Reactivity of methacrylates in anionic copolymerization with methyl methacrylate by n-BuLi

Monomer reactivity ratios, r₁ and r₂ were determined in the anionic copolymerizations of methyl methacrylate (MMA, M₁) with ethyl (EtMA), isopropyl (i-PrMA), tert-butyl (t-BuMA), benzyl (BzMA), α-methylbenzyl (MBMA), diphenylmethyl (DPMMA), α,α-dimethylbenzyl (DMBMA), and trityl (TrMA) methacrylates (M₂) by use of n-BuLi as an initiator in toluene and THF at -78°C. The order of the reactivity of the monomers towards MMA anion was DPMMA > BzMA > MMA > EtMA > MBMA > i-PrMA > t-BuMA > TrMA > DMBMA in toluene and TrMA > BzMA > MMA > DPMMA > EtMA > MBMA > i-PrMA > DMBMA > t-BuMA in THF. Except for the extremely low reactivity of TrMA and DPMMA in toluene due to steric hindrance, the order was explained in terms of the polar effect of the ester groups. A linear relationship was found between log (1/r₁) and Taft's σ* values of the ester groups, where the ρ* value was 1.1. The plots of log (1/r₁) vs. the ¹H_a (cis to the carbonyl) and ¹³C_ß chemical shifts of the monomers were also on straight lines. The polymer obtained in the copolymerization of MMA with TrMA in toluene by n-BuLi at -78°C was a mixture of poly-MMA and a copolymer, suggesting that there exist two kinds of growing centers.     

Effective insulating properties of autooxidized monolayers using organic ditellurides

Dialkyl ditellurides adsorb on Au(111) surfaces by wet deposition to form highly resistive autooxidized monolayers (AMs) due to the automatic formation of oxidized tellurium species after the adsorption of ditellurides on the surfaces under air in contrast to the case of the lighter dichalcogenides such as disulfides and diselenides. The ditelluride AMs could be applied to the selective fabrication of effective resistance, ferroelectric layers, piezoelectric parts, and/or new imaging systems using the feature of tellurium oxide in small device circuits.     

Stereoselective synthesis of optically active 3-hydroxy-7,8-dihydro-beta-ionol-glucosides

A stereocontrolled synthesis of optically active beta-D-glucopyronosides 6a, b and 11a, b was accomplished via the 7,8-saturated alcohols 4a, b, efficiently prepared by an asymmetric transfer hydrogenation of the alpha,beta-acetylenic ketone 1 and subsequent catalytic hydrogenation. Simultaneous separation of these four glucosides by HPLC was also performed. This work is useful not only in order to confirm the stereochemistries of the trace amount of glucosides in plants but also to clarify their biosynthesis.     

Split flow and bypass flow systems for monolithic capillary columns in liquid chromatography

Split flow and bypass flow systems were assembled using Nano Y Connectors with low dead volume commercially available for capillary liquid chromatography (LC). The split ratio could be controlled by changing the dimension of restriction tubing and applied back pressure to the restriction tubing. The split flow system allowed us to use valve injectors and pumps commercially available for capillary LC. The reproducibility of the present split flow system was acceptable. The relative standard deviation for six successive measurements was 0.4% for the retention time, whereas that for the peak height and peak area was 1-3% depending on the analytes. The bypass flow system uses two Nano Y Connectors, where the eluent split at the first Nano Y Connector, which is located in the inlet of the separation column, is merged again into the effluent from the column at the second Nano Y Connector. The bypass flow system could avoid on-column detection and allowed us to use flow cells, leading to an approximate three times improvement in signal-to-noise. The present flow systems were evaluated by using aromatic hydrocarbons and alkylbenzenes as test analytes.     

Group-selective hydroalumination: a novel route to stereogenic tert-alcohol centers

[reaction: see text]. A new group-selective reaction is described, that is, the hydroalumination of bis-alkynyl alcohols armed with an adjacent stereogenic center, giving stereo-defined tert-alcohols of potential utility in natural product synthesis.     

Submillimeter wave esr and far infrared spectroscopy measurements of CuGeO3

Submillimeter wave ESR and far infrared transmission measurements of first inorganic spin-Peierls system CuGeO₃ have been performed using the single crystals. Our new results are discussed in connection with the magnetic properties of the spin-Peierls systems and the recent neutron measurements of CuGeO₃.     

Variations of natural 13C and 15N abundances in the rat tissues and their correlation

The 13C and 15N abundances of the tissues of rats fed with a constant diet were measured by mass spectrometry. Isotopic discrimination was larger in 15N than in 13C compared to diet. The extents of discrimination of 13C and 15N differed depending on tissues, but highly correlated each other.     

Some reactions of mono substituted pyrazine monoxides

The reactions of the monoxides of propylpyrazine and phenylpyrazine with phosphoryl chloride or acetic anhydride were investigated. Except in the case of the reaction of 2-propylpyrazine 1-oxide with acetic anhydride, chlorination or acetoxylation occurred on the pyrazine ring in all cases; moreover, these reactions occurred preferentially at the position poorest in π-electron density. The N-oxidation and the successive chlorination of monochloro-phenylpyrazines were also investigated, and the structures of the products were confirmed.