Unambiguous Determination of the Absolute Configurations of Acetylene Alcohols by Combination of the Sonogashira Reaction and the CD Exciton Chirality Method – Exciton Coupling between Phenylacetylene and Benzoate Chromophores

The CD exciton chirality method was applied to various phenylacetylene alcohols to determine their absolute configurations; the long axis polarized –^* transition (_max=252nm) of the 4-methoxyphenylacetylene chromophore couples with the transition (_max=257nm) of the 4-methoxybenzoate group to generate intense exciton split CD Cotton effects, from the signs of which the absolute configurations of phenylacetylene alcohols were unambiguously determined. As an extension of the results, a new methodology for determining the absolute configurations of acetylene alcohols having the HCCCH(OH)-moiety by combination of the Sonogashira reaction and the CD exciton chirality method has been developed and applied. Since the –^* transition of acetylene triple bond is located below 180nm, it is difficult to observe ideal bisignate CD Cotton effects due to the exciton coupling between acetylene and benzoate chromophores. To observe the ideal exciton split Cotton effects necessary for the unambiguous determination of absolute configuration, the terminal acetylene group was converted, by the Sonogashira reaction, to the 4-methoxyphenylacetylene moiety, which exhibits an intense –^* absorption band polarized along the long axis of the chromophore at 252nm. As a partner of exciton coupling, 4-methoxybenzoate showing a –^* band at 257nm was introduced into the alcohol moiety, and the benzoates formed showed intense bisignate CD Cotton effects, from the signs of which the absolute configurations of original acetylene alcohols could be determined in an unambiguous manner.     

Synthesis and structural,electrochemical, and optical properties of Ru(II) complexes with azobis(2,2'-bipyridine)s

Two new ditopic ligands, 5,5"-azobis(2,2'-bipyridine) (5,5"-azo) and 5,5"-azoxybis(2,2'-bipyridine) (5,5"-azoxy), were prepared by the reduction of nitro precursors. Mononuclear and dinuclear Ru(II) complexes having one of these bridging ligands and 2,2'-bipyridine terminal ligands were also prepared, and their properties were compared with previously reported Ru(II) complexes having 4,4"-azobis(2,2'-bipyridine) (4,4"-azo). The X-ray crystal structure showed that 5,5"-azo adopts the trans conformation and a planar rodlike shape. The X-ray crystal structure of [(bpy)(2)Ru(5,5"-azo)Ru(bpy)(2)](PF(6))(4) (Ru(5,5"-azo)Ru) showed that the bridging ligand is in the trans conformation and nearly planar also in the complex and the metal-to-metal distance is 10.0 A. The azo or azoxy ligand in these complexes exhibits reduction processes at less negative potentials than the terminal bpy's due to the low-lying pi level. The electronic absorption spectra for the complexes having 5,5"-azo or 5,5"-azoxy exhibit an extended low-energy metal-to-ligand charge-transfer absorption. The ligands, 5,5"-azo and 5,5"-azoxy, and the mononuclear complex, [(bpy)(2)Ru(5,5"-azo)](2+), isomerize reversibly upon light irradiation. The low-energy MLCT state sensitizes the isomerization of the azo moiety in this complex. While [(bpy)(2)Ru(4,4"-azo)Ru(bpy)(2)](PF(6))(4) exhibits light switch properties, namely, significant electrochromism and a large luminescence enhancement, upon reduction, Ru(5,5"-azo)Ru does not show these properties. The radical anion formation upon reduction of these complexes has been confirmed by ESR spectroscopy.     

Levels of artificial radionuclides and uranium in rain water collected from Ibaraki (Japan) following the Tomsk-7 accident in Russia

Measurements of some selected radionuclides were carried out in rain waters collected from Ibaraki Prefecture, Japan, following the nuclear accident at Tomsk-7, Russian Federation, in April 1993. The concentrations obtained for artificial radionuclides were⁹⁰Sr1.8 mBq l^–1,¹³⁷Cs0.1 Bq l^–1,¹³¹I0.1 Bq l^–1 and¹²⁹I4 Bq l^–1. Uranium (²³⁸U) concentrations in rainfalls in April 1993 were 6.3–39 ng l^–1. These data were compared to control values obtained previously and there was no appreciable influence on the radioactivity levels in Japan after the Tomsk-7 accident. Since only limited data on the concentrations of¹²⁹I and uranium in rain water are available, these new analytical results contribute to understanding the background levels for these nuclides.     

Rapid and simultaneous analysis of dichlorvos, malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid in citrus fruit by flow-injection ion spray ionization tandem mass spectrometry

A simple method for the rapid and simultaneous analysis of dichlorvos (DDVP), malathion, carbaryl, and 2,4-dichlorophenoxy acetic acid (2,4-D) in citrus fruit, which uses flow-injection ion spray ionization tandem mass spectrometry, has been developed for the first time. The method involves the combined use of stable isotopically labeled internal standards (DDVP-d₆, malathion-d₁₀, carbaryl-d₇, and 2,4-D-d₅) and a multiple reaction monitoring technique. The average recoveries for the pesticides at the same concentrations as their tolerance levels (DDVP: 0.1-0.2 μg g⁻¹; malathion: 0.5-4.0 μg g⁻¹; carbaryl: 1.0 μg g⁻¹; 2,4-D: 1.0-2.0 μg g⁻¹) ranged from 90 to 119% with the relative standard deviation (R.S.D.) ranging from 1.0 to 13.1% (n = 5). Analysis time, including sample preparation and determination, was only 15 min. The present method is effective for screening DDVP, malathion, carbaryl, and 2,4-D in citrus fruit.     

Photoinduced rotational isomerization mechanism of 2-chlorobenzaldehyde in low-temperature rare-gas matrices by vibrational and electronic spectroscopies

Rotational isomerization of 2-chlorobenzaldehyde in low-temperature rare-gas matrices has been investigated by vibrational and electronic spectroscopies with aids of the density functional theory (DFT) and configuration interaction single (CIS) calculations. Infrared spectrum of the less stable O-cis isomer, produced from the more stable O-trans isomer upon UV irradiation, is measured with an FT-IR spectrophotometer. The enthalpy difference between the O-cis and O-trans isomers is estimated to be 9.7±0.2 kJ mol⁻¹ from the temperature dependence of the infrared band intensities. Analyses of the infrared and electronic absorption spectral changes after UV irradiation and the phosphorescence spectra measured at various excitation wavelengths suggest that the rotational isomerization occurs via the intersystem crossing from S₁ to T₁.     

Mechanism of Mukaiyama-Michael Reaction of Ketene Silyl Acetal: Electron Transfer or Nucleophilic Addition?

Mechanism of Mukaiyama-Michael reaction of ketene silyl acetal has been discussed. The competition reaction employing various types of ketene silyl acetals reveals that those bearing more substituents at the beta-position react preferentially over less substituted ones. However, when ketene silyl acetals involve bulky siloxy and/or alkoxy group(s), less substituted compounds react preferentially. The Lewis acids play an important role in these reactions. Enhanced preference for the more sterically demanding Michael adducts is obtained with Bu(2)Sn(OTf)(2), SnCl(4), and Et(3)SiClO(4) in the former reaction while TiCl(4) gives the highest selectivity for the less sterically demanding products in the latter case. These results are interpreted in terms of alternative reaction mechanisms. The reaction of less bulky ketene silyl acetals are initiated by electron transfer from these compounds to a Lewis acid. On the other hand, bulkier ketene silyl acetals undergo a ubiquitous nucleophilic reaction. Such a mechanistic change is discussed based on a variety of experimental results as well as the semiempirical PM3 MO calculations.     

Light-driven molecular hinge: a new molecular machine showing a light-intensity-dependent photoresponse that utilizes the trans-cis isomerization of azobenzene

[reaction: see text] A new class of molecular machine exhibits a hingelike motion upon photoirradiation. The motion (close and open) can be operated by alternate irradiation with UV and visible light. The trans/trans and cis/cis isomers are thermally stable at 40 degrees C, and the photochemical closure reaction (from trans/trans to cis/cis isomer) is dependent on the intensity of the light used because of the short-lived intermediate (trans/cis isomer).     

Comparison of a radiation counting method and ICP-MS for the determination of99Tc in environmental samples

Results of⁹⁹Tc measurements between radiation and non-radiation counting methods were compared using four radiation sources for which⁹⁹Tc has been previously determined with a gas-flow proportional counter or a GM counter. Each⁹⁹Tc source consisted of a stainless steel planchet bound by mylar films. Seaweeds collected from the Irish Sea were analyzed and⁹⁹Tc was electroplated on the planchet. The⁹⁹Tc in each sample was separated and measured again by inductively coupled plasma mass spectrometry (ICP-MS). Tc was continuously removed from each sample with 2M HNO₃ and 2M NaOH. After the solution containing Tc was adjusted to 0.1M HNO₃, Tc was extracted on a novel extraction chromatographic resin to separate it from Ru. The total recoveries for Tc on the planchet samples were almost the same with an average of 91%. The results of⁹⁹Tc measurements by both radiation and non-radiation counting methods agreed well with each other.     

High Pressure Synthesis of Cycloadduct of Fullerene C60 with 2H-Pyran-2-one∗∗

Under high pressure conditions, fullerene C₆₀ smoothly reacts with 2H-pyran-2-one to give a [4+2] cycloadduct, which can be reduced to an alcohol derivative.

     

Low-temperature growth of high-Tc superconducting films by plasma-enhanced metal-organic chemical vapor deposition

Plasma-enhanced MOCVD in which metal-organic compounds are sublimated directly into the growth chamber is studied for the first time as a new low-temperature process for growing superconducting YBa₂Cu₃O-_-x thin films. Y(THD)₃, Ba(THD)₂, Cu(THD)₂ and oxygen are used as metal sources and oxydizing agent. Emission spectroscopy reveals that activated metal-organic compounds and activated oxygen species are present during film growth. Superconducting YBa₂Cu₃O_7-x films whose zero-resistivity temperature are 50 K and 82 K are grown at 550°C and 600°C.