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.     

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.     

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.     

Tropical Weyl Group Action via Point Configurations and τ-Functions of the q-Painlevé Equations

Starting from certain point sets in the projective plane, we construct a tropical (or subtraction-free birational) representation of Weyl groups over the field of τ-functions. In particular, our construction includes E ₈ ⁽¹⁾ , E ₇ ⁽¹⁾ , E ₆ ⁽¹⁾ and D ₅ ⁽¹⁾ as affine cases; each of them gives rise to the q-difference Painlevé equation.     

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.