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101.
Tsuboyama A Takiguchi T Okada S Osawa M Hoshino M Ueno K 《Dalton transactions (Cambridge, England : 2003)》2004,(8):1115-1116
The synthesis, structure, and photophysical properties of a new cyclometalated dinuclear iridium complex, (ppy)2Ir(mu-BPB)Ir(ppy)2 [ppy = 2-phenylpyridine, BPB = 1,4-bis(pyridin-2-yl)benzene], have been investigated. 相似文献
102.
Sumio Kato Masataka Ogasawara Mikio Sugai Shinichi Nakata 《Catalysis Surveys from Asia》2004,8(1):27-34
Studies on the role of oxygen vacancy in structural change of nonstoichiometric perovskites and a property of oxygen-deficient perovskite-related K2NiF4 compounds are reviewed.The structural changes on which the authors focused are cation ordering and lattice distortion. The relationship between the distortion and oxygen vacancy was investigated by comparing the structures of Sr2(Sr1-xMx)TaO6-d (M = Ca2+ and Nd3+) solid solutions. It was found that distortion of a perovskite-type lattice decreased with an increasing amount of oxygen vacancies. In order to investigate the relationship between the cation ordering on octahedral sites and oxygen vacancy, structures of stoichiometric Sr2-xLaxCo1-yTa1+yO6 and oxygen-deficient Sr2-xLaxMg1-yTa1+yO6-d solid solutions were compared. The authors' work reveals that the cation ordering affects the amount of oxygen vacancies in addition to cation charge and size. 相似文献
103.
Shigendo Enomoto Ken-ichi Kumagai Taro Tamura Miki Hasegawa Kyoko Nakada Toshihiko Hoshi Michio Kobayashi 《Monatshefte für Chemie / Chemical Monthly》2004,29(1):471-481
Fluoranthene (FA) forms a 1:1 van der Waals complex with benzene in cyclohexane. The 1H NMR spectrum of this complex shows that the FA moiety in the complex state has five kinds of hydrogen atoms and that the 1H NMR peaks assigned to the protons attached to the naphthalene skeleton are largely shifted to higher magnetic field on complex formation with benzene. These observations indicate that the complex takes the structure of CS symmetry, in which the benzene molecule mainly interacts with the electronic system localized on the naphthalene moiety of FA. The present ab initio calculations reproduce well the 1H NMR spectral shifts mentioned above and the experimentally predicted CS structure of the complex. According to the PPP calculations for the electronic absorption spectral changes on the complex formation, the FA-benzene complex is considered to take a sandwich type structure. 相似文献
104.
To find an effective extraction and removal method for palladium(II), which is one of the main fission products from an acidic nuclear spent fuel solution, the extraction behavior of palladium(II) from a nitric acid medium by an acidic chelating extractant, 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5-one (HPMTP) and a tertiary amine of high molecular weight, tri-n-octylamine (TOA), has been studied by spectrophotometry. A noticeable antagonistic extraction effect was observed in the extraction system under the given conditions. To understand this phenomenon, a preliminary investigation was performed to explain the mechanism of this reaction. According to the theory of corresponding solutions (TCS), the association reaction between HPMTP and TOA is proposed in the organic phase. An associated species, HPMTP·TOA, formed through hydrogen bonding in a chloroform medium might be the main reason why an antagonistic extraction effect occurred. The association constant between HPMTP and TOA was calculated to be 2.86±0.05. 相似文献
105.
Takashi Kumagai Tomohiro Anki Akihito Konishi Hiroyuki Kurata Kenta Katsumoto Takeshi Kawase 《Tetrahedron》2010,66(46):8968-8973
Carboxylic acids were heated at 150 °C in DMF in the presence of 1.25 equiv of thionyl chloride to give corresponding N,N-dimethylamides in good yields. Tandem chlorination and amidation reactions occurred in the one-pot procedure. Dicarboxylic acids needed prolonged reaction time to produce bisamides in good yields. Some benzamides were efficiently converted into corresponding 1,2-diaryl-1,2-diketones (benzils) under acyloin condensation conditions in the presence of 4,4′-di-tert-butylbiphenyl (DBB) in THF. Ultrasonic irradiation effectively accelerates the reaction, but it is not critical. However, the presence of DBB is fatal to the reaction. Although a few synthetic methods for benzils from benzoic acids have been reported so far, this method is one of the most convenient and highly reproducible procedures. 相似文献
106.
Satoshi Motodate Takuya Kobayashi Mikio Fujii Prof. Tomoyuki Mochida Dr. Taichi Kusakabe Shigeki Katoh Prof. Hiroyuki Akita Prof. Keisuke Kato 《化学:亚洲杂志》2010,5(10):2221-2230
Bis(oxazoline)‐palladium(II) catalyzed carbonylation of homopropargyl alcohols afforded acyclic methoxyacrylate 2 and 6‐membered lactone 3a , 3b , 3d , 3e , 3f , 3g , 3h , 3i , 3j , 3k in good combined yield. In the case of propargyl alcohols, 5‐membered lactones 3p , 3q , 16 were obtained in moderate yields. The one‐pot synthesis of kawa lactones 3a , 3r , 3s and formal synthesis of dihydroxycystothiazole A and dihydroxycystothiazole C are presented. To elucidate the stereochemistry of (+)‐annularin G and (?)‐annularin H, the first asymmetric syntheses of these natural products were achieved. 相似文献
107.
108.
Asako Shimada-Fujiwara Akiko Hoshi Yutaka Kameo Mikio Nakashima 《Journal of chromatography. A》2009,1216(18):4125-4127
The dependence of Th recovery on hydrofluoric acid (HF) concentration in nitric acid (HNO3) solutions (1–5 mol/dm3) containing 1 × 10−6 mol/dm3 of Th and various concentrations of HF and the elution behavior were studied using a commercially available UTEVA (for uranium and tetravalent actinide) resin column. Thorium recovery decreased with an increase in HF concentration in the sample solutions. The concentration of HF at which Th recovery started to decrease was ∼1 × 10−4 mol/dm3 in 1 mol/dm3 HNO3 solution, ∼1 × 10−3 mol/dm3 in 3 mol/dm3 HNO3 solution, and ∼1 × 10−2 mol/dm3 in 5 mol/dm3 HNO3 solution. When Al(NO3)3 (0.2 mol/dm3) or Fe(NO3)3 (0.6 mol/dm3) was added as a masking agent for F− to the Th solution containing 1 × 10−1 mol/dm3 HF and 1 mol/dm3 HNO3, Th recovery improved from 1.4 ± 0.3% to 95 ± 5% or 93 ± 3%. Effective extraction of Th using UTEVA resin was achieved by selecting the concentration of HNO3 and/or adding masking agents such as Al(NO3)3 according to the concentration of HF in the sample solution. 相似文献
109.
Harada S Kumagai N Kinoshita T Matsunaga S Shibasaki M 《Journal of the American Chemical Society》2003,125(9):2582-2590
Full details of our direct Michael addition of unmodified ketones using new asymmetric zinc catalysis are described. Et(2)Zn/(S,S)-linked-BINOL complexes were successfully applied to direct 1,4-addition reactions of hydroxyketones. The first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was effective for 1,4-addition of 2-hydroxy-2'-methoxyacetophenone (3). Using 1 mol % of (S,S)-linked-BINOL 1 and 2 mol % of Et(2)Zn, we found that a 1,4-addition reaction of beta-unsubstituted enone proceeded smoothly at 4 degrees C to afford products in high yield (up to 90%) and enantiomeric excess (up to 95%). In the case of beta-substituted enones, however, the first generation Et(2)Zn/(S,S)-linked-BINOL 1 = 2/1 system was not at all effective. The second generation Et(2)Zn/(S,S)-linked-BINOL 1 = 4/1 with MS 3A system was developed and was effective for various beta-substituted enones to afford products in good dr, yield (up to 99%), and high enantiomeric excess (up to 99% ee). With the Et(2)Zn/1 = 4/1 systems, catalyst loading for beta-unsubstituted enone was reduced to as little as 0.01 mol % (substrate/chiral ligand = 10 000). The new system was also effective for 1,4-addition reactions of 2-hydroxy-2'-methoxypropiophenone (9) to afford chiral tert-alcohol in high enantiomeric excess (up to 96% ee). Mechanistic investigations as well as transformations of the Michael adducts into synthetically versatile intermediates are also described. 相似文献
110.
Asako Shimada Tomoko Haraga Akiko Hoshi Yutaka Kameo Mikio Nakashima Kuniaki Takahashi 《Journal of Radioanalytical and Nuclear Chemistry》2010,286(3):765-770
In order to analyze actinide elements in radioactive metal waste, the dissolution and chemical separation conditions were optimized. The surfaces of a type 304 stainless steel plate and of pipe waste sampled from the prototype advanced thermal reactor (Fugen) were dissolved in mixed acid solution (HNO3:HCl:H2O = 1:1:4). The resulting solution was evaporated to dryness and dissolved with 2 mol/dm3 of HNO3 to prepare sample solutions. In order to analyze trivalent actinide elements in the sample solution containing a large amount of Fe(III) (>0.1 g) using TRU resin, the effect of Fe(III) concentration on the recovery of Am(III) and reduction effect of Fe(III) to Fe(II) with ascorbic acid were studied. On the basis of results of this study, chemical separation scheme was constructed and Pu and Am in the sample solutions were separated. Thorium and U in the sample solutions were separated with UTEVA resin. High recoveries for all experimented elements were obtained from the analysis of spiked sample solutions, the effectiveness of the method was confirmed. 相似文献