Mutual Kinetic Resolution in Aldol Condensation between 2-Phenylpropanal and 4,5-Dihydro-5-methyl-2-(trimethylsiloxy)-3-(trimethylsilyl)furan

The titanium(IV) chloride-mediated aldol condensation between title compounds proceeds with high diastereoselectivity (Cram) to give $\text{3a}$ exclusively (99% purity).     

Reaction of α-chloroketones with 1,4-dianion of acetophenone n-ethoxy-carbonylhydrazone

1,4-Dianion of acetophenone N-ethoxycarbonylhydrazone (2) reacts with α-chloroketones such as phenacyl chloride, 1-chloroacetone, 3-chloro-2-butanone, and 1,3-dichloroacetone to give pyrazoline derivatives in good yields. In the reactions of 2-chlorocyclohexanone and 3-chloro-2-norbornanone with 2, cis-chlorohydrin and exo-chlorohydrin were selectively obtained, respectively.     

Sol-Gel Products News

Journal of Sol-Gel Science and Technology -     

α + 14C molecular states in 18O

The possible existence of α + ¹⁴C molecular states in ¹⁸O is investigated in a coupled-channel orthogonality-condition model. Comparison with experiment, specifically E1, E2 transition probabilities and reduced α-widths, shows that the assumption of a single molecular configuration for the so-called dipole band is inappropriate. The result of calculation further makes it possible to single out a few molecular bands in ¹⁸O.     

237Np and 57Fe Mössbauer study of NpFeGa5

⁵⁷Fe and ²³⁷Np Mössbauer ōmeasurements have been performed for NpFeGa₅, which is one of the so-called neptunium 1-1-5 compounds. The ⁵⁷Fe Mössbauer spectra below T _N = 118 K show the magnetically ordered state. The magnitude of the hyperfine magnetic field at the ⁵⁷Fe nucleus is determined to be 1.98 ± 0.05 T at 10 K. From the ²³⁷Np Mössbauer spectrum at 10 K, the hyperfine magnetic field at the ²³⁷Np nucleus is 203 T and the hyperfine coupling constant is determined to be 237 T/μ_B using the Np atomic magnetic moment of 0.86 μ_B determined by the neutron diffraction study.     

Ultraviolet photoemission spectroscopy of (TaSe4)2I

The vacuum ultraviolet photoemission spectra of quasi-one-dimensional charge density wave ( CDW ) system, (TaSe₄)₂I, were measured for photon energies between 32 and 100 eV at room temperature ( in the normal phase ) and at about 100 K ( in the CDW phase ). The spectrum of Ta 4f core-levels has shown no additional splitting due to the two different Ta sites. The spectra of the valence and conduction bands have revealed the resonant enhancement for the excitation of the Ta 5p core states, which demonstrates the remarkable hybridization of Ta 5d orbitals with Se 4p orbitals with binding energies smaller than 4 eV. In the CDW phase, the partial cross section decreases for both Ta 5d bands and Se 4p bands with Ta 5d components.     

Synthesis of 2-aminoazulene derivatives. Nucleophilic and palladium-catalyzed amination of 2-substituted azulene

Amination of 2-substituted azulene was carefully examined using several types of amines, and the scope and limitation of substrates and reagents in these direct nucleophilic aminations were found. The synthesis of 2-aminoazulenes was successfully achieved by the reaction of 2-bromoazulene with several amines via palladium-catalyzed amination.     

Theoretical study of resonant-tunneling and confining phenomena with mass variation in unsymmetrical rectangular double-barrier structures

Analytical expressions for the transmission coefficient and the resonance condition in unsymmetrical rectangular double-barrier structures are derived theoretically by taking into account the mass difference between well and barrier layers. It is found that resonant tunneling with a transmission peak equal to 1 (unity resonance) and resonant tunneling with a transmission peak less than 1 (below unity resonance) may occur in the unsymmetrical double-barrier structures. Two independent conditions are required for unity-resonant transmission: One is the Phase-Difference Condition for Resonance (PDCR) and the other is the Maximum Condition for the Peak Value (MCPV). The below-unity resonant transmission occurs when only condition PDCR holds. It is believed that the two conditions are useful for calculating values of the transmission coefficient and the resonance energy for the unsymmetrical double-barrier structures. They may be useful for resonant tunneling-device fabrication. Furthermore, wave functions of an electron at resonance level are calculated and the confining phenomenon is confirmed.     

Optical and time-resolved electron paramagnetic resonance studies of the excited states of para-methylcinnamic acid and para-methylcinnamate anion

Time-resolved electron paramagnetic resonance (EPR), fluorescence, and phosphorescence spectra have been observed for the excited states oftrans-p-methylcinnamic acid (p-MeCA) andtrans-p-methylcinnamate anion (p-MeCA^?) in rigid organic glasses at 77 K. With a stretched-polymer-film technique, we assigned the resonance fields in the time-resolved EPR spectra of the lowest excited triplet (T₁) states ofp-MeCA andp-MeCA^?. From the analysis of these spectra we concluded that the deviation from planar structure in the T₁ state is small inp-MeCA andp-MeCA^? and the direction of C=O iss-cis to the ethylenic C=C bond inp-MeCA. The deprotonation appears to have little effect on the zero-field splitting (ZFS) parameters. The ZFS parameters were calculated theoretically using semiempirical molecular orbitals. The sublevel preferentially populated by intersystem crossing (ISC) is T _y in bothp-MeCA andp-MeCA^?. However, following the deprotonation ofp-MeCA, (P _y?P _z)/(P _x?P _z) changes from 5.7 inp-MeCA to 2.1 inp-MeCA^? (P _i are relative populating rates; thex andy axes are close to the long and short in-plane molecular axes, respectively, andz-axis is perpendicular to the molecular plane). The fluorescence lifetimes indicate that the deprotonation has little effect on the sum of the three ISC rate constants for the three T₁ sublevels. A decrease in acidity ofp-MeCA upon excitation has been observed.