Radical alkenylation of alpha-halo carbonyl compounds with alkenylindiums

Alkenylation reaction of alpha-halo carbonyl compounds with alkenylindiums proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties as well as a styryl group could be introduced by this method. The geometry of the carbon-carbon double bonds of the alkenylindiums was retained. Preparation of an alkenylindium via a hydroindation of 1-alkyne followed by radical alkenylation established an efficient one-pot strategy. [reaction: see text]     

Temperature dependence on the binding of butyl orange by bovine serum albumin

The binding of 4′-dibutylaminoazobenzene-4-sulfonate anion (butyl orange) by bovine serum albumin has been examined quantitatively by an equilibrium dialysis method at 5, 10, 15, 20, 25, and 35°C. The first binding constants and the thermodynamic parameters for the formation of the first dye anion-protein complex have been calculated. The peculiar temperature dependence of the first binding constant could be observed. That is, the value of the first binding constant increases with increasing temperature until it reaches a maximum value at approximately 18°C and then decreases with raising temperature. Accordingly, this binding process is exothermic above 18°C and is endothermic below 18°C. Near 18°C the process exhibits athermal reaction. From the thermodynamic data obtained, it is evident that the favorable free energy of the binding is accompanied by an entropy gain and that the enthalpies of the binding vary from a positive (unfavorable) value below 18°C to a negative (favorable) one above 18°C. Furthermore an apparent temperature dependence of the thermodynamic functions was observed. That is, ΔF° becomes larger in absolute magnitude as the temperature increases. The positive quantity of ΔS° tends to decrease with increasing temperature. All these facts can be interpreted satisfactorily in terms of hydrophobic interactions between hydrophobic portions of the dye and nonpolar parts of the albumin.     

Observation of THz coherent transition radiation from single-bunch beam at KURRI-LINAC as an intense pulsed light source

A single-bunch beam has been generated using a developed high-speed avalanche-type pulser in KURRI-LINAC in order to lift restrictions of the spectral resolution in the spectroscopic study and the delay time in the time-resolved measurement. Both of the rise and fall times of the developed pulser are 110 ps. The observation of CTR has confirmed the single-bunch beam. The degree of impurity of single bunch has been estimated to be 1.5% by the analysis of the interferogram.     

Infrared-microwave double resonance of propynal by using the 3.51 μm HeXe laser

The 3.51 μm HeXe laser is magnetically tuned over a wavenumber of 0.2 cm^?1 and used for infrared absorption and double resonance spectroscopy. Eight rotation-vibration lines of propynal in the ν₂ band are assigned by the Stark effect. Eleven microwave transitions in the v₂ = 1 vibrational state are observed by the method of infrared-microwave double resonance. The rotational constants of the excited state and the band origin of the vibration ν₂ are determined from the observed spectra.     

Role of Al or Eu on thermoluminescence of Al- and/or Eu-doped SiO2 crystals

Although SiO₂ crystals have been used in electroluminescence devices and thermoluminescence (TL) dosimeters, the emission mechanism of TL has not yet been clearly explained. Recently, as we could get amorphous and highly pure SiO₂ prepared by the sol-gel method, we have investigated the TL emission mechanism using Al³⁺- and/or Eu³⁺-doped SiO₂ crystalline samples prepared by the heat-treatment under much lower temperature that the melting point of SiO₂. The TL spectrum of the Eu³⁺-doped sample displayed several peaks, including two main peaks due to the electron transitions from ⁵D₂ to ⁷F₅ (ca. 570 nm) and from ⁵D₀ to ⁷F₂ (ca. 610 nm). As doping concentration increased, all the peak intensities reduced from maximum values except that due to the electron transition from ⁵D₀ to ⁷F₂. These observations are thought to result from a cross-relaxation process due to the lack of inversion symmetry at the Eu³⁺ site.     

Collinear fast atomic-beam laser spectroscopy at riken garis/igisol

We have constructed a fast atomic-beam collinear laser spectroscopy system connected to the on-line isotope separator facility GARIS/IGISOL at RIKEN. This system is potentially powerful in studying refractory elements. To test the system, an off-line collinear experiment was made on stable Hf isotopes produced by means of laser ablation technique. For production of radioactive Hf isotopes, the use of the inverse kinematics of a fusion reaction,⁹Be(¹⁶⁶Er,xn)^175-x Hf, was investigated. The radioactive isotope¹⁶⁹Hf was successfully extracted from GARIS/IGISOL and accelerated up to 30 keV.     

Reduction of elemental selenium by samarium diiodide: Selective synthesis of diorganyl selenides and diselenides

The reduction of elemental selenium by samarium diiodide led to selective formation of selenolate anion species (Se²⁻ and Se₂²⁻), the alkylation of which provided dialkyl selenides and diselenides, respectively, in excellent yields.     

Trans-hydrometalation of alkynes by a combination of InCl3 and DIBAL-H: one-pot access to functionalized (Z)-alkenes

[reaction: see text] Triethylborane-induced hydrometalation of alkynes proceeds in an anti manner to afford the corresponding (Z)-alkenylmetal compounds stereoselectively, where dichloroindium hydride would play a key role. A variety of functional groups including hydroxy, carbonyl, and carboxy groups were tolerant under the reaction conditions. Following iodolysis and cross-coupling reaction of the (Z)-alkenylmetal species show the usefulness of this strategy.     

Synthesis of tricyclic compounds as steroid 5alpha-reductase inhibitors

A series of 4-phenoxybutyric acid derivatives attached to a tricyclic skeleton were prepared and evaluated as 5alpha-reductase inhibitors. Structure activity relationships for these compounds in terms of rat epididymis (type 2) 5alpha-reductase inhibitory activities reveal that 1) the substitution pattern at the 11-position of dibenz[b,e]oxepin influenced potency, 2) higher lipophilicity of the tricyclic skeleton improved potency, whereas the existence of a basic nitrogen atom in this skeleton was detrimental to potency, and 3) isobutyl substitution at the 8 positon of the azepine skeleton was tolerated. Among the tricyclic compounds studied, 4-[3-[5-benzyl-8-(2-methyl)propyl-10,11-dihydrodibenz[b,f]azepine- 2-carboxamido]phenoxy]butyric acid (26) was the most potent inhibitor of rat type 2 5alpha-reductase at 0.1 microM.     

Triethylborane-mediated hydrogallation and hydroindation: novel access to organogalliums and organoindiums

Hydrogallation of carbon[bond]carbon multiple bonds proceeds in the presence of triethylborane as a radical initiator. Several functionalities do not interfere with this reaction. Resulting alkenyl- and alkylgallium species can be trapped by several electrophiles. Highly regioselective radical addition of an indium hydride reagent to alkynes is also achieved. Various functionalities are tolerant under the reaction conditions. The reaction proceeds with complete anti stereoselectivity. Alkenylindiums obtained via hydroindation can be employed for the following cross-coupling reaction with aryl halides in one pot.