Ru3(CO)12-catalyzed silylation of benzylic C-H bonds in arylpyridines and arylpyrazoles with hydrosilanes via C-H bond cleavage

Ruthenium-catalyzed silylation of sp3 C-H bonds at a benzylic position with hydrosilanes gave benzylsilanes. For this silylation reaction, Ru3(CO)12 complex showed high catalytic activity. This silylation proceeded at the methyl C-H bond selectively. For this silylation reaction, pyridyl and pyrazolyl groups, and the imino group in hydrazones, can function as a directing group. Several hydrosilanes involving triethyl-, dimethylphenyl-, tert-butyldimethyl-, and triphenylsilanes can be used as a silylating reagent. Coordination of an sp2 nitrogen atom to the ruthenium complex is important for achieving this silylation reaction.     

Analysis of free fatty acids by a micro-liquid chromatograph directly coupled with a mass spectrometer through a vacuum nebulizing interface

A liquid chromatograph directly coupled with a quadrupole mass spectrometer through a vacuum nebulizing interface was applied to the analysis of various free fatty acids. Chemical ionization mass spectra of the C₇? C₂₂ free fatty acids were first examined using either methanol or benzene as the reagents. Then the practical compositional analysis of the fatty acids were performed with various biological samples such as bean oil, rape oil, palm oil and milk fat where most of the fatty acids are included as their triglycerides.     

Kinetics of the interconversion of parahydrogen and orthohydrogen catalyzed by paramagnetic complex ions

The rate constants of para-/orthohydrogen (p-/o-H2) nuclear spin isomerization have been measured by means of 1H NMR in deuterated solvents at 298.2 K. The indicated reaction is catalyzed by paramagnetic complex ions giving rate constants that are proportional to the concentrations of the catalysts. The second-order rate constants are directly proportional to the squares of the magnetic moments for the solvated metal complexes for two classifications: M(solv)m2+, M = 3d transition metals; Ln(solv)n3+, where in 1:9 D2O-CD3CN the aqua complexes are the predominant species, Ln = lanthanides. The other 3d transition metal complexes with different ligands show rate constants that also depend on the sizes of ligands. Whereas the correlation between the second-order rate constants and magnetic moments is consistent with Wigner's theory, the size of catalyst shows a more modest effect on the rate constants than expected. The effective collision radii of the complexes, calculated from the rate constants, proved to be approximately constant for each series of solvated metal complexes.     

Synthesis of substituted polymethylenes by radical polymerization of alkyl N,N-dialkylfumaramates and maleamates: Relative reactivity of the isomers

Bulk polymerization of alkyl N,N-dialkylfumaramates (FAE) and maleamates (MAE) was performed in the presence of a radical initiator. It has been found that FAE is more reactive than MAE when the reactivity of the two geometrical isomers was compared for their homo- and copolymerizations. From investigation on the effect of ester and N-substituents of these monomers, it has been found that the isopropyl ester shows a higher reactivity than the methyl ester and that N-ethyl and n-butyl substitution gives polymers with high molecular weight of more than several thousands. The resulting substituted polymethylenes from FAE and MAE were characterized and compared with each other. The isomerization of MAE to FAE with morpholine as an isomerization catalyst and monomer-isomerization radical polymerization were also investigated.     

Radiation-induced emission from golden hamster embryo cells

Emission from high-energy-electron-irradiated golden hamster embryo (GHE) cells has been studied over the temperature range 12–300 K both by a one-shot-single-photon-counting method and by photocurrent measurements with an oscilloscope. Emission from the irradiated phosphate buffered saline (PBS) also has been studied. The emission spectra from PBS at 12 and 77 K show a maximum around 330 and 380 nm, respectively, which are the same spectra as those from irradiated pure H₂O. The emission from irradiated GHE consists of the new band at 480 nm in addition to the emission from H₂O. The 480 nm emission is observed at the temperature range of 12–300 K, though the emission at 300 K is much lower than that at low temperature. The 480 nm emission is ascribed to the transition from excited organic substances in GHE cells. The intensity of 480 nm emission at 300 K increases linearly with increasing irradiation-dose in the range of 11–600 Gy.     

Polymerization of tetraallyl ammonium chloride

The radical polymerization of tetraallyl ammonium chloride (TAAC) was carried out in water using azo-initiator as compared to that of diallyl dimethyl ammonium chloride (DADMAC); the rate of polymerization was quite low for TAAC, around one-third of DADMAC. Kinetic discussion revealed the importance of degradative chain transfer in the polymerization of TAAC. The cyclopolymerizability of TAAC was estimated kinetically as the ability of 5-membered monocyclic radical to form a bicyclic ring, giving the cyclization constant of 21 mol/L at [M] = 2 mol/L. Gelation occurred at around 20% conversion.     

Ruthenium-catalyzed formation of aryl(diphenyl)phosphine oxides by reactions of propargylic alcohols with diphenylphosphine oxide

1,1-Diaryl-1-penten-4-yn-3-ols react with diphenylphosphine oxide in the presence of a thiolate-bridged diruthenium complex as a catalyst and give high yields of aryl(diphenyl)phosphine oxide products via an initial substitution followed by a cyclization at the produced allene intermediate. [reaction: see text]     

Determination of traces of molybdenum in sea water by combined anion-exchange — graphite furnace atomic absorption spectrometry

Summary Traces of molybdenum in sea water have been preconcentrated by anion-exchange from acidified samples in the presence of sodium azide. Molybdenum adsorbs strongly on a column of Bio-Rad AG 1 (Cl^–) and can be stripped easily by elution with 2 mol/l NH₄Cl — 2 mol/l NH₄OH solution. Molybdenum in the effluent is determined by graphite furnace atomic absorption spectrometry. The combined method allows to determine traces of molybdenum in sea water as well as non-saline water on a 100 ml sample basis. The method gives a relative standard deviation of better than 8% at a molybdenum level of 10 g 1^–1 of sea water.

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Bestimmung von Molybdänspuren in Meereswasser mit Hilfe einer Kombination von Anionenaustausch und elektrothermischer Atomabsorptionsspektrometrie

     

Studies of the polymerization of diallyl compounds. XXVII. Copolymerization of diallyl tartrate with several vinyl monomers

The radical copolymerization of diallyl tartrate (DATa) (M₁) with diallyl succinate (DASu), diallyl phthalate (DAP), allyl benzoate (ABz), vinyl acetate (VAc), or styrene (St) was investigated in order to disclose in more detail the characteristic hydroxyl group's effect observed in the homopolymerization of DATa. In the copolymerization with DASu or DAP as a typical diallyldicarboxylate, the dependence of the rate of copolymerization on monomer composition was different for different copolymerization systems and unusual values larger than unity for the product of monomer reactivity ratios, r₁r₂, were obtained. In the copolymerization with ABz or VAc (M₂), the r₁ and r₂ values were estimated to be 1.50 and 0.64 for the DATa/ABz system and 0.76 and 2.34 for the DATa/VAc system, respectively; the product r₁r₂ for the latter copolymerization system was found again to be larger than unity. In the copolymerization with St, the largest effect due to DATa monomer of high polarity was observed. Solvent effects were tentatively examined to improve the copolymerizability of DATa. These results are discussed in terms of hydrogen-bonding ability of DATa.