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21.
22.
Ohnishi YY Matsunaga T Nakao Y Sato H Sakaki S 《Journal of the American Chemical Society》2005,127(11):4021-4032
Ruthenium-catalyzed hydrogenation of carbon dioxide to formic acid was theoretically investigated with DFT and MP4(SDQ) methods, where a real catalyst, cis-Ru(H)2(PMe3)3, was employed in calculations and compared with a model catalyst, cis-Ru(H)2(PH3)3. Significant differences between the real and model systems are observed in CO2 insertion into the Ru(II)-H bond, isomerization of a ruthenium(II) eta1-formate intermediate, and metathesis of the eta1-formate intermediate with a dihydrogen molecule. All these reactions more easily occur in the real system than in the model system. The differences are interpreted in terms that PMe3 is more donating than PH3 and the trans-influence of PMe3 is stronger than that of PH3. The rate-determining step is the CO2 insertion into the Ru(II)-H bond. Its deltaG(o++) value is 16.8 (6.8) kcal/mol, where the value without parentheses is calculated with the MP4(SDQ) method and that in parentheses is calculated with the DFT method. Because this insertion is considerably endothermic, the coordination of the dihydrogen molecule with the ruthenium(II)-eta1-formate intermediate must necessarily occur to suppress the deinsertion. This means that the reaction rate increases with increase in the pressure of dihydrogen molecule, which is consistent with the experimental results. Solvent effects were investigated with the DPCM method. The activation barrier and reaction energy of the CO2 insertion reaction moderately decrease in the order gas phase > n-heptane > THF, while the activation barrier of the metathesis considerably increases in the order gas phase < n-heptane < THF. Thus, a polar solvent should be used because the insertion reaction is the rate-determining step. 相似文献
23.
Labeling experiments using several deuterated lipids were pursued to study the biosynthesis of macrocyclic isoprenoidal lipids of thermophilic methanogenic archaea, Methanothermobacter thermautotrophicus. The isopropylidene terminal of geranylgeranyl group of monomeric precursor appeared to be important for the CC bond formation at the hydrophobic end in the macrocyclic lipids. A mechanism involving a radical trigger at the allylic methyl group is proposed for this CC bond formation. 相似文献
24.
Takeshi SasakiHirotsugu Takizawa Kyota UhedaTakahiro Yamashita Tadashi Endo 《Journal of solid state chemistry》2002,166(1):164-170
Two new high-pressure phases of binary boron-sulfur compounds, B2S3-II and B2S3-III, were synthesized at 3-6.2 GPa. A single crystal of B2S3-III was grown and the structure was determined (tetragonal, space group I41/a, a=16.086(2) Å, c=30.488(4) Å; V=7888(1) Å3, Z=100, R=3.0% and Rw=2.8% for 3047 observed data [I>3.00σ(I)]. The structure of B2S3-III consists of two kinds of macrotetrahedra built up from 20 and 34 BS4-tetrahedra. These macrotetrahedra connect each other to form an interpenetrating zincblende-type structure by sharing BS4-tetrahedra at the corners of those. B2S3-III is anticipated having a rather disordered structure. From the UV-Vis diffuse reflectance spectrum, the optical band gap of B2S3-III was estimated to be 3.7 eV. 相似文献
25.
Mikio Hori Tadashi Kataoka Hiroshi Shimizu Akihiko Tomoto 《Tetrahedron letters》1981,22(37):3629-3632
1-Benzoyl-2-methy1-3,4-dihydro-2-thianaphthalene () underwent novel intermolecular 1,4-rearrangement in refluxing toluene to give an enol ether , while rearrangement of 2-phenyl derivative proceeded intramolecularly in refluxing xylene to afford a 1,4-rearranged enol ether . On the other hand, ylides were refluxed in alcohols to afford some ring-opened products . 相似文献
26.
6-Cyanomethylene ( 2 ), which was prepared via 1 by substitution with malononitrile, has been catalytically hydrogenated to the α-(aminomethylene)-9-(methoxymethyl)-9H-purine-6-acetonitrile ( 3 ) in good yield using N,N-dimethylformamide-benzene as solvent over Pd-C under medium pressure. Intermediate 3 was derived to aldehyde 5 by hydrolysis with acid or base. Substitution of 3 with amines gave the corresponding alkylamines 6 and 7 . Reaction of 3 with hydrazine and acetamidine hydrochloride gave pyrazole derivative 8 and pyrimidine derivative 9 , respectively. 相似文献
27.
The behavior of aluminum compounds in animals was made clear by using non-destructive neutron activation analysis instead
of radiotracer method. Basic aluminum sucrose sulfate (BASS) and dried aluminum hydroxide gel (DAHG) were orally administered
to rats. The residual BASS and DAHG on gastric walls of rats were determined by neutron activation analysis. It was obtained
the following results that BASS was found at the longer time in the stomach. For reason, it is seemed that BASS is hydrolyzed
in gastric juice. And it could not find the aluminum in liver, kidney and spleen. 相似文献
28.
Hideki Namba Okihiro Tokunaga Tadashi Tanaka Yoshimi Ogura Shinji Aoki Ryoji Suzuki 《Radiation Physics and Chemistry》1993,42(4-6):669-672
The fundamental research work with simulated coal-fired flue gas was performed in JAERI to get basic data for electron beam treatment of flue gas from thermal power plants in Japan. The standard condition of the experiments was set to be the same as that of next large scale pilot test in Nagoya. The concentrations of NOx and SOx were 225 ppm and 800 ppm, respectively. The temperature of the system was 65°C. The effect of multiple irradiation was observed for NOx removal. The target SOx and NOx removals (94% and 80%, respectively) with low NH3 leakage (less than 10 ppm) were achieved at 9 kGy irradiation with 0.9 NH3 stoichiometry during 7 hours continuous operation. The facility for the pilot plant (12,000 Nm3/hr) has just built at the site of Shin-Nagoya power plant of Chubu Electric Power Company and will be started in full operation in November 1992. 相似文献
29.
The racemic structure of (1RS,3RS)-1,2,3,4-tetrahydro-6,7-dihydroxy-1-methyl-3-isoquinolinecarboxylic acid [(1RS,3RS)-1] was examined based on the melting point, solubility, and IR spectrum, with the aim of optical resolution by preferential crystallization. (1RS,3RS)-1 was indicated from these results to exist as a conglomerate. The successive optical resolution by preferential crystallization of (1RS,3RS)-1 yielded (1S,3S)- and (1R,3R)-1 with optical purities of 85--95% at 66--81% degrees of resolution, which were fully purified by recrystallization. 相似文献
30.
Muliadi Ramli Nasrullah Idris Kenichi Fukumoto Hideaki Niki Fujio Sakan Tadashi Maruyama Koo Hendrik Kurniawan Tjung Jie Lie Kiichiro Kagawa 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1379-1389
A TEA CO2 laser (350 mJ–1.5 J, 10.6 μm, 200 ns, 10 Hz) was focused onto a metal sub-target under He as host gas at 1 atmospheric pressure with a small amount of impurity gas, such as water and ethanol vapors. It was found that the TEA CO2 laser with the help of the metal sub-target is favorable for generating a strong, large volume helium gas breakdown plasma at 1 atmospheric pressure, in which the helium metastable-excited state was then produced overwhelmingly. While the metal sub-target itself was never ablated. The helium metastable-excited state produced after the strong helium gas breakdown plasma was considered to play an important role in exciting the atoms. This was confirmed by the specific characteristics of the detected H emission, namely the strong intensity with low background, narrow spectral width, and the long lifetime. This technique can be used for gas and solid samples analysis. For nonmetal solid analysis, a metal mesh was introduced in front of the nonmetal sample surface to help initiation of the helium gas breakdown plasma. For metal sample, analysis can be carried out by combining the TEA CO2 laser and an Nd–YAG laser where the Nd–YAG laser is used to ablate the metal sample. The ablated atoms from the metal sample are then sent into the region of helium gas breakdown plasma induced by the TEA CO2 laser to be excited through the helium metastable-excited state. This technique can be extended to the analysis of other elements, not limited only to hydrogen, such as halogens. 相似文献