Spectrophotometric and Polarographic Studies on 9,10-Anthradione-2-Sodium Sulfonate

The effect of solvent structure on the rates of redox reactions in alcohol+water mixture was discussed by some authors. The rate of photoreduction of 9,10-anthraquinone-2-sulfonate was decreased by addition of H₂SO₄ but was unchanged by increase of ionic strengh with (NH₄)₂SO₄. The magnitude of the decrease in presence of acid was greater with ethanol or isopropanol than with N-ethylacetamide as substrate. The formation of semiquinone and carbonate radical anions was observed⁽⁴⁾ during the direct photoreaction. The electron transfer from the carbonate anion to sulfoanthraquinone in the first excited triplet state was the controlling step of this process. Therefore, anthraquinone β-sodium sulfonate is efficient sensitizers of the photooxidation of organic substrates in aqueous media.     

Highly efficient orthopalladated complexes of second and third benzyl amine for catalyzing the Suzuki cross‐coupling reaction

In this work, ortho‐palladated complexes [Pd(µ‐Cl)(C₆H₄CH₂ NRR′‐κ²‐C,N)]₂ and [Pd(C₆H₄CH₂NH₂‐2‐C,N)Cl(Y)] were tested in the Suzuki–Miyaura cross‐coupling reaction. Cyclopalladated Pd(II) complexes as thermally stable catalysts can activate aryl bromides and chlorides. These complexes were active and efficient catalysts for the Suzuki–Miyaura reaction of aryl bromides and even less reactive aryl chlorides. The cross‐coupled products of a variety of aryl bromides and aryl chloride with phenylboronic acid in methanol as solvent at 60 °C were produced in excellent yields. Copyright © 2010 John Wiley & Sons, Ltd.     

Mössbauer studies on Al−Co ferrites

Mössbauer spectroscopy studies have been performed on the spinel CoAl_xFe_2?xO₄ (2<-x<-1.7) in the temperature range 77–750 K using either a liquid nitrogen bath cryostat or a furnace. The samples are magnetic at 77 K giving spectra that have magnetic sextets coexisting with a central line which increases in population with the Al-content indicating relaxation effects. The data shows that Al possesses no preference to either tetrahedral or octahedral sites of the ferrite over the whole range of concentration. The Mössbauer hyperfine interaction parameters and magnetic transition temperatures were determined. As expected the hyperfine field and Curie temperature decrease when the Al-content increases.     

Conductivity and Structural Investigations in Lacunary Pb6Ca2Li2(PO4)6 Apatite

Prismatic crystals of Pb₆Li₂Ca₂(PO₄)₆ were obtained by solid-state reaction. They were characterized by IR spectroscopy and chemical analyses. The structure as determined by X-ray diffraction study on single crystal revealed that the compound is isostructural to the hexagonal phase Pb₈Na₂(PO₄)₆. Crystal data for Pb₆Li₂Ca₂(PO₄)₆: space group P63/m (No. 176), a=b=9.6790(15) Å, c=7.1130(7), Z=1, R=0.039. In the compound, lithium was found to preferentially occupy the site (I) and the structure is stabilized by interactions between electron lone pairs of lead (II) ions. Electrical conductivity measured in a wide range of temperature is governed by a hopping mechanism of Li ions in tunnels.     

Reduction of Cd(II) and Mn(II) at the Dropping Mercury Electrode in the Presence of 1,3,5-Trihydroxybenzene in Aqueous Sodium Perchlorate

Reduction of Cd²⁺ at the dropping mercury electrode in solutions of 1, 3, 5-trihydroxybenzene was carried out in nonbuffer solutions of 0.1 M NaClO₄. The polarogram consists of two waves, the first wave can be taken in quantitative determination of Cd²⁺ in solutions containing 3.5 mM 1, 3, 5-trihydroxybenzene in 0.1 M NaClO₄. Mn²⁺ produces single well-defined diffusion controlled irreversible wave whose half-wave potential shifts to a more negative value with increasing 1, 3, 5-trihydroxybenzene. Me(II) forms two weak complexes, MX₁ and MX₂ at 25°. The behaviour of this metal ions is summarized.     

Synthesis of New Fused and Spiro 1,5‐Benzodiazepines

[1,3‐Dihydro‐4‐phenyl(1,5)benzodiazepin‐2‐ylidene]malononitrile 1_a was treated with formaline and some different primary amines to give the corresponding pyrimido(1,5)benzodiazepines 2_a–d . Treatment of compound 1_a with halo reagents yielded the corresponding pyrrolobenzodiazepines 3_a,b . The reaction of compound 1_a with active methylenes, bidentates, S,S‐ and N,S‐acetals afforded the corresponding spiro(1,5)‐benzodiazepines 4_a‐c–8_a,b , respectively.     

Kinetics of aquation of trans-dichlorobis(N,N′-dimethylethylenediamine)cobalt(III) ion in water–methanol in water–propan-2-ol media

The complex trans-[Co(dmen)2Cl2]Cl (dmen=N,N-dimethylethylenediamine) has been prepared and characterized by elemental analysis, u.v.-vis. and i.r. spectra. The kinetics of the primary aquation of trans-[Co(dmen)2Cl2] in H2O, H2O–MeOH and H2O–i-PrOH have been examined over a wide range of solvent compositions and temperatures (40–55°C). Plots of rate constants (log k) versus the reciprocal of the dielectric constant of the medium (Ds–1) and Grunwald–Winstein values of the solvent (Y) were found to be non-linear. The variation of enthalpies (H) and entropies (S) of activation with solvent composition has been determined. Plots of H or S versus the mole fraction of each solvent exhibit extrema at x2=ca. 0.16 and 0.27 for MeOH and at x2=ca. 0.03 and 0.14 for i-PrOH. Furthermore, the cycle relating the free energy of activation in H2O to that in H2O–co-solvent shows that the stabilizing influence of the changes in the solvent structure is greater on the emergent five-coordinate cation in the transition state than that on the complex ion in the initial state, with the difference becoming greater as the mole fraction of the co-solvent increases.     

Synthesis of 6-benzyl- and 6-phenethyl-2,4-diamino-5,6,7,8-tetrahydropyrimido[4,5-d]pyrimidines

The preparation of ten aralkyl derivatives of 2,4-diamino-5,6,7,8-tetrahydropyrimido[4,5-d]pyrimidines ( 6 ) has been accomplished. The title compounds were prepared in a simple one step reaction from 2,4,6-triaminopyrimidine ( 4 ), formaldehyde ( 2 ), and either substituted benzylamines ( 1a-d ) or substituted phenethylamines ( 1e-j ). This modified Mannich reaction has been shown to be a general method for such derivatives. Elemental analysis, ¹H nmr and mass spectral data have confirmed the proposed structures. None of the compounds exhibited either antimalarial or antitrypanosomal activity.     

X-ray scattering and density-functional theory calculations to study the presence of hydrogen-bonded clusters in liquid N-methylacetamide

A structural investigation of liquid N-methylacetamide (NMA) is performed by x-ray scattering and density functional theory (DFT). Experimental data are analyzed to yield the total structure function SM(Q) and the pair correlation function g(r). The DFT calculations, using the standard triple zeta valence basis set augmented by a diffuse function for carbon, nitrogen and oxygen atoms, are performed on the one hand to study the structure and stability of the two possible conformers cis and trans. On the other hand, they are meant to examine some possible clusters which may describe the intermolecular arrangement in liquid NMA. Among two series of dimers and trimers associations, the spectra are particularly interpreted in terms of: Trans NMA dimers and trimers which resemble the short-range crystal structure, mixed cis and trans trimers and cis cyclic trimers. The H-bonding parameters and the intermolecular energy for each model are described.