A highly stereocontrolled total synthesis of dysiherbaine

A total synthesis of dysiherbaine, a potent agonist of AMPA-KA type glutamate receptors, has been accomplished in completely stereocontrolled manner starting from tri-O-acetyl-D-galactal in 25 steps and in 3% overall yield.     

A Novel Synthesis of 1-Isochromanols via Hetero Diels-Alder Reaction of Carbonyl Compounds with 1-Trimethylsilyloxy-benzocyclobutene as a Precursor of α-Oxy-o-Quinodimethane Under Mild Condition

Reaction of 1-trimethylsilyloxybenzocyclobutene(1) with carbonyl compounds catalyzed by tris(dimethylamino)sulfur (trimethylsilyl)difluoride (TASF) at room temperature gave 1-isochromanol derivatives as corresponding hetero Diels-Alder adducts in good yields.     

Effect of the degree of polynomials in the Savitzky—Golay method for calculation of second-derivative spectra

The second-derivative spectra of absorption curves simulated by a Gaussian function were obtained by using Savitzky—Golay cubic (CPC) and quintic polynomial convolutions (QPC), based on 17 points assumed to be at 0.25-nm intervals. For data obtained directly from the simulated curves (real-type data), the second derivatives agreed with the true values if the widths at half height of the peaks were > 15 nm for CPC and 5 nm for QPC. But when integer values obtained from the real-type data were used to simulate a 12-bit A/D conversion, considerable noise appeared on the second-derivative spectra of peaks wider than the above values, obtained by both CPC and QPC. This occurred because the rounding errors introduced by the A/D conversion formed small shoulders on the digitally reproduced absorption curves, which were enhanced by the differentiation to generate noise. The noise was more intense in QPC than in CPC, thus CPC is preferable for peaks that are not very narrow.     

Synthesis of thiophene/phenylene co‐oligomers. II [1]. Block and alternating co‐oligomers

We report the synthesis of block and alternating thiophene/phenylene co‐oligomers that is based either on the Suzuki coupling reaction or on the Grignard reaction. These reaction schemes enable us to obtain the target compounds at reasonably high yields. The resulting materials have been fully characterized through the solid‐state ¹³C nmr and Fourier‐transform ir as well as the ¹H nmr. Of these, the solid‐state ¹³C nmr and ir are particularly useful in characterizing the materials of higher molecular weight, since those materials are difficult to dissolve in organic solvents.     

Spectroscopic Study of Acid-base Equilibria and Ion Pairing in Supercritical Methanol

Acid-base equilibria between 2,5-dichlorophenol (DCP) and various bases (LiOH, NaOH, and KOH) were studied in ambient to supercritical methanol, by measuring the absorption spectrum of DCP at alkali metal hydroxide molalities ranging up to 10 mmol⋅kg⁻¹, at temperatures up to 250 °C and a pressure of 25.0 MPa. The spectrum was deconvoluted into contributions for the acidic (HA) and basic (A⁻) forms of DCP, taking into account a blue shift of the phenolate (A⁻) spectrum due to the effect of ion pairing with an alkali metal cation. Degrees of dissociation of DCP determined from the spectra suggested that the dissociation constant of DCP has a maximum around 150 °C, whereas that of KOH decreases with temperature. The phenolate-alkali metal ion pairing was examined from the peak shift of the phenolate spectrum in the presence of Li⁺, Na⁺, and K⁺. A smaller cation radius and higher temperature (thus a lower dielectric constant for methanol) give rise to stronger electrostatic interaction in the ion pair. The basicities of the alkali metal hydroxides in supercritical methanol were compared using DCP as an indicator, and were shown to follow the order LiOH < NaOH ≤ KOH. This order is the same as that for the catalytic effect of alkali metal hydroxides on the methylation of phenol in supercritical methanol (Takebayashi et al.: Ind. Eng. Chem. Res. 47:704–709, 2008). Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

In situ monitoring of the H concentration change near an electrode surface through electrolysis using slab optical waveguide pH sensor

The H⁺ concentration change was monitored near an electrode surface through an electrolysis using a slab optical waveguide technique. Indium tin oxide transparent electrode modified by porous insulating polymer to which methyl red was covalently immobilized was used as a guiding layer, and the absorbance change of the polymer film was monitored. H⁺ generation at the vicinity of the electrode through the oxidation of ascorbic acid could be monitored by this technique.