α-Thioureidoalkylation of 4-alkyl- and 4-phenylthiosemicarbazides

Previously unknown 1,3-dialkyl-4,5-bis[4-alkyl(phenyl)thiosemicarbazido]imidazolidine-2-thiones and 4,5,7-trialkylperhydroimidazo[4,5-e]-1,2,4-triazine-3,6-dithiones have been synthesized by the α-thio-ureidoalkylation of 4-alkyl(phenyl)thiosemicarbazides using 1,3-dialkyl-4,5-dihydroxyimidazolidine-2-thiones.     

Stereoselective Synthesis and Anticancer Activities of New Podophyllotoxin Derivatives:4-β-Cyano-4-Deoxy-4'-Demethylepipodophyllotoxin and 4-β-Carboxyl-4-Deoxy-4'-Demethylepipodophyllotoxin

Podophy1lotoxinl,isolatedfromPodoPhyllumpeIatumL.orPodoPhyllumemodiL.,showshighantitUmoractivity.But,itcatmotbeusedasantitUmoragentclinicallybecauseofitsseriousside-effect.Itssemisyntheticderivatives,EtoPoside2andTeniposide3,arewide-usedasboortantanticancerdrugs'.Howevef,theyhaveseverallimitationssuchaspoorwatersolubilitymetabolicinachvahonanddevelopmentofdrugresistance.Toovercometheselindtations,manyderivahvesofpodophyllotoxinhavebeensynthesizedinmanylaboratories2~5.Ithasbeenrecognisedt…     

Synthesis and oxidative polycondensation of 4, 4−diethynylbiphenyl

Summary 4,4-Diethynylbiphenyl was synthesized. By polycondensing it an oligomer with alternating biphenyl (-4,4) and diacetylene chains was obtained.     

Crystal and molecular structure of 4(3-acryloyloxy)octyloxy- and 4(3-acryloyloxy)hexyloxy-4′-cyanobiphenyls

The molecular and crystal structures of N≡C-C₆H₄-C₆H₄-O-(CH₂)₈-O-CO-CH=CH₂ (4(3-acryloyloxy)octyloxy-4′-cyanobiphenyl) (I) and N≡C-C₆H₄-C₆H₄-O-(CH₂)₆-O-CO-CH=CH₂ (4(3-acryloyloxy)hexyloxy-4′-cyanobiphenyl) (II) were determined by X-ray diffraction. The structures of I and II are stereotype. The space group of I and II is C2/c, Z = 8; lattice parameters I: a = 34.677(7)?, b = 9.452(2)?, c = 13.004(3) ?, β = 99.30(3)°; II: a = 30.858(6) ?, b = 9.504(2) ?, c = 13.082(2) ?, β = 92.78(3)°. The planar extended molecules I and II are packed in the unit cell to give clearly differentiated aliphatic and aromatic regions throughout the whole crystal. All intermolecular contacts are concentrated in the aromatic region. The molecular packing is very loose but the aromatic areas of I and II fully coincide. The only free parameter of the structure is the length of the aliphatic chain (CH₂)n (n = 8 and 6). According to DSC data, compound I possesses enantiotropic mesomorphism and II possesses monotropic mesomorphism.     

IR absorption spectra and structure of 4-cyano-4′,-p-alkoxybiphenyls

The IR absorption spectra of 4-cyano-4,-p-alkoxybiphenyls were investigated experimentally (in the range 100–3200 cm^–1 at 100–400 K), and they were interpreted on the basis of a calculation of the frequencies, forms, and intensities of the normal vibrations of various conformers of the propyloxycyanobiphenyl molecule. Temperature and phase changes in the parameters of the IR spectrum are explained by a change in the conformational composition and intermolecular interactions in the investigated liquid crystals.Institute of Physics, Ukrainian Academy of Sciences. Saratov State University. Translated from Zhurnal Strukturnoi Khimii, Vol. 34, No. 2, pp. 105–111, January–February, 1993.     

The Synthesis of l-Ethyl-1''''-(4-vinylbenzyl)-4, 4''''-bipyridinium Chloride and Iodide and its Electrochromic Property

A new compound 1-ethyl-1'-(4-vinylbenzyl)-4, 4'-bipyridinium chloride and iodide has been synthesized. The cyclic voltammogram and impedance spectra indicated that a layer of viologen's electrochromic (EC) film could be deposited on conductive ITO glass working electrode. With polyelectrolyte as ionic conduction layer, solid EC devices based on this compound have been assembled and their thickness was about 2.35 mm. When different voltages were added, they showed blue or violet red color. After optimization, its response time was less than 50 ms, the number of redox circulation was over 107 and the color of coloration states could be kept for 3 days. This kind of EC device can meet the demand of electronic ink.     

Corrected values of osmotic and activity coefficients of aqueous NaTcO4 and HTcO4 at 25°C

Published isopiestic molalities for aqueous NaTcO₄ and HTcO₄ solutions at 25°C have been reexamined. Our calculations indicate that published smoothed values of the osmotic coefficients and mean molal activity coefficients _± of NaTcO₄ are substantially in error, by up to 100% for and 300% for _±. Published smoothed values of and _± for HTcO₄ solutions are in somewhat better agreement with the input data, but the reported are sometimes higher and sometimes lower than experimental values, by up to 6%. Consequently, we have reanalyzed isopiestic data for these two systems, and find that errors arose in representing the data mathematically. We report parameters for an extended form of the specific ion interaction equations and for Pitzer's equations, and corrected values of and _± are tabulated for aqueous NaTcO₄ and HTcO₄.     

Synthesis and application of 4-dipropylaminodiazabenzene-4′-isothiocyanate to the derivatization and chromatographic separation of biogenic amines

Summary The physicochemical properties of biogenic monoamines, their polar character, lability and trace amounts found in the biological material create great analytical difficulties in their identification and separation. The selective chromatographic separation of those amines is greatly facilitated by their derivatization [1]. Based on theoretical considerations, 4-dipropylaminodiazabenzene-4′-isothiocyanate (DPABITC) was synthetized and applied to the preparation of thiocarbamoyl derivatives of the amines. The coloured derivatives were separated by TLC. Presented at Balaton Symposium on High Performance Separation Methods, Siófok, Hungary, September 1–3, 1999     

Powder diffraction data and mesomorphic properties of 4-butyloxyphenyl 4′-decyloxybenzoate

Unit cell parameters calculated from X-ray powder diffraction data are presented for the crystalline phase of a liquid crystal 4-butyloxyphenyl 4′-decyloxybenzoate: a = 23.098 (4) Å, b = 5.974 (6) Å, c = 12.357 (10) Å, β = 121.5283 (788)°, unit-cell volume V = 1453.56 ų. Temperature dependent X-ray diffraction data confirmed the existence of smectic A and smectic C mesophases and a more ordered, tilted crystalline smectic phase. Possibility of existence of previously reported smectic B phase as well as another crystalline phase was refuted.     

Ab initio quantum mechanical calculations of energy,geometry, vibrational frequencies and IR intensities of tetraphosphorus tetrasulphide, α-P4S4(D2d), and vibrational analysis of As4S4 and As4Se4

Geometry, vibrational frequencies and IR intensities are calculated for α-P₄S₄ by scaled quantum mechanical calculations at the 6-31G*/SCF and STO-3G*/SCF levels. For both basis sets the frequencies are scaled with factors close to or equal to those found for P₄S₃, and based on these results a revised assignment is proposed. The α-P₄S₄ force field is transferred to the isostructural As₄S₄ and As₄Se₄ molecules and rescaled, and based on a good fit to experimental frequencies a new assignment is also proposed for these compounds.     

Synthesis,mesomorphic and dielectric properties of 4-(cyanomethoxy)phenyl 4-alkoxybenzoates, 4-(cyanomethoxy)-4′-alkoxyazo- and -azoxybenzenes

Preparation methods were developed for homologs of 4-(cyanomethoxy)phenyl 4-alkoxybenzoates (C₇, C₈, C₉), 4-(cyanomethoxy)-4′-alkoxyazo (C₂, C₃, C₆), -azoxybenzenes (C₃, C₆) whose composition and structure were proved by elemental analysis and ¹H NMR spectra. 4-(Cyanomethoxy) group destabilizes the mesophase, consequently, only four among the compounds obtained exhibit the thermotropic nematic mesomorphism.     

Spectral and electrochemical study of coordination molecules Cu4OX6L4: 3-Pyridylmethanol and 4-pyridylmethanol Cu4OBrnCl(6−n)(pm)4 complexes

The tetranuclear Cu₄OBr_nCl_(6−n)(pm)₄ complexes, where pm = 3-pyridylmethanol (3-pm), 4-pyridylmethanol (4-pm) and n = 0−6 with trigonal bipyramidal coordination of copper(II) were prepared and their infrared and electronic absorption spectra as well as cyclic voltammograms in nitromethane solutions were measured. The molecules exhibit strong single infrared Cu₄O stretching absorptions between 580 and 530 cm⁻¹ which are in linear correlations with the number of halides, n. Far infrared absorptions assigned to Cu-Br, Cu-Cl, and Cu-N stretching vibrations appear at higher wavenumbers for 3-pm complexes compared with those for 4-pm complex molecules. Two strongly overlapped d–d bands in the region 11300–13100 cm⁻¹ assigned to and e(d _xz, d _yz) → a ₁(d _z ²) transitions in the trigonal bipyramidal coordination of the copper(II) atoms were resolved by Gaussian analysis. Both, 3-pm and 4-pm ligands produce in the complex molecules almost the same ligand field. The maxima of the Gaussian d–d components vary with the parameter n and are for both series of the complexes deviated from linearity, more for the low-energy d–d bands than for high-energy analogues. The electrochemical reduction in nitromethane is significantly less reversible for 4-pm complex molecules compared with that of 3-pm analogues. Formal reduction potentials E′ _c for 3-pm complexes were observed in the range 478 (n = 0)−599 (n = 6) mV. The plot E′ _c vs. n is significantly deviated from linearity. It is suggested that the reducing electrons enter the half-filled d _z ² orbital of the copper(II) atom. The different spectral and electrochemical results obtained for 3-and 4-pm complexes are explained by different structural distortions, bond lengths, and charge distributions produced by halide ligand variations. The results are also discussed with previously reported data on analogous pyridine, 3-methylpyridine and 4-methylpyridine complexes.     

Theoretical study of the stability and electronic structure of Al(BH4)n=1→4 and Al(BF4)n=1→4 and their hyperhalogen behavior

Using density functional theory (DFT), we have systematically calculated the equilibrium geometries, electronic structure, and electron detachment energies of Al(BH(4))(n=1→4) and Al(BF(4))(n=1→4) at the B3LYP/6-311+G(2d,p) level of theory. The electron affinities of Al(BH(4))(n) not only exhibit odd-even alternation, just as seen in (BH(4))(n), but also, for n = 3 and 4, show a remarkable behavior: whereas the electron affinities of BH(3) and BH(4) are, respectively, 0.06 and 3.17 eV, those of Al(BH(4))(3) and Al(BH(4))(4) are 0.71 and 5.56 eV. Results where H is replaced by F are also very different. The electron affinities of BF(3) and BF(4) are, respectively, -0.44 and +6.86 eV, and those of Al(BF(4))(3) and Al(BF(4))(4) are 1.82 and 8.86 eV. The results demonstrate not only marked difference when H is replaced by F but also substantially enhanced electron affinities by almost 2 eV when BH(4) and BF(4) units are allowed decorate a metal atom, confirming the recently observed hyperhalogen behavior of superhalogen building blocks.     

Electrical and electro-optical parameters of 4ʹ-octyl-4-cyanobiphenyl nematic liquid crystal dispersed with gold and silver nanoparticles

Thermodynamical, dielectric, optical and electro-optical characterisation of pure 8CB and its composites with gold and silver nanoparticles have been studied. Thermodynamical studies suggest a decrease in clearing temperature of the nanocomposite systems as compared to the pure system. Dielectric parameters of pure nematic liquid crystal and nanocomposites in the homeotropic and planar aligned samples have been measured in the frequency range of 1–35 MHz. Ionic conductivity increases significantly in nematic and smectic A_d (SmA_d) phases, whereas dielectric anisotropy is almost unchanged for both the nanocomposites. Threshold voltage for Freederick transition, switching voltage and splay elastic constant have decreased in the case of nanocomposite systems. Relaxation frequency and activation energy of an observed relaxation mode corresponding to molecular rotation about the short axis increase in the SmA_d phases of both the nanocomposites. The optical study suggests that due to dispersion of nanoparticles, the optical band gap has decreased.     

Crystal and Molecular Structure of 4-Phenyl-cyclohexanone Semicarbazone

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Determination of the ground- and excited-state dipole moments of 4’-(hexyloxy)-4-biphenylcarbonitrile and 4-isothiocyanatophenyl 4-pentylbicyclo [2,2,2] octane-1-carboxylate nematic liquid crystals and their mixtures

The dipole moments of the ground and excited states of 4′-(hexyloxy)-4-biphenylcarbonitrile and 4-isothiocyanatophenyl 4-pentylbicyclo [2.2.2] octane-1-carboxylate nematic liquid crystals and their mixtures prepared in chloroform and dichloromethane were studied at room temperature. The dipole moments of the ground states of the all samples were calculated according to the Guggenheim–Smith method. The dipole moments of their excited states were determined with the help of the Lippert equation by measuring the absorption and fluorescence spectra, solvent polarity and refractive index values. It was determined that dipole moments of the excited states were higher than those of the ground states. Moreover, the dipole moments of the ground and excited states of two nematic liquid crystals were also estimated by using molecular mechanic method (Gaussian09 program (DFT/B3LYP 6-31G(dp)). The results obtained are interpreted in detail.     

Synthesis and Structure of Ag_3PSe_4

The title compound Ag3PSe4 was synthesized by the reaction of Ag powder,P2Se5 and Se in a molar ratio of 1:1:1 at 500℃ and structurally characterized by X-ray crystallography.The crystal belongs to orthorhombic,space group Pmn21 with cell parameters:a=7.689(4),b=6.660(3),c=6.379(4)A,V=326.7(3)A^3,Z=2,Dc=6.816g/cm^3,Mr=670.42,F(000)=584,μ=31.302mm^-1,R=0.0606,wR=0.1289 and S=1.012,The 3-D structure can be regarded as constructed from the stacking of puckered Ag-P-Se honeycomb-like sheets along the c direction,in which the Ag,P and Se atoms are bonded to each other to form a chair-like six-membered ring,and the rings then build the sheets by sharing edges.     

Photophysics properties of 4-formacyl-triphenylamine and 4,4''''-bisformacyl-triphenylamine

The photophysical processes of 4-formacyl-triphenylamine (FTA) and 4,4'-bisformacyl-triphenyl-amine (BTA) have been studied. The fluorescences of FTA and BTA with donor (triamine) and acceptor (formacyl) moieties show the twisted intramolecular charge transfer (TICT) emission in polar solvents and photoinduced charge transfer (ICT) emission in nonpolar solvents. These could be supported by the solvent effect, temperature effect and the quenching process by strong electron-deficient compounds.     

Synthesis and Structure of 4—Nitrobenzaldehyde Thiosemicarbazone

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