Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra

The thermal decomposition of Co(NO₃)₂·6H₂O (1) as well as that one of NO[Co(NO₃)₃] (Co(NO₃)₂·N₂O₄) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N₂ atmosphere, cobalt oxides are finally formed whereas in H₂/N₂ (10% H₂) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO₃, NO₂, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.     

Use of 1-alkyl-3-methylimidazolium hexafluorophosphate room temperature ionic liquids as chelate extraction solvent with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione

Possible use of room temperature ionic liquids (RTILs) as chelate extraction solvent was evaluated by using 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), 1-hexyl-3-methylimidazolium hexafluorophosphate ([hmim][PF₆]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([omim][PF₆]). These RTILs showed high extraction performance for divalent metal cations with 4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedione (Htta). The extracted metals were back-extracted into 1 mol dm⁻³ nitric acid quantitatively. Furthermore, the extracted species were estimated as neutral hydrated complexes M(tta)₂(H₂O)_n (n= 1 or 2) for M = Ni, Cu and Pb and anionic complexes M(tta)₃⁻ for M = Mn, Co, Zn and Cd.     

β-Ketoaldehydes in the synthesis of 6-alkyl-3-cyano-2(1H)-pyridinethiones

An efficient synthesis of 6-alkyl-3-cyano-2(1H)-pyridinethiones by the reactions of the sodium salts of -ketoaldehydes with cyanothioacetamide was developed. Pyridinethiones undergo selectiveS-alkylation with haloacetonitriles and haloacetophenones followed by cyclization to the corresponding thieno[2,3-b]pyridines.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 727–731, April, 1995.This study was financially supported by the Russian Foundation for Basic Research (Project No. 94-03-08-823).     

Ab initio studies of the protonation of CO,N2 and NO+: Calculation of the minimum energy reaction paths

Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO⁺, COH⁺, and HCOH²⁺ from CO by protonation. The protonation of N₂ to give NNH⁺ and HNNH²⁺ and of NO⁺ to form HNO²⁺ and NOH²⁺ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed.     

New insight into the oxidative chemistry of noradrenaline: competitive o-quinone cyclisation and chain fission routes leading to an unusual 4-[bis-(1H-5,6-dihydroxyindol-2-yl)methyl]-1,2-dihydroxybenzene derivative

Oxidation of 5×10⁻³ M noradrenaline in aqueous phosphate buffer, pH 7.4, with K₃Fe(CN)₆, NaIO₄ or Fe²⁺/EDTA/H₂O₂ followed by extraction with ethyl acetate and acetylation with Ac₂O/Pyr led to a main reaction product which was isolated and identified as 4-[bis-(1H-5,6-diacetoxyindol-2-yl)methyl]-1,2-diacetoxybenzene, an unprecedented [bis-(indol-2-yl)methyl]-benzene derivative unsubstituted on the 3-position of the indole rings. This product was also obtained in 40% yield by reaction of 5,6-dihydroxyindole with 3,4-dihydroxybenzaldehyde. Other components of the oxidation mixture were 1-acetyl-3,5,6-triacetoxyindole, derived from noradrenolutin, and 5,6-diacetoxyindole, originating from cyclisation/dehydration of the o-quinone of noradrenaline, along with some 3,4-diacetoxybenzaldehyde. Inspection of the aqueous phase revealed the presence of 3,4-dihydroxymandelic acid and 3,4-dihydroxybenzaldehyde, derived from oxidative breakdown of the 2-amino-1-hydroxyethyl chain via a p-quinomethane intermediate. These results disclose new aspects of the oxidative chemistry of noradrenaline beyond the aminochrome stage and provide a route to novel [bis-(indol-2-yl)methyl]-benzene derivatives of potential pharmacological interest.     

Synthesis of bridgedhead azolo[3,2-a]pyrimidines and imidazo[2,1-b]thiazines through ring transformation of 2H-pyran-2-ones

Suitably functionalized 3-carbomethoxy/cyano-2H-pyran-2-ones are excellent synthons for the synthesis of arenes and heteroarenes of therapeutic importance. The compounds 6-aryl-3-cyano-4-methylsulfanyl-2H-pyran-2-ones have been transformed into bridgedhead azolopyrimidines and imidazothiazines through thermal and base-induced ring transformation reactions with aminoazoles and imidazolidin-2-thiones, respectively.     

Anomalies of the partition coefficient and properties of crystals in the region of low concentrations of an isomorphous admixture. 1. Unusual decomposition of solid solutions of the NaCl—CdCl2 system

Solid solutions NaCl—CdCl₂ were studied in an interval of CdCl₂ concentrations of 0.05—3 mol.% by Raman spectroscopy. The molecular form Na₂CdCl₄ decomposes: Na₂CdCl₄ 2Na⁺ + Cd²⁺ + 2Cl₂ ^– + 2e^–; 2Na + 2e^– 2Na⁰. Free sodium atoms form color centers of crystal (F centers) in the region of jumpwise changing the partition coefficient of CdCl₂ in NaCl (K jump).     

Synthesis of 2-Acetoxy- and 2-Hydroxy-2,3-dihydronaphtho[1,8-bc]pyran

Summary 2-Acetoxy- and 2-Hydroxy-2,3-dihydronaphtho[1,8-bc]pyranes were synthesized by decomposition of 1-hydroperoxy-1,2-dihydroacenaphthylene in acetic acid in the presence of perchloric acid.

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Synthese von 2-Acetoxy- und 2-Hydroxy-2,3-dihydronaphtho[1,8-bc]pyran

Zusammenfassung 2-Acetoxy- und 2-Hydroxy-2,3-dihydronaphtho[1,8-bc]pyrane konnten durch Zersetzung von 1-Hydroperoxy-1,2-dihydroacenaphthylen in Essigsäure in Anwesenheit von Perchlorsäure synthetisiert werden.

     

The reactions of 2-benzoylpyridine with [RuHCl(CO)(PPh3)3] and [(C6H6)RuCl2]2

The reactions of [RuHCl(CO)(PPh₃)₃] and [(C₆H₆)RuCl₂]₂ with 2-benzoylpyridine have been examined, and two novel ruthenium(II) complexes – [RuCl(CO)(PPh₃)₂(C₅H₄NCOO)] and [RuCl₂(C₁₂H₉NO)₂] – have been obtained. The compounds have been studied by IR and UV–Vis spectroscopy, and X-ray crystallography. The molecular orbital diagrams of the complexes have been calculated with the density functional theory (DFT) method. The spin-allowed singlet–singlet electronic transitions of the compounds have been calculated with the time-dependent DFT method, and the UV–Vis spectra of the compounds have been discussed on this basis.