Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

Oscillatory reaction using immobilized catalase.

Oscillation is found in many biological systems, and among them the enzymatic oscillatory reaction has been well studied using an enzyme solution. We show in this study for the first time that oscillation occurs when catalase is immobilized to controlled pore glass (CPG). The oscillatory wave mode changes with the distance among the CPG, electrode, or dialysis membrane. The lower substrate concentration results in oscillation with a longer period. This tendency agrees with a previous study using an enzyme solution. Furthermore, we show that the oscillation occurs when no dialysis membrane is used. These results show the wider applicability of the system to analysis or novel device fabrication.     

220-MHz NMR spectra of acrylic monomer–2-substituted 1,3-diolefin alternating copolymers

An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN–IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA–CLP and AN–CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN–CLP alternating copolymer. The AN–IP and MMA–IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin. The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory.     

Swelling effect onα-relaxation in high density polyethylene

Summary Swelling effects of carbon tetrachloride on the mechanical relaxations in the crystal mat and the melt-crystallized samples of high density polyethylene were studied using a torsion pendulum. A very strong-relaxation peak appears by swelling at the low temperature side of the original-relaxation for the crystal mat. It was shown that this strong-relaxation originates from the slippage between the highly swollen lamellae. For the melt-crystallized sample, the-relaxation peak is decreased by swelling, but its temperature is unchanged. This behavior suggests that the-relaxation in the melt-crystallized sample originates mainly from deformation process of intermosaic block region. The swelling effect on-relaxation was also discussed.

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Zusammenfassung Quellungseffekte von Tetrachlorkohlenstoff auf das mechanische Relaxationsverhalten in Einkristall-Matten und schmelzkristallisierten Proben von linearem Polyäthylen wurden mit den Torsionspendeln untersucht. Ein sehr starkes-Maximum tritt durch die Quellung bei tieferen Temperaturen als der der-Relaxation in den nicht gequollenen Einkristall-Matten auf. Es wird gezeigt, daß diese starke-Relaxation auf das Gleiten der ausreichend gequollenen Lamellen zurückzuführen ist. Bei schmelzkristallisierten Proben wird das-Maximum durch die Quellung erniedrigt, seine Temperaturlage wird jedoch nicht verändert. Dies zeigt, daß die-Relaxation in der schmelzkristallisierten Probe hauptsäcblich auf Deformations-Prozessen in den Blöcken beruht. Auch die Quellungseffekte auf die-Relaxationen wurden diskutiert.

     

Ionic conduction of the perovskite-type halides

The ionic conduction in the perovskite-type halides, CsPbCl₃, CsPbCl₃ and KMnCl₃, was studied. Measurements were made of ac conductivity at temperatures from 150°C to the melting point, and of ionic transport number using the Tubandt, EMF and ion-blocking methods. The effects of impurity doping on the ionic conductivity of CsPbCl₃ were also studied using the samples of composition, CsPb_0.99M_0.01Cl_2.99 (M = Li, Na, K, Ag). It was concluded that these materials are halide-ion condcutors. The ionic conductivities of CsPbCl₃ and CsPbBr₃ are close to those of the well known halide-ion conductors, PbCl₂ and PbBr₂. The ionic transport numbers were found to be > 0.9 for CsPbCl₃ and CsPbBr₃, and about 0.99 for KMnCl₃. The conduction was considered to be caused by the migration of halide-ion vacancies V_X (X = Cl, Br). The activation energies for the migration of V_X were 0.29 eV for CsPbCl₃, 0.25 eV for CsPbBr₃ and 0.39 eV for KMnCl₃. The vacancy diffusion coefficients of these materials were found to be verylarge. However, the impurity doping did not increase the ionic conductivity markedly because of small dopant solubility.     

Dielectric properties and conductivity of styrene-methacrylic acid copolymers and partially neutralized salts

Dielectric and conductivity measurements have been carried out on styrene-methacrylic acid copolymers and their salts in the glass transition region, stressing the comparison of polymers neutralized to different extents. A simple monomer-dimer equilibrium between carboxylic acid groups is applicable to the pure acid polymers, which explains the increase of both the glass transition temperature and of the dielectric strength with concentration of methacrylic acid. The dielectric data indicate that very few sodium carboxylate groups can dissolve in the matrix of the pure salt, whereas the presence of carboxylic acid groups in partly neutralized polymers enhances the dissolution of the salt groups in the matrix. Considerable differences are observed between the partly neutralized polymer and the blend consisting of pure acid and pure salt copolymers, which suggests that exchange of cations between acid and salt groups is quite slow even at high temperatures. The conductivity of the ionomers appears to be related to the diffusion of carriers through the matrix.