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.     

Determination of triazine pesticides and related compounds in environmental water by liquid chromatography-mass spectrometry.

A method for the determination of 5 triazine herbicides and 12 degradation products in environmental water samples using liquid chromatography-electrospray ionization mass spectrometry (LC/ESI/MS) has been developed. The pesticides in water were extracted with two types of solid phase: a styrene-divinylbenzene copolymer and a graphitized carbon black. Desorption solvents for the extracted compounds were acetone for the styrene-divinylbenzene copolymer and methanol for the graphitized carbon black. Overall recoveries from ground water and river water ranged from 73% to 111%. The limits of detection (LODs) were 0.2 to 28 ng l(-1). This method was applied to several ground water samples.     

Phase rotation scheme of laser-produced ions for reduction of the energy spread

In order to widely spread out particle beams utilized in cancer therapy, laser-produced ions are developed as the injection beam for an ion synchrotron dedicated for cancer therapy. Such a laser ion source is expected to contribute largely to the realization of compactness of the size and low cost of the cancer therapy accelerator. The energy spectrum of the laser-produced ions, however, has no peak, but their intensities decrease exponentially according to the increase of the energy. For the purpose of modifying such a situation, we have proposed a scheme to rotate the beam in the longitudinal phase space with the use of the RF electric field, which is phase-adjusted with the pulse laser. We aim for a reduction of the energy spread of ± 5% selected by an energy analyzer and slits to ±1% by such phase rotation. For this purpose, a quarter wavelength resonator with two gaps with the same resonant frequency as the source laser has already been fabricated, together with its RF power source. The above phase rotation system and its recent experimental realization are presented.     

Discrimination of poly(vinyl chloride) samples with different plasticizers and prediction of plasticizer contents in poly(vinyl chloride) using near-infrared spectroscopy and neural-network analysis.

In the recycling of poly(vinyl chloride) (PVC), it is required to discriminate every plasticizer for quality control. For this purpose, the near-infrared spectra were measured for 41 kinds of PVC samples with different plasticizers (DINP, DOP, DOA, TOTM and Polyester) and different plasticizer contents (0-49%). A neural-network analysis was applied to the near-infrared spectra pretreated by second-derivative processing. They were discriminated from one another. The neural-network analysis also allowed us to propose a calibration model which predicts the contents of plasticizers in PVC. The correlation coefficient (R) and the root-mean-square error of prediction (RMSEP) for the DINP calibration model were found to be 0.999 and 0.41 wt%, respectively. In comparison, a partial least-squares regression analysis was carried out. The R and RMSEP of the DINP calibration model were calculated to be 0.993 and 1.27 wt%, respectively. It is found that a near-infrared spectra measurement combined with a neural-network analysis is useful for plastic recycling.     

Quasi-monocyclic near-infrared pulses with a stabilized carrier-envelope phase characterized by noncollinear cross-correlation frequency-resolved optical gating.

Precise characterization of noncollinear optical parametric amplifier idler pulses that have bandwidths of more than an octave with a center wavelength at 990 nm was demonstrated. The method employed was cross-correlation frequency-resolved optical gating with broadband sum-frequency mixing to take advantage of the idler's angular dispersion. Compression to near the transform limit was achieved to produce quasi-monocyclic near-infrared pulses by use of a deformable membrane mirror.     

Improved method for measurement of rhodanese activity using methanethiosulfonate as sulfur donor substrate and its application to human serum.

We have developed a sensitive method for the measurement of rhodanese activity in human serum which is based on the colorimetric method for the determination of thiocyanate produced from methanethiosulfonate and cyanide as substrates. Thiocyanate gives a red complex with ferric ion in an acidic condition. The present method is about 70-fold more sensitive than the conventional method using cyanide and thiosulfate as substrates and correlates well (r = 0.997) with the conventional method in bovine liver rhodanese. Within-run precision of the method is 0.91% for 420 units/l serum and the calibration curve is linear up to 1850 units/l. The normal value for human serum, determined by the present method on 31 healthy persons, was 20.9 +/- 20.0 units/l (mean +/- 2S.D.). Rhodanese activity was clearly elevated in some serum samples which were observed at abnormal values in some biochemical diagnostic tests and showed significant positive correlations with guanase activity (r = 0.728, p less than 0.01) and glutamic-oxalacetic transaminase activity (r = 0.625, p less than 0.01).     

Magnetic interactions in a series of paramagnetic Ln(III) complexes with a chelated imino nitroxide radical

The magnetic interactions in a new series of isostructural imino nitroxide radical lanthanide(III) complexes, [Ln(hfac)₃(IM2py)] (Ln = Gd–Yb: IM2py = 2-(2′-pyridyl)-4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-1-oxy; hfac = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione), are examined by considering the intrinsic paramagnetic contribution of the Ln(III) ion from the corresponding [Ln(hfac)₃(pybzim)] with a diamagnetic pybzim(2-(2-pyridyl)benzimidazole) ligand; the Ln(III)–IM2py interaction being antiferromagnetic for the 4f⁷ to 4f¹³ Ln(III) complexes and negligibly small for the other complexes. This series is the first example reverse to the previous cases for the series of Ln–Cu or Ln–aminoxyl(NIT) radical (4,5-dihydro-4,4,5,5-tetramethyl-1H-imidazoline-3-oxide-1-oxy) complexes, other than only a few examples of semiquinone Ln complexes. This reverse nature of the magnetic interaction, as compared with the NIT complexes, validates the empirical approach by O. Kahn et al. [Inorg. Chem. 38 (1999) 3692; J. Am. Chem. Soc. 122 (2000) 3413] in the spin-coupled systems for a series of Ln(III) complexes.     

Vibrational frequencies and infrared absorption intensities of 1,2-dibromoethane

Infrared and Raman spectra of 1,2-dibromoethane CH₂BrCH₂Br and CD₂BrCD₂Br were observed in the liquid state, and the fundamental frequencies were determined by comparison with those of related molecules. Infrared absorption intensities of fundament bands were measured in the liquid state, and the intensity data were interpreted on the basis of the valence-optical theory. From the converged value of a population ratio, the energy difference between the trans and gauche isomers was determined, which was in good agreement with the value obtained from the temperature effect of the IR spectrum.     

Basic properties of alkaline earth metal oxides and their catalytic activity in the decomposition of diacetone alcohol

The effect of CO₂ adsorption on the catalytic activity of alkaline earth metal oxides in the title reaction reveals that the number of active (basic) sites follows the order MgO>CaO>SrO>BaO, and the order of base strength is MgO

CO₂ , () : MgO>CaO>SrO>BaO, : MgO