Cyanide-Free One-Pot Synthesis of Methacrylic Esters from Acetone

Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF₃CH₂, and n-C₆F₁₃CH₂CH₂ esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C₆F₁₃CH₂CH₂ esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d₆ and MeOH-d₄, with DBU in acetonitrile afforded deuterated MMA (MMA-d₈) in 70 % yield.     

Charge density study under high pressure

The experimental and analytical method of the high-pressure powder experiment at BL10XU, SPring-8, is described. There is no doubt that BL10XU must be one of the most appropriate beam lines for high pressure X-ray diffraction experiment taking advantage of third generation synchrotron source. As an example of the advanced charge density study under high pressure, the structural change of Cs₂Au₂Br₆ by applying pressure is studied by Rietveld/MEM analysis. It reveals that the structural change of Cs₂Au₂Br₆ by applying pressure occurs basically at electron level, such as valence state change and chemical bonding, which may be called the electronic phase transition.     

Magnetism in electron-doped copper oxides

We report muon spin relaxation/rotation measurements on sintered powder samples of Nd_2−x Ce _x CuO_4−y and a large single crystal of Nd₂CuO_4−y . We find an electronic phase diagram which is quite similar to that of hole-doped superconductors such as La_2−x Sr _x CuO_4−y , although the doping of electrons into the system is less efficient in destroying the static moments on the copper spins. Static magnetic order in Nd₂CuO_4−y appears below about 250 K, and two spin reorientations are seen atT=75 K andT=35 K. Measurements of the magnetic field penetration depth have been unsuccessful due to the rare-earth paramagnetism of these materials.     

μSR studies of heavy fermion systems

We have performed both zero field and high transverse field measurements at dilution refrigerator temperatures on a number of heavy electron systems, examining the superconducting and magnetic properties of these interesting materials. Among the materials studied to date are UBe₁₃, URu₂Si₂ and U₆Fe. The magnetic field penetration depth in the superconducting state of UBe₁₃ is greater than 10000 Å, as no increase in the transverse field relaxation rate is observed belowT _c . A sharp increase in the precession frequency is seen, starting atT _c . This frequency shift shows little temperature dependence at low temperature; we found no clear evidence for unconventional superconductivity in this material. Zero field measurements in URu₂Si₂ show the weak antiferromagnetic transition at 17.5 K. Finally, we we found no clear evidence for unconventional superconductivity in this material. Zero field measurements in URu₂Si₂ show the weak antiferromagnetic transition at 17.5 K. Finally, we have observed relaxation in high transverse field due to the formation of a flux lattice in U₆Fe, a material where the electron effective mass is rather lighter than in other heavy fermion systems. The relaxation exhibits a sharp onset atT _c=3.9 K, and is flat at low temperatures as expected for a conventional superconductor.     

Dicationic ((−)-sparteine)palladium-catalyzed enantioselective aldol reaction of aldehydes with 1-phenyl-1-trimethylsilyloxyethene, proceeding via a palladium enolate

A dicationic ((−)-sparteine)palladium complex underwent a superior catalytic enantioselective aldol reaction of aldehydes with 1-phenyl-1-trimethylsilyloxyethene performing satisfactorily, starting with ((−)-sparteine)PdCl₂ and AgSbF₆ as catalyst precursors (1 mol % loading) in the presence of 3 Å molecular sieves over the reaction.     

Reduction of dislocation density and improvement of optical quality in ZnO layers by MgO-buffer annealing

Optical properties of ZnO thin films with/without MgO-buffer annealing were investigated by low and room temperature photoluminescence measurements. The ZnO films were grown on c-sapphire substrates by plasma-assisted molecular-beam epitaxy employing a thin MgO-buffer layer. Dislocation density of ZnO layer was reduced from 5.3 × 10⁹ to 1.9 × 10⁹ cm⁻² by annealing MgO-buffer prior to the growth of ZnO. The intensity of free exciton emission from the sample with MgO-buffer annealing was almost twice of that from the sample without annealing, while the deep level emission from the sample with MgO-buffer annealing was about 1/3 of that without annealing. The MgO-buffer annealing improves optical quality of overgrown ZnO films.     

Phase transitions of lanthanide monophosphides with NaCl-type structure at high pressures

Lanthanide monophosphides LnP (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Tm and Yb) with a NaCl-type structure have systematically been prepared at high temperatures. Using synchrotron radiation, X-ray diffractions of LnP have been studied up to 61 GPa at room temperature. The NaCl---CsCl transition for CeP is found at around 25 GPa. First-order phase transitions of LnP (Ln = La, Pr and Nd) with the crystallographic change occur at around 24, 26 and 30 GPa, respectively. The structure of the high pressure phases of these phosphides is a body center tetragonal structure (Ln: 0, 0, 0; P: 1/2, 1/2, 1/2; space group P4/mmm), which can be seen as the distorted CsCl-type structure. The Pr---P distance in the high pressure form of PrP is 2.789 Å. This almost agrees with the sum of covalent radii of Pr and P. The Pr---P bond has the covalent character at very high pressures. Similar results are also obtained for LaP and NdP. The pressure-induced phase transitions of SmP, GdP, TbP, TmP and YbP occur at around 35, 40, 38, 53 and 51 GPa, respectively. The structure of the high pressure phase is unknown. The phase transitions of LnP with many f-electrons are not due to the mechanism of the ordinary NaCl---CsCl transition. The transition pressures of LnP increase with decreasing the lattice constants in the NaCl-type structure, which decrease with increasing atomic number of the lanthanide atoms.