Ion exchangers as catalysts. II. Catalytic decomposition of hydrogen peroxide with resin-ethylenediamine-copper(II) complex ions

Summary The slow decomposition of H₂O₂ in the presence of Dowex-50 W resin in the form of an ethylenediaminecopper(II) complex ion in water is accompanied by an induction period. The reaction is first order with respect to [H₂O₂] and the rate constant (perg of dry resin) was deduced. Autocatalytic behaviour was found for the H₂O₂ decomposition with 2% crosslinked divinylbenzene. The induction period disappeared and the reaction rate increased when the decomposition was carried out with a resin in the form of a peroxo-copper complex, which proves that the formation of an intermediate (active species) retards the reaction rate. The precursor of the active species, formed during the induction period, was not the amine-copper(II) complex ion but a product of the latter with H₂O₂. It proved impossible to carry out the decomposition in acid or buffer solutions, in which the resin is regenerated.     

Elucidation of the structures of 3-alkylthio-, 3-benzylthio-, 2-arylthio- and 2-heteroarylthio-N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamines by one- and two-dimensional NMR spectroscopy

Nucleophilic addition of alkyl- and benzylthiols to benzoquinone diimine (1) gave the corresponding 3-alkylthio- or 3-benzylthio-1,4-phenylenediamines (2-5). However, addition of aryl- or heteroarylthiols to 1 formed 2-arylthio- or 2-heteroarylthio-1,4-phenylenediamines (6-14). The structures of 2-14, obtained in 55-91% yields, were confirmed in CDCl3 or DMSO-d6 solution using 1D (NOE difference, coupled 13C NMR spectra, APT and DEPT) and 2D NMR techniques [DQCOSY, NOESY, HETCOR and heteronuclear multiple bond coherence (HMBC)] that resulted in unambiguous proton and carbon NMR resonance assignments. The substituent-induced 13C NMR chemical shift differences were calculated in 2-14 relative to carbon atoms in the model compound N1-(1,3-dimethylbutyl)-N4-phenyl-1,4-phenylenediamine (DMBPPD) (15) (a reduced form of benzoquinone diimine).     

Übergangsmetall-carben-Komplexe. LXXX. α-Alkoxy- und α,α-dialkoxysubstituierte Phenylacetyl-(pentacarbonyl)metallate und Pentacarbonyl[alkoxy(benzyl)-carben]-Komplexe des Chroms und Wolframs

Vibrational Spectra of Dichlorophosphorylmethylamine CH₃? NH? P(?O)Cl₂ and its Adducts with SbCl₅ and SnCl₄ The vibrational spectra of liquid samples and solutions, as well as cryoscopic molecular weight determinations show that CH₃? NH? P(?O)Cl₂ exists largely in the dimeric form. The association occurs through hydrogen bridges. The adducts SbCl₅ · CH₃? NH? P(?O)Cl₂ and SnCl₄ · 2 CH₃? NH? P(?O)Cl₂ are formed through addition via an oxygen atom. The ligands have cis-configuration in the tin compound.     

Synthesis of Heterocycles via 2-Thioxo-1,2-dihydropyridine-3-carbonitrile Derivative

The present study aimed to investigate the synthetic potentiality and chemical reactivity of 2-thioxo-1,2-dihydropyridine-3-carbonitrile derivative 1. This goal performed via its reaction with each of 1-chloroacetone and iodomethane to afford the corresponding 2-alkylthio derivatives 3 and 9, respectively. Compound 3 underwent intramolecular cyclization to afford the corresponding thieno[2,3-b]pyridine derivative 4 which in turn, reacted with dimethylformamide/dimethylacetal followed by hydrazine hydrate and nitrous acid to afford the corresponding pyridothienopyrimidine and pyridothienopyridazine derivatives 6 and 8, respectively. On the other hand, Compound 9 reacted with hydrazine hydrate to give 3-aminopyrazolo[3,4-b]pyridine derivative 10, which diazotized with nitrous acid to give the corresponding diazonium salt 11. Compound 11 coupled with several active –CH₂-containing reagents to synthesize the corresponding pyridopyrazolo-triazines 15, 24, 29, and 31. The formulas of all newly synthesized heterocyclic compounds were elucidated by considering the data of IR, ¹H NMR, Mass spectral data, as well as data from elemental analyses.     

Nano-sized Co(II)-8-hydroxyquinolate complex thin film via surface layer-by-layer chemical deposition method: Optimized factors and optical properties

An extensive study was performed and reported for evaluation and optimization of the factors affecting thin film formation of nano-sized Co(II)-8-hydroxyquinolate complex by surface layer-by-layer chemical deposition method. The formation of uniform thin films of nano-crystalline metal complex is heavily dependent on several important factors. Variation in metal and ligand concentrations (1:1–1:3) was found to show insignificant contribution to the molar stoichiometric ratio of the synthesized thin film of nano-sized Co(II)-8-hydroxyquinolate. The number of dipping cycles (2–50) was characterized by strong influence on the thin film thickness. The dependence of the immersion time (2–50 s) was proved to influence the crystal growth and homogeneity of the thin film. The role of pH of metal and ligand solutions was identified by strong contribution in development and formation of deposited Co(II)-8-hydroxyquinolate complex thin film. Finally, the role of solvent on the thin film formation was also studied and evaluated. Metal analysis, SEM, EI-MS, FT-IR and TGA were applied as monitoring techniques of these factors. The optical properties of Co(II)-8-hydroxyquinolate complex were also studied and the complex thin films were characterized by the highest optical transition from π–π* or n, π* states with energy gap in the UV-range at 3.13 eV. The lowest optical transition resulted from d–d transition or metal centered transition with energy 1.5 eV while, the optical transition at 2.35 eV is the contribution of metal ligand or ligand metal transition. In the light of the optical measurement, Co(II)-8-hydroxyquinolate complex can be considered as an organic semiconductor with the potential applications in the design of organic light-emitting diodes (OLEMs).     

Numerical and experimental study of turbulent impinging twin-jet flow

The two dimensional impinging circular twin-jet flow with no-cross flow is studied numerically and experimentally. The theoretical predications are carried out through numerical procedure based on finite volume method to solve the governing mass, momentum, turbulent kinetic energy and turbulent kinetic energy dissipation rate. The parameters studied were jet Reynolds number (9.5 × 10⁴  Re  22.4 × 10⁴), nozzle to plate spacing (3  h/d  12), nozzle to nozzle centerline spacing (l/d = 3, 5 and 8) and jet angle (0°  θ  20°). It is concluded that the stagnation primary point moves away in the radial main flow direction by increasing the jet angle. This shift becomes stronger by increasing the nozzle to nozzle centerline spacing (l/d). A secondary stagnation point is set up between two jets. The value of pressure at this point decreases by decreasing Reynolds number and/or increasing the jet angle.

The sub atmospheric region occurs on the impingement plate. It increases strongly by increasing Reynolds number and decreases as the jet angle and/or a nozzle to plate spacing increases. The spreading of jet decreases by increasing nozzle to plate spacing. The intensity of re-circulation zone between two jets decreases by increasing of h/d and jet angle. The increase of turbulence kinetic energy occurs within high gradient velocity.     

Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases

The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.     

Crystal Structures and Spectral Studies of [Ph3Sn(O2AsMe2)], [Bu2ClSn(O2AsMe2)] and [PhClSn(O2AsMe2)(μ‐OMe)]2

[Ph₃Sn(O₂AsMe₂)] ( 1 ) and [PhClSn(O₂AsMe₂)(μ‐OMe)]₂ ( 3 ) have been synthesized by treatment of Ph₃SnCl and Ph₂SnCl₂ with Na(O₂AsMe₂) in methanol, respectively. [Bu₂ClSn(O₂AsMe₂)] ( 2 ) has been prepared by the reaction of Bu₂SnCl₂ with HO₂AsMe₂ in methanol. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/n with a = 699.8(1), b = 1961.4(2), c = 1433.6(2) pm, β = 95.17(1)°, and Z = 4. 2 also crystallizes monoclinic in the space group P2₁/m, the cell parameters being a = 480.6(1), b = 1992.7(2), c = 808.8(1) pm, β = 103.726(5)°, and Z = 2. Both compounds form infinite chains with alternating (Me₂AsO₂)^? and (R₃Sn)⁺ or (R₂ClSn)⁺ units. The dimer 3 consists of 8‐membered (OSnOAs)₂ rings in which the tin atoms are bridged by methanolate bridges. It crystallizes triclinic in the space group with a = 822.8(2), b = 910.4(2), c = 929.2(2) pm, α = 77.04(3)°, β = 82.35(3)°, γ = 68.69(3)°, and Z = 1 for the dimer. The vibrational and mass spectra of 1 , 2 and 3 are given and discussed.