Caesium carbonate supported on hydroxyapatite‐encapsulated Ni0.5Zn0.5Fe2O4 nanocrystallites as a novel magnetically basic catalyst for the one‐pot synthesis of pyrazolo[1,2‐b]phthalazine‐5,10‐diones

A novel nanomagnetic basic catalyst of caesium carbonate supported on hydroxyapatite‐coated Ni_0.5Zn_0.5Fe₂O₄ magnetic nanoparticles (Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃) was prepared. This new catalyst was fully characterized using Fourier transform infrared spectroscopy, transmission and scanning electron microscopy, X‐ray diffraction and vibrating sample magnetometry techniques, and then the catalytic activity of this catalyst was investigated in the synthesis of 1H‐pyrazolo[1,2‐b]phthalazine‐5,10‐dione derivatives. Also, Ni_0.5Zn_0.5Fe₂O₄@HAP‐Cs₂CO₃ could be reused at least five times without significant loss of activity and could be recovered easily by applying an external magnet. Thus, the developed nanomagnetic catalyst is potentially useful for the green and economic production of organic compounds. Copyright © 2015 John Wiley & Sons, Ltd.     

Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Magnetic field effect on indole exciplexes: an anomalous dielectric dependence

Individual exciplex formation between various aromatic hydrocarbons, anthracene, pyrene, all-s-trans-1,4-diphenylbuta-1,3-diene and a heteroaromatic amine, 1,2-dimethylindole, was investigated by steady-state fluorescence and magnetic field effect (MFE). A comparative study was carried out with two other exciplex systems 9-cyanophenanthrene-1,2-dimethylindole and 9-cyanophenanthrene-N-methylindole. The extent of charge transfer and dielectric dependence of MFE reveals the potential role of specific interactions related to exciplex geometry.     

Comments concerning the HPLC separation of acrolein from other C3 carbonyl compounds as 2,4-dinitrophenylhydrazones: A proposal for improvement

The separation of the toxicologically important aldehyde acrolein from other carbonyl compounds by high performance liquid chromatography after derivatization to 2,4-dinitrophenylhydrazones is critically discussed on the basis of a selection of published methods. A method is proposed whereby the compounds acrolein, acetone, and propanal may be reproducibly separated to baseline by a reversed phase HPLC procedure employing a ternary mixture of methanol, water, and acetonitrile as mobile phase.     

Catalysis by Ir(III), Rh(III) and Pd(II) metal ions in the oxidation of organic compounds with H2O2

Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H₂O₂. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd.     

The chemisorption of pentacene on Si(0 0 1)-2 × 1

Adsorption structures of the pentacene (C₂₂H₁₄) molecule on the clean Si(0 0 1)-2 × 1 surface were investigated by scanning tunneling microscopy (STM) in conjunction with density functional theory calculations and STM image simulations. The pentacene molecules were found to adsorb on four major sites and four minor sites. The adsorption structures of the pentacene molecules at the four major sites were determined by comparison between the experimental and the simulated STM images. Three out of the four theoretically identified adsorption structures are different from the previously proposed adsorption structures. They involve six to eight Si-C covalent chemical bonds. The adsorption energies of the major four structures are calculated to be in the range 67-128 kcal/mol. It was also found that the pentacene molecule hardly hopped on the surface when applying pulse bias voltages on the molecule, but was mostly decomposed.     

Synthesis of vinyl-substituted oxiranes and their transformation to dihydrofurans

The reaction of dimethylsulfonium methylide with the carbonyl function of 2-arylidene-cyclohexanones obtained from 2-methylcyclohexanone affords the corresponding spirooxiranes. The application of this reaction to 2,2-dimethyl-6-(5-methylfurfurylidene)cyclohexanone and 2,2-dimethyl-6-(5-chlorofurfurylidene)cyclohexanone leads to substituted 4,4-dimethyl-1-furyl-1,-3,4,5,6,7-hexahydroisobenzofurans.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1439–1443, August, 1994.     

The design of molecules containing planar tetracoordinate carbon

A novel preference for planar tetracoordination was observed over the conventional tetrahedral arrangement in a new series of C₅H₂, C₅H₄, C₅H₄^1+/2+ and related compounds. The stability of these molecules is assessed with the ring-opening barriers, HOMO-LUMO gap, singlet-triplet energy differences and nucleus independent chemical shift values.     

Opening of epoxides with aromatic amines promoted by indium tribromide: a mild and efficient method for the synthesis of β-amino alcohols

A mild and efficient synthesis of β-amino alcohols by aminolysis of epoxides promoted by indium tribromide is described. The methodology is regio- and chemoselective and works well with independence of the epoxide or the aromatic amine used. In addition, the reaction can be carried out in a wide variety of undried solvents under air.     

Palladium-catalyzed C-N bond formation: synthesis of 1-aryl-1H-pyrazoles from β-bromovinyl aldehydes and arylhydrazines

Cyclic and acyclic β-bromovinyl aldehydes are cyclized with an array of arylhydrazines in toluene at 125 °C in the presence of a palladium catalyst and a phosphorus chelating ligand together with NaO^tBu to give 1-aryl-1H-pyrazoles in moderate to good yields.