+ne dianhydride (BTDA) in an aprotic solvent. The synthesized monomers showed crystalline melting at 269 and 271°C. Elemental analysis, differential thermal analysis (DTA), infrared (IR), nuclear magnetic resonance (¹H-NMR) and mass spectral studies were carried out to characterize the synthesized monomers. Thermogravimetric analysis (TGA) of the synthesized monomers showed their thermal stability at 410–400°C. A detailed study and NMR investigation of the first step of condensation reaction was carried out and indicated the formation of a transient charge transfer complex. Thermal cyclization of the formed intermediate, however, gave the required monomers. A preliminary study demonstrated that melt-polymerization of the synthesized monomers gave thermallystable, tough polymers.     

High-pressure syntheses of novel binary nitrogen compounds of main group elements

The application of high-pressure methods in the search for novel materials usually requires additional effort compared to syntheses at ambient pressure. Depending on the desired p/T conditions different methods may be used. Special techniques and experimental apparatus such as shock waves, diamond anvil cells, and multianvil presses, which have been applied mainly by earth scientists and physicists in the past, are increasingly being applied by synthetic chemists and material scientists. A series of fascinating discoveries have been made recently as is demonstrated by three examples of binary nitrogen compounds: 1) Diazenides, compounds with N(2)(2-) ions, were obtained as single-phase products and structurally characterized for the first time. 2) At 11 GPa and 1800 K a phosphorus(V) nitride was prepared, which contains tetragonal PN(5) pyramids as a novel structural motif. 3) Macroscopic amounts of spinel silicon nitride were synthesized by shock-wave techniques, which allows the comprehensive characterization and possibly the implementation of this new hard material.     

主族元素取代的11-钨铜杂多配合物的合成、表征及性质研究

合成了ⅡA,ⅣA,ⅤA族元素为取代原子的3个系列钨铜杂多配合物.经ICP,TG曲线确定其化学式为K8[CuZ(OH2)W11O39].xH2O和K17,18[Z′(CuW11O39)2].xH2O(Z=Mg,Ca;Z′=Sr,Ba,Sn,Pb,Sb,Bi).通过TG-DTA,IR,XRD,XPS,183W-NMR等手段对合成配合物结构进行了表征,并对其进行了讨论.结果表明,新配合物具有典型的Keggin结构,且主族元素进入到配合物的骨架中.由于新配合物中CuⅡ具有顺磁性,导致XPS,183W-NMR的测试结果表现出特殊性;用循环伏安法测定了新配合物的电化学性质,表明均为可逆氧化还原过程,还对导电性和热稳定性进行了研究.     

Esterified porphyrazine complexes: Synthesis,characterization, aggregation behavior,and theoretical study

Magnesium porphyrazine having eight 5-hydroxypentylthio groups at the peripheral positions, was synthesized from 2,3-bis(5-hydroxypentylthio) maleonitrile. By the esterification reaction of octakis(5-hydroxypentylthio) porphyrazinato] Mg(II) with 3,4,5-trimethoxybenzoic acid in dicyclohexylcarbodiimide and toluene-p-sulfonic acid, esterified MgPz appending [5-thiopentyl 2-methoxy-4,6-bis(trifluoromethyl) benzoate] substituent was obtained. Further reaction of the metal-free porphyrazine with Co(II), Cu(II), Zn(II), and Fe(II) acetates have produced the metallo-porphyrazines. By reacting FePzCl with pyridine or pyrazine, the monomeric bis-axial and the oligomeric complexes were synthesized as the novel stable complexes, respectively. Their characterizations were performed by using elemental analysis, FT-IR, ¹H-NMR, ¹³C-NMR, mass and UV-Vis spectral data. The aggregation investigations carried out in different concentrations indicate that 3,4,5-trimethoxybenzyloxy-substituted porphyrazine compounds do not have any aggregation behavior in different concentrations. Quantum chemical computations were also done to the structural and electronic properties of target compounds.     

Synthesis,spectroscopic and magnetic characterization of some iron(III)-nucleotide compounds

Summary Magnetic moments and⁵⁷Fe M?ssbauer spectra at various temperatures of polycrystalline samples of some Fe^III-nucleotide compounds are described and have been characterized by u.v.-visible and fluorescence spectroscopy. Conclusions regarding the binding of iron(III) to nucleic acids are discussed.     

Mass-spectrometric study of permethyl compounds of group IVB elements

Russian Chemical Bulletin -     

New aluminum‐based ionic liquids: Synthesis,characterization, and theoretical study

Synthesis, characterization, spectral and molecular parameters of some new room‐temperature ionic liquids (tetraalkylammonium bromotrichloro aluminum [R₄N]⁺[AlCl₃Br]⁻) have been studied in the present study. All synthesized ionic liquids were characterized by IR, ¹H, ¹³C, and ⁸¹Br‐NMR. In addition, synthesized structures were optimized at the B3LYP/LANL2DZ level of theory and then the structures, molecular specifications, and infrared spectra of these were extracted using Gaussian 03 program. Theoretical data show good agreement with the experimental results. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 20:398–404, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20564     

Organotin gibberellates: Synthesis,spectroscopic characterization and antitumour activity

The synthesis and characterization of di-n-butyl-, tri-n-butyl- and triphenyltin gibberellates are reported. Their antitumour activities in vitro against a panel of seven human tumour cell lines are given and compared with those of drugs used clinically. Copyright © 1998 John Wiley & Sons, Ltd.     

Two new phosphinic amides: Synthesis,crystal structure,and theoretical study of hydrogen bonding

Two novel phosphinic amides, (C₆H₅)₂P(O)(NH?cyclo?C₇H₁₃) (I) and (C₆H₅)₂P(O)(NH?cyclo?C₆H₁₁) (II) were synthesized and characterized by spectroscopic methods and X-ray crystallography. Both compounds crystallize in the orthorhombic chiral space group P2₁2₁2₁ and in both structures, the N—H···O hydrogen bonds lead to one-dimensional arrangements along the a axis. The molecular geometries and vibrational frequencies of I and II were investigated with quantum chemical calculations at the B3LYP/6–311G^** level of theory. Furthermore, the hydrogen bonds were studied by means of the Bader theory of atoms in molecules (AIM) and natural bond orbital (NBO) analysis.     

Synthesis and characterization of trisubstituted heteropolytungstogermanates containing group 3A elements

Six new compounds, α,β-KaHb[GeW9M3(H2O)3O37].xH2O(M = Al, Ga,In; a + b =7) and α-K9H5[Ge2W18Ga6(H2O)3O74].20H2O, were synthesized from the lacunary precursors α and β-GeW9O34 10- and characterized by elemental analysis, spectroscopy and electrochemistry. Tungsten-183 NMR spectra of the title complexes consist of two lines with intensity ratio 2:1 as expected for trisubstituted heteropoly anions. The intensity ratio of α-Ga compound is 1:2, which is different from others(2:1). With the help of FAB mass spectrum, we concluded that it is a dimer with D3h, structure in aqueous, and the others exist by monomers with C3c structures.     

Synthesis theoretical and experimental spectroscopic characterization of isoniazid-benzoic acid drug complexes: Insilico and invitro biological evaluations

New organic charge-transfer molecules were synthesised by salt formation from isoniazid and benzoic acid/aspirin compounds acting as acceptor and donor molecules. The synthesised charge transfer complexes were characterized and structurally confirmed by various instrumental techniques such as UV–visible, FT-IR, powder XRD, and NMR spectroscopic methods. Initially, compounds are studied molecular docking analysis with different kinds of proteins, such as 1HNY.pdb, 1PGG.pdb and 4-COX.pdb. Docking results have been compared with molecular electrostatic potential mapping and Mulliken charge distribution methods. Results show that both complexes IAC and IBC have almost the same binding constant value with 1HNY.pdb. Besides, IBC has a more binding constant than the IAC with inflammatory proteins (1PGG.pdb and 4-COX.pdb). The reactivity of the complexes is explained by the chemical potential and electrophilic index derived by the frontier molecular orbitals using the DFT method. These results show a more electrophilic index of IBC than the IAC indicating, more electron affinity nature of IBC. This is also reflected in the in-vitro biological studies, which shows IAC having better activity in anti-diabetic studies whereas IBC has better activity in anti-inflammatory studies. For the sake of complex ability, all biological and molecular docking experimental results are compared with standard drug molecules.     

Complexes of Al(III) with 3'4'-dihydroxy-flavone: characterization, theoretical and spectroscopic study

Complex formation between aluminium chloride and 3'4'-dihydroxyflavone (3'4'diOHF) in methanol has been studied by UV-visible and Raman spectroscopies combined with quantum chemical calculations. Job's method of continuous variation and the molar ratio method were applied to ascertain the stoichiometry composition of the chelate in pure methanol. A 1:1 complex was indicated by both the methods. Geometry optimizations of free and complexed molecules by AMI and DFT methods show that structural modifications of the ligand, induced by complexation, are minor, and are localized on the chelating site. The good agreement between experimental and theoretical electronic spectra of both 3'4'diOHF and complex confirm the structural models. The great similarities between Raman spectra of the free and complexed form constitute an another proof of the absence of pronounced electronic and geometric changes, and notably demonstrate that the quinoidal form induced by the deprotonation of the two hydroxyl groups does not participate in the 3'4'diOHF complex structure. Whereas no complexation occurs in acidic medium, complexes of high stoichiometry are formed in alkaline medium. (Al(3'4'diOHF)2)- and (Al(3'4'diOHF)3)3- species are observed in methanol in the presence of sodium acetate or sodium methanoate.     

Polymerization of Chrysoidine with chemical and enzymatic oxidative preference: Synthesis,characterization, and spectroscopic study

Chrysoidine (CHRY) is a type of azo‐dye extensively used in industry. This study delineates 2 routes as enzymatically and oxidatively polycondensation of chrysoidine for the syntheses of poly (chry‐enz) and poly (chry‐ox), respectively. The molecular structures of enzymatically and oxidatively polymerized chrysoidine were described by the FT‐IR, UV‐Vis, ¹H‐NMR, and ¹³C‐NMR techniques. The molecular structures were obtained to be different as in the cyclization process of the enzymatic polymerization. Solvatochromic behavior in selected polar solvents on the optical properties of poly (chry‐ox) were studied. Further characterization was implemented by fluorescence (PL), electrochemical, thermogravimetric (TG‐DTA), cyclic voltammetry (CV), and differential scanning calorimetry (DSC) measurements. The number of average molecular weight of poly(chry‐ox) was found to be higher than that of poly(chry‐enz). Photoluminescence (PL) measurements enlightened the response of poly (chry‐ox) with intense light emissions upon a bicolor irradiation by Ultra‐Violet and visible light. CV technique was utilized to make a comment about HOMO‐LUMO energy levels and electrochemical ( ) band gaps of the polymers. Optical and electrochemical band gaps of poly (chry‐enz) were lower than those of poly (chry‐ox), proving the successful synthesis of π‐conjugated structure of poly (chry‐enz). To further make comments about the features of the polymers, scanning electron microscopy (SEM) images were exemplified to study the surface forms of the polymers. Surface morphology of poly (chry‐enz) was seen as agglomerates of grains toward the out‐of‐plane direction. As the polymerization method was changed, the morphology was transformed into a flat‐smooth surface present with visible holes for poly (chry‐ox).     

Gamma resonance spectroscopic study of compounds containing the π-allylirontricarbonyl group

The gamma resonance (GR) spectra of a series of -allylirontricarbonyl compounds and -cyclopentadienyldicarbonyl complexes of iron have been recorded. The relationship between the GR spectra of these compounds and the electronic structure of the iron atom in the complexes has been examined. It has been shown that tetrahydrofuran, benzene, and acetonitrile do not react with -allylirontricarbonyl chloride, whereas dimethylformamide decomposes it with the formation of high-spin complexes of iron. The formation of the [-C₃H₅Fe(CO₃)]^– anion in the reduction of [C₃H₅Fe(CO₃)]I by naphthalene-sodium in benzene has been confirmed.     

Synthesis, FT-Raman, FT-IR, NMR spectroscopic characterization and antimicrobial activity of new mixed aza-oxo-thia macrocyclic compounds

Series of new mixed aza-oxo-thia macrocyclic ligands {2,6,12,16-tetraaza-1,7,11,17-tetraoxo-9,19-dithia-[(4′-methyl-5′,4,3′)(14′-methyl-15′,14,13′)]ditriazine}cyclocosane (L ₁ ); {2,6,13,17-teraaza-1,7,12,18-tetraoxo-9,10,20,21-tetrathia-[(4′-methyl-5′,4,3′)(15′-methyl-14′,16′,15)]di-triazine}cyclodocosane (L ₂ ); {2,6,14,18-tetraaza-1,7,13,19-tetraoxo-10,22-dithia-[(4′-methyl-5′,3′,4)(16′-methyl-15′,17′,16)]ditriazine}cyclotetracosane (L ₃ ) and {2,6,15,19-tetraaza-1,7,14,12-tetraoxo-10,11,23,24-tetrathia-[(4′-methyl-5′,4,3′)(17′-methyl-8′,17,16′)]ditriazine}cyclohexa-cosane (L ₄ ) were synthesized. The structural features of the compounds have been studied by elemental analyses, Mass, FT-Raman, FT-IR, ¹H and ¹³C NMR spectroscopy. The antimicrobial activities of the ligands were evaluated using disk diffusion method in dimethyl sulfoxide as well as the minimal inhibitory concentration (MIC) dilution method, against 9 bacteria. The obtained results from disk diffusion method were assessed in side-by-side comparison with those of Penicillin-g, Ampicillin, Cefotaxime, Vancomycin, Oflaxacin, and Tetracyclin, well-known antibacterial agents. The results from dilution procedure were compared with Gentamycin as antibacterial and Nystatin as antifungal. The antifungal activities are reported on five yeast cultures namely Candida albicans, Kluyveromyces fragilis, Rhodotorula rubra, Debaryomyces hansenii, and Hanseniaspora guilliermondii, and the results are referenced with Nystatin, Ketaconazole, and Clotrimazole, commercial antifungal agents. In most cases, the compounds show strong antifungal activity in the comparison tests.