Reaction of alkynyltrimethylsilanes with a hypervalent organoiodine compound: A new general synthesis of alkynyliodonium salts

New general methods for the synthesis of alkynyl(phenyl)iodonium tetrafluoroborate 2 from alkynyltrimethylsilanes 1 utilizing the combination of iodosylbenzene and triethyloxonium tetrafluoroborate or boron trifluoride etherate were developed. The medium effect observed in the reaction was also discussed.     

A facile synthesis of novel chiral phosphonoacetates bearing a stereogenic phosphorus atom

Novel chiral phosphonoacetates bearing a stereogenic phosphorus atom were successfully synthesized by enzyme-catalyzed kinetic resolution of racemic phosphonoacetates.     

Solute dependence of mobility of solvent molecules in solvophobic solute solutions: Dielectric relaxation of nonpolar solute/alcohol mixtures

The dielectric relaxation spectra of alcohol/nonpolar solute mixtures are measured at several temperatures (-15 degrees C < or = T < or = 25 degrees C) and for several molar fractions of solute (0 < or = X(s) < or = 0.114) in the frequency range of 200 MHz < or = nu < or = 20 GHz. The double-Debye-type function is used for fitting of the spectra of mixtures, and the mean dielectric relaxation times (tau(mean)) of alcohol molecules are determined. In the systems having strong interaction between alcohol and nonpolar solutes, tau(mean) becomes shorter with an increase in the concentration of the solutes. On the other hand, tau(mean) becomes longer in the system having weak interaction between alcohol and nonpolar solutes. These results contradict with our intuitive predictions, do not correspond to mixing enthalpy, and are not explained by the hydrodynamic theory. They are attributed to the mechanism of the coupling between long-range electrostatic interactions and concentration fluctuation caused by the addition of solutes, which is suggested by Yamaguchi et al. based on the mode-coupling theory (Yamaguchi, T.; Matsuoka, T.; Koda, S. J. Chem. Phys. 2004, 120, 7590).     

Effect of pressure on the vibrational structure of insensitive energetic material 5-nitro-2,4-dihydro-1,2,4-triazole-3-one

The Raman spectra of alpha form 5-nitro-2,4-dihydro-1,2,4-triazole-3-one (alpha-NTO, space group P) were measured in a high-pressure vessel diamond anvil cell (DAC). The pressure was increased to 27.6 GPa. In general, Raman bands show a blue shift because of the nature of the molecule packing as a high-pressure effect, but some particular bands exhibited a red shift, disappearance, split, or slight shifting in our experiments. Those red-shifting bands concerning hydrogen bonds, i.e., carbonyl and amino groups, are likely to work as a stabilizer against stimuli to the molecule or crystal. This stabilizing nature might characterize the insensitivity of NTO. Molecular dynamic (MD) calculations were performed to reveal the high-pressure effect of the alpha-NTO crystal. The coordinates of individual atoms in the crystal structure were obtained using X-ray diffraction analysis. The pressure dependence of the power spectra of the correlation functions of the C=O bond length in NTO was calculated. A unique high-pressure effect of the alpha-NTO crystal was found on the power spectra. The peak frequency in the power spectrum of the C=O stretching vibration exhibited a red shift with an increase in pressure to 10.0 GPa, while the peak intensity considerably decreased under the same pressure process, because this bond length increased with an increase in pressure to 10.0 GPa. At a pressure of >20.0 GPa, a blue shift appeared. These results of the MD calculations are in good agreement with our experimental data.     

Study of γ d → π + π − d Reaction in an Energy Region of 0.67 ≤ E γ ≤ 1.08 GeV

Double charged pion photoproductions from the deuteron have been studied at Research Center for Electron Photon Science (ELPH), Tohoku University. Tagged photon beams in an energy range of 0.67 ≤ E _γ ≤ 1.08 GeV were impinged on the liquid deuteron target. Produced charged particles were observed with the Neutral Kaon Spectrometer2 (NKS2). The γ d → π ⁺ π ^? d process was clearly separated among the three charged tracks. We obtained the photon energy dependence of the normalized yields of this process.     

Study of Strangeness Photoproduction on the Neutron in the Threshold Region

Photoproduction of the neutral kaon on the deuteron has been investigated at the Research Center for Electron Photon Science, Tohoku University. We constructed the Neutral Kaon Spectrometer-2 for the detection of charged particles from the decay of the neutral kaon and the hyperon. We obtained a momentum distribution of K ⁰ with the inclusive measurement. It was consistent with the previous measurement. The total cross section of γ + d → K ⁰ + Λ + p was estimated from the measured integral cross section of γ + d → Λ + X. The total cross section with respect to the photon energy was compared with the theoretical calculations. It favored the Saclay-Lyon A model calculation with the ratio of the neutral to charged coupling constants of the axial-vector meson, K ₁, as ~ ?1.5. The energy dependence and the magnitude of the total cross section were similar to the total cross section of γ + p → K ⁺ Λ.