Optical damping constants in narrow gap semiconductors

Optical damping constants due to free carriers of HgSe, Zn _x Hg_1–x and Cd _x Hg_1–x Se were estimated from far infrared reflection spectra at 5 and 10 K. The damping mechanism was explained by the Drude type scattering below plasma frequency and by doubly ionized impurity scattering in the higher frequency range.     

Preparation and characterization of 6-substituted 1,8-diazabicyclo[5.4.0]undec-7-ene

The lithium 1,8-diazabicyclo[5.4.0]undec-6-ide ( 1 ) prepared from 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and n-butyllithium reacts with alkyl halides and carbonyl compounds such as benzophenone, acetophenone, and benzaldehyde to give 6-substituted DBU derivatives in good yields. The reaction behavior of 6-substi-tuted DBU was also investigated.     

Ion optical evaluation of a miniature double-focusing mass spectrograph

A new miniature double-focusing mass spectrograph has been designed and constructed. The ion optical system was designed based on Mattauch-Herzog geometry. The mass spectrograph employs a focal plane detector consisting of a microchannel plate, a phosphor layer, a fiber-optic plate and a charge-coupled device. For the evaluation of the ion optics of the instrument, the energy and angular focal planes were investigated both experimentally and by simulation. Double focusing was satisfactorily achieved along a straight line over a wide mass range, and the experimental and simulated results were mutually consistent. A second-order element of the transfer matrix was also measured experimentally and proved to be in good agreement with the simulated result.     

Facile synthesis of 2,4-dioxo-1,2,3,4-tetrahydroquinazolines by sulfur-assisted carbonylation with carbon monoxide

2,4-Dioxo-1,2,3,4-tetrahydroquinazolines were easily synthesized in excellent yields by sulfur-assisted carbonylation of 2′-aminobenzamides with carbon monoxide in the presence of a base, such as DBU or DBN.     

Phosphorescence and photochemical properties of benzophenone included within alkali metal cation-exchanged ZSM-5 zeolites

The phosphorescence properties of benzophenone included within alkali metal cationexchanged ZSM-5 zeolites were investigated to clarify the effects of the micro-environment of hostadsorbents on the electronic excited states of guest-molecules included within the restricted void spaces. Benzophenone included within such cation-exchanged ZSM-5 zeolites was found to exist in both a protonated and hydrogen-bonded form. It was found that exchanging the cations dramatically affects the ratio of their contents. Photolysis of these systems revealed that both benzhydrol and benzpinacol were the main products, their yields strongly depending on the kind of the cations exchanged. Especially, the protonated species was found to play a significant role in the photoreactions observed with benzophenone included within zeolite cavities.     

Facile and efficient synthesis of lactols by a domino reaction of 2,3-epoxy alcohols with a hypervalent iodine(III) reagent and its application to the synthesis of lactones and the asymmetric synthesis of (+)-tanikolide

The domino reaction of 2,3-epoxy-1-alcohol derivatives, namely tetrasubstituted 2,3-epoxy-1-alcohols and 2- or 3-alkyl trisubstituted 2,3-epoxy-1-alcohols, with PhI(OCOCF(3))(2) in the presence of H(2)O is described in detail. In this reaction, several types of lactol derivatives can be directly obtained from the 2,3-epoxy-1-alcohol derivatives in a single operation. The obtained lactols were successively converted into the corresponding lactones. This reaction is applicable to the construction of optically active lactone compounds. The asymmetric total synthesis of (+)-tanikolide, an antifungal marine natural product, has been effectively achieved by using this reaction.     

1,5-Polymerization of 1-thioacylaziridines

Four thioacylaziridines, 1-thioaroyl-, 1-(N-phenylthiocarbamyl)-, 1-(aryloxythiocarbonyl)-, and 1-(aryldithiooxycarbonyl)aziridines, were found to undergo 1,5-polymerization to giving polymers of polyiminothioether, polyisothiourea, polyiminothiocarbonate, and polyiminodithiocarbonate structure, respectively. The 1,5 polymerization may be explained by the kinetic factors rather than the thermodynamic ones.     

Palladium-catalyzed transformation of cyclobutanone O-benzoyloximes to nitriles via C-C bond cleavage

Palladium-catalyzed transformation of cyclobutanone O-benzoyloximes to a variety of nitriles is described. The reaction may proceed via two important steps, that is, (i) oxidative addition of the N-O bond of oximes to Pd(0) to give a cyclobutylideneaminopalladium(II) species and (ii) beta-carbon elimination of this species to afford a reactive alkylpalladium species. The kind of products is very dependent on the nature of substituents on the cyclobutane ring. The direction of the C-C bond cleavage is controlled by the kind of ligand employed. The sequential reaction composed of the C-C bond cleavage and the subsequent intra- and intermolecular C-C bond formations via the corresponding alkylpalladium species is also demonstrated. For example, an oxime having an alkynyl moiety at a suitable position reacts with a variety of alkenes to afford nitriles bearing dienylcyclopentane moiety in moderate to good yields.     

Photocatalytic reduction of CO2 with H2O on TiO2 and Cu/TiO2 catalysts

Photoinduced reduction of CO₂ by H₂O to produce CH₄ and CH₃OH has been investigated on wellcharacterized standard TiO₂ catalysts and on a Cu²⁺ loaded TiO₂ catalyst. The efficiency of this photoreaction depends strongly on the kind of catalyst and the ratio of H₂O to CO₂. Anatase TiO₂, which has a large band gap and numerous surface OH groups, shows high efficiency for photocatalytic CH₄ formation. Photogenerated Ti³⁺ ions, H and CH₃ radicals are observed as reactive intermediates, by ESR at 77 K. Cu-loading of the small, powdered TiO₂ catalyst (Cu/TiO₂) brings about additional formation of CH₃OH. XPS studies suggest that Cu⁺ plays a significant role in CH₃OH formation.