Phosphorylation of pyridoxal azomethines. Synthesis of phosphorus containing azomethines and furopyridines

New O-phosphorylated pyridoxal derivatives have been synthesized through the reaction of azomethines with Р^V acid chlorides. 2-Chloro-2-thioxo-5,5-dimethyl-1,3,2-dioxaphosphinanes and diethylchlorothiophosphate have been employed as phosphorylating agents. Regardless of the nature of the phosphorylating agent, the reaction is regioselective at phenolic hydroxyl group. The structure of final products is determined by the nature of the substituent at the nitrogen atom. If R is alkyl or cycloalkyl group, the products of the reaction represent phosphorylated pyridoxal imines, whereas phosphorylated furopyridines are formed in the case R is aryl substituent.     

α-Diphenylphosphino-N-(pyrazin-2-yl)glycine as a ligand in Ni-catalyzed ethylene oligomerization

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Bromination regiochemistry of 4-Phenyl-2,7-dichloro-2H-chryseno-[6,5-e][1,2]phosphinine 2-oxide

Regioselective bromination of 4-phenyl-2,7-dichloro-2H-chryseno[6,5-e][1,2]phosphinine 2-oxide proceeded in the position 3 with the formation of 3-bromo-4-phenyl-2,7-dichloro-2H-chryseno[6,5-e][1,2] phosphinine 2-oxide; the structure of its 2-tert-butylamino derivative was established by XRD analysis and correlation spectroscopy.     

Improvement of the efficiency of electrochemical refining of cobalt

To improve the purity of cobalt produced by electrochemical refining, the optimal electrolyte composition and electrolysis mode were determined and a method for diminishing the electrochemical activity of impurity metals in anodic dissolution of the raw metal and a system for deep purification of the electrolyte solution to remove impurities were developed. Cathode deposits with a conditional cobalt content exceeding 99.999 wt %, found in an analysis for the 11 main impurities, were obtained by using the above results in refining of K1A cobalt (≥99.30 wt % Co) in an electrolyzer of distinctive design.     

3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis,Crystal Structures,Gas Adsorption,and Magnetic Properties

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc²⁻) [Co₃(btdc)₃(bpy)₂]·4DMF, 1; [Co₃(btdc)₃(pz)(dmf)₂]·4DMF·1.5H₂O, 2; [Co₃(btdc)₃(dmf)₄]∙2DMF∙2H₂O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co₃(RCOO)₆}, connected either by btdc^2– ligands (1, 3) or by both btdc^2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N₂, O₂, CO, CO₂, CH₄ adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m²⋅g⁻¹ and promising gas separation performance with selectivity factors up to 35.7 for CO₂/N₂, 45.4 for CO₂/O₂, 20.8 for CO₂/CO, and 4.8 for CO₂/CH₄. The molar magnetic susceptibilities χ_p(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μ_eff (300 K) ≈ 4.93 μ_B. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2.     

New Blood Coagulation Factor XIIa Inhibitors: Molecular Modeling,Synthesis, and Experimental Confirmation

In the modern world, complications caused by disorders in the blood coagulation system are found in almost all areas of medicine. Thus, the development of new, more advanced drugs that can prevent pathological conditions without disrupting normal hemostasis is an urgent task. The blood coagulation factor XIIa is one of the most promising therapeutic targets for the development of anticoagulants based on its inhibitors. The initial stage of drug development is directly related to computational methods of searching for a lead compound. In this study, docking followed by quantum chemical calculations was used to search for noncovalent low-molecular-weight factor XIIa inhibitors in a focused library of druglike compounds. As a result of the study, four low-molecular-weight compounds were experimentally confirmed as factor XIIa inhibitors. Selectivity testing revealed that two of the identified factor XIIa inhibitors were selective over the coagulation factors Xa and XIa.     

Aromaticity and tautomerism—VII: Empirical resonance energy and conjugation energy of pyrazole and isoxazole from heats of dehydration data

The dehydration of various 4,5-dihydro-4- and -5-hydroxy derivatives of pyrazole and isoxazole has been investigated. Heats of dehydration of 4,5-duiydro-4-hydroxy-1,3,5-tripbenylpyrazole and 4,5-dihydro-5-hydroxy-isoxazole are evaluated and used to assess the empirical resonance energy and conjugation energy of pyrazole and isoxazole. The former possesses resonance stabilisation comparable to pyrrole but that of the latter is low.     

Determination of the content and localization of magnesium in bioapatite of bone

Using x-ray diffraction, electrothermal atomization atomic absorption spectroscopy, and scanning electron microscopy with an x-ray microanalysis, we have studied the phase decomposition of biogenic and synthetic Mg-containing apatite at 900°C with formation of β-tricalcium-magnesium phosphate (β-TCMP). Employing simplified model representations, we obtained a relation that couples the initial Mg concentration with the degree of transformation of apatite into β-TCMP. It is shown that for the β-TCMP contents measured in bioapatite samples and on replacement of calcium by magnesium to about 8% in this phase the calculated range of Mg concentrations coincides with that available in literature sources (0.2–0.6 wt. %). A comparative investigation of the products of decomposition of biogenic and synthetic apatite by the methods of analysis of the composition and structure has established that the formation of β-TCMP is limited by both the insufficient concentration of magnesium and the small sizes of the crystals. The results of the investigations carried out together with the experimental data known from the literature are indicative of the nonuniform distribution of magnesium in the bulk of crystals of biogenic and synthetic apatite, with its predominant localization at the surface sites of the lattice. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 821–826, November–December, 2005.