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21.
Heating a toluene solution of Cp*(CO)(C5H5N)FeSiMe2NPh2 led to insertion of pyridine into the iron-silicon bond to form Cp*(CO)Fe[eta3(C,C,C)-C5H5NSiMe2NPh2]. 相似文献
22.
Three acyclic polythioethers containing 2-thienyl units at both ends were synthesized and the effect of substituent on the extraction of copper(II) was studied. The methyl groups in the terminal thiophene ring have imparted an appreciable degree of increase in the percent extraction of copper(II), while the introduction of chlorine atoms into the 2-thienyl unit resulted in the reverse effect. Among the counter dye anions examined, tetrabromophenolphthalein ethylester was the best one for copper(II) extraction. The composition of extracted species was evaluated to be 122 (Cu(II)/polythioether/dye anion). Quantitative extraction of copper(I) was attained as complexes with various triphenylmethane dyes, i.e., bromocresol green, bromothymol blue, bromo-phenol blue and pyrogallol red. Copper(I) in organic phase was completely back-extracted with 2 mole/l sulfuric acid containing 10% hydrogen peroxide. 相似文献
23.
Akiko Tsuhako Jing-Qian He Mariko Mihara Naoko Saino Sentaro Okamoto 《Tetrahedron letters》2007,48(52):9120-9123
Ketones and aldehydes were effectively reduced to the corresponding alcohols (or their silyl ethers) by the reaction with CaH2 and R3SiCl in the presence of a catalytic amount of ZnCl2. In the absence of the carbonyl substrate, the reagent reduced R3SiCl to the corresponding hydrosilane under mild reaction conditions. 相似文献
24.
Summary A new type of end-point indication for the complexometric titration of iron(III) is proposed. A 10% carbon tetrachloride solution of Amberlite LA-1 is applied for the extraction of the thiocyanate complexes. Very sharp color change of the organic phase from red to pale yellow gives the accurate end point for titrations with 0.01M EDTA as in the Variamine Blue B method.
Zusammenfassung Eine neue Methode zur Endpunktanzeige bei der komplexometrischen Titration, von Eisen(III) wird vorgeschlagen. Eine 10%ige Tetrachlorkohlen-stofflösung von Amberlite LA-1 wird zum Ausschütteln der Thiocyanatkomplexe angewendet. Ein sehr scharfer Farbumschlag der organischen Phase von rot nach blaßgelb zeigt den Endpunkt für Titrationen mit 0,01-m ÄDTA so genau wie bei der Variaminblau-B-Methode an.相似文献
25.
Fukuji Higashi Yuko Mihara Ikuo Takahashi Wen-Hsin Chen Tech-Chou Chang 《Journal of polymer science. Part A, Polymer chemistry》1985,23(11):2851-2856
The reaction promoted by Vilsmeier adduct derived from tosyl chloride (TsCl) with N,N-dimethylformamide (DMF) was successfully applied to the preparation of copolyesteramides of high molecular weights directly from aromatic dicarboxylic acids, diamines, and bisphenols. The polycondensation was significantly affected by the reaction of activated dicarboxylic acids with bisphenols and diamines. Addition of a mixture of bisphenols and diamines likely caused gelation of the reaction mixtures, resulting in insoluble polymers, especially with high mol % diamines. Stepweise addition of them, however, gave the homogeneous reaction mixtures and copolymers of better solubility. These phenomena were studied in terms of sequence length distribution of polyester units, which was estimated by thermal analyses of the random copolymers prepared under various conditions for the initial reaction with bisphenols. 相似文献
26.
Yan YG Li QX Huo SJ Ma M Cai WB Osawa M 《The journal of physical chemistry. B》2005,109(16):7900-7906
A versatile two-step wet process to fabricate Pt, Pd, Rh, and Ru nanoparticle films (simplified as nanofilms hereafter) for in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) study of electrochemical interfaces is presented, which incorporates an initial chemical deposition of a gold nanofilm on the basal plane of a silicon prism with the subsequent electrodepostion of desired platinum group metal overlayers. Galvanostatic electrodeposition of Pt, Rh, and Pd from phosphate or perchloric acid electrolytes, or potentiostatic electrodeposition of Ru from a sulfuric acid electrolyte, yields sufficiently "pinhole-free" overlayers as evidenced by electrochemical and spectroscopic characterizations. The Pt group metal nanofilms thus obtained exhibit strongly enhanced IR absorption. In contrast to the corresponding metal films electrochemically deposited directly on glassy carbon and bulk metal electrodes, the observed enhanced absorption for the probe molecule CO exhibits normal unipolar band shapes. Scanning tunneling microscopic (STM) images reveal that fine nanoparticles of Pt group metals are deposited around wavy and stepped bunches of Au nanoparticles of relatively large sizes. This ubiquitous strategy is expected to open a wide avenue for extending ATR surface-enhanced IR absorption spectroscopy to explore molecular adsorption and reactions on technologically important transition metals, as exemplified by successful real-time spectroscopic and electrochemical monitoring of the oxidation of CO at Pd and that of methanol at Pt nanofilm electrodes. The spectral features of free water molecules coadsorbed with CO on Pt, Pd, Rh, and Ru are also discussed. 相似文献
27.
Tomoyuki Manaka Shin‐Ichiro Nagayama Wannaporn Desadee Naoki Yajima Takuya Kumamoto Toshiko Watanabe Tsutomu Ishikawa Masatoshi Kawahata Kentaro Yamaguchi 《Helvetica chimica acta》2007,90(1):128-142
Nucleophilic ring‐opening reactions of 3‐aryl‐1‐benzylaziridine‐2‐carboxylates were examined by using O‐nucleophiles and aromatic C‐nucleophiles. The stereospecificity was found to depend on substrates and conditions used. Configuration inversion at C(3) was observed with O‐nucleophiles as a major reaction path in the ring‐opening reactions of aziridines carrying an electron‐poor aromatic moiety, whereas mixtures containing preferentially the syn‐diastereoisomer were generally obtained when electron‐rich aziridines were used (Tables 1–3). In the reactions of electron‐rich aziridines with C‐nucleophiles, SN2 reactions yielding anti‐type products were observed (Table 4). Reductive ring‐opening reaction by catalytic hydrogenation of (+)‐trans‐(2S,3R)‐3‐(1,3‐benzodioxol‐5‐yl)aziridine‐2‐carboxylate (+)‐trans‐ 3c afforded the corresponding α‐amino acid derivative, which was smoothly transformed into (+)‐tert‐butyl [(1R)‐2‐(1,3‐benzodioxol‐5‐yl)‐1‐methylethyl]carbamate((+)‐ 14 ) with high retention of optical purity (Scheme 6). 相似文献
28.
Yoshida T Sakakibara K Asami M Chen KH Lii JH Allinger NL 《Journal of computational chemistry》2003,24(3):319-327
The MM3 force field has been extended to deal with the lithium amide molecules that are widely used as efficient catalysts for stereoselective asymmetric synthesis. The MM3 force field parameters have been determined on the basis of the ab initio MP2/6-31G* and/or DFT (B3LYP/6-31G*, B3-PW91/6-31G*) geometry optimization calculations. To evaluate the electronic interactions specific to the lithium amides derived from the diamine molecules properly, the Lewis bonding potential term for the interaction between the lithium atom and the nonbonded adjacent electronegative atom such as nitrogen was introduced into the MM3 force field. The bond dipoles were evaluated correctly from the electronic charges on the atoms calculated by fitting to the electrostatic potential at points selected. The MM3 results on the molecular structures, conformational energies, and vibrational spectra show good agreement with those from the quantum mechanical calculations. 相似文献
29.
Tomoya Kitazume Zaiju Jiang Kana Kasai Yuma Mihara Mamie Suzuki 《Journal of fluorine chemistry》2003,121(2):205-212
The utility of reusable ionic liquid-proline (or aldolase antibody 38C2) reaction system, proceeding the aldol reactions, is described. Further, obtained α-chloro-β-hydroxy compounds were transformed to the optically active α,β-epoxy carbonyl compounds. The aldolase antibody 38C2-ionic liquid system was able to reuse in Michael additions and the reaction of fluoromethylated imines. 相似文献
30.
Houjou H Kanesato M Hiratani K Mandon D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4576-4583
Novel diiron complexes with an Fe2(mu-OMe)2 core were studied as models of the active site of nonheme iron-containing enzymes. X-ray crystal structures of the complexes showed the existence of two types of ligand folding-parallel and twisted-both of which have four virtually equivalent phenolato groups sticking out from the Fe2O2 rhombic plane. Cyclic voltammetry measurements revealed two or more distinct redox waves in a region of relatively high potential, in addition to known Fe(II)/Fe(III) redox waves in a region of lower potential. These new peaks were assigned to the high-valence state of iron atoms, that is, Fe(III)Fe(IV) and Fe(IV)Fe(IV), resonating with the phenoxyl radical(s). The split width of the redox waves ranged from 0.14 to 0.20 eV, which may be a measure of the electronic interaction of the phenolate groups through the Fe2(mu-OMe)2 core. 相似文献