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.     

Reaction of C3 and C4 ketoses with alkenals and alkenones in water

Treatment of 1,3-dihydroxyacetone and acrolein with aqueous KOH gave a tetrahydrofuran derivative, 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octane, in 80% yield. Similarly, 6-alkyl substituted 1,4-dihydroxy-3,7-dioxabicyclo[3.3.0]octanes were obtained by reaction of 1,3-dihydroxyacetone with various α,β-unsaturated aldehydes. In the cases of long chain alkenals, the reaction was effectively accelerated in the presence of organic co-solvent. On the other hand, the corresponding tricyclic products were synthesized by reaction of 1,3-dihydroxyacetone with cyclic enones, such as 2-cyclopentenone and 2-cyclohexenone. This method was successfully applied to the reaction of a tetrulose in the absence of any protecting groups.     

A simple and sensitive method for the determination of hydroxylamine in fresh-water samples using hypochlorite followed by gas chromatography.

A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively.     

Sub-critical crack growth rate of soda-lime-silicate glass and less brittle glass as a function of fictive temperature

Sub-critical crack growth rates of soda-lime-silicate glass and less brittle glass with different fictive temperatures were compared using the DCDC method under both dry and humid atmospheres in order to investigate the origin of the unique mechanical features of the less brittle glass developed by Ito and his collaborators. In both dry and humid atmospheres, the crack velocity of the soda-lime-silicate glass was slower than that of the less brittle glass. For both glasses, the glass sample with higher fictive temperature showed a slower crack growth rate under both dry and humid atmospheres. These observations can be explained by the tendency for the plastic flow at the crack tip; the soda-lime-silicate glass is expected to show easier plastic flow under tension than the less brittle glass, and also the samples with higher fictive temperatures are expected to show easier plastic flow, leading to greater fracture toughness, K_IC, and slower crack growth rate.     

Hydrolysis of acetals in water under hydrothermal conditions

A simple method for the hydrolysis of acetals and ketals was accomplished in neutral water or aqueous media by hydrothermal treatment without using acidic reagents. The deacetalization reaction was effectively accelerated in the presence of calcium chloride. Because no acidic catalysts were employed, neutralization of the reaction mixture was not necessary after the reaction. This sequence was successfully applied to the hydrolysis of chitosan, a biodegradable polyaminosaccharide.     

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.