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.     

Catalytic Hydrosilylation of Furan, Thiophene, and Pyridine Aldimines

The addition of hydrosilanes (HSiEt₃, HSiMe₂Ph, H₂SiPh₂) to the CH=N bond of heterocyclic azomethines has been studied in the presence of monovalent complexes of rhodium and palladium. The effect on the reaction of the CF₃ group of the aldimines, which were obtained from O-, S-, and N-heteroaromatic aldehydes and 2-trifluoromethylaniline, has been clarified, as were other regularities of the processes being studied. A series of corresponding furans, thiophenes, and pyridine amines has been synthesized.     

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.     

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.     

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.     

Recent studies on phosphorus-bridging carbonyl derivatives: organophosphorus analogs of aldehydes and ketones

Reactions of disodium tetracarbonylferrate, Na₂Fe(CO)₄, with sterically hindered dialkylaminodichlorophosphines, R₂NPCl₂ (R₂N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R₂NP)₂COFe₂(CO)₆ as the major products. The phosphorus-bridging carbonyl group in (i-Pr₂NP)₂COFe₂(CO)₆ has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993.     

杂氮硅三环成环反应的研究

本文报导了与硅原子直接相连的有机基团(R)对杂氮硅三环成环速率的影响。利用气相色谱检测成环反应的产物之一——乙醇的生成速率和数量,并同与硅相连的R基团对成环反应速率的影响作比较。实验结果表明五种杂氮硅三环成环速度顺序为Cl_2CH—>ClCH_2—>ClCH_2CH_2CH_2—>CH_2=CH—>CH_3—,这与理论推断相符。