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33.
Ken-ichi Sato Shoji Akai Akira Yoshitomo Yoshimitsu Takai 《Tetrahedron letters》2004,45(44):8199-8201
The merits of an indirect protecting method for hydroxyl groups using allyl groups via allyloxycarbonyl groups in the synthesis of antennary β-d-mannopyranosyl disaccharides from β-d-galactopyranosyl disaccharides were studied. Regioselective allyloxycarbonylation and conversion reactions involving simultaneous double SN2 nucleophilic substitution at C-2′ and C-4′ of benzyl O-[β-d-galactopyranosyl]-(1-4)-3,6-di-O-benzyl-2-deoxy-2-N-phthalimido-β-d-glucopyranoside were examined for comparison with the direct allylation method. The required β-d-mannopyranosyl disaccharide having proper protecting groups was obtained using this indirect method in 52% yield. In contrast, the reported direct allylation method using methyl O-(β-d-galactopyranosyl) disaccharide gave the corresponding β-d-mannopyranosyl disaccharide in only 7.5% yield. 相似文献
34.
Structure, stability, and electronic and NMR properties of [(Salen)Mn(III)](+)-derived intermediates/reactants in the epoxidation/amination of unfunctionalized olefins, namely [(Salen)Mn(V)O](+) (1-oxo), [(Salen)Mn(IV)O] (2-oxo), and [(Salen)Mn(V)N] (3), have been studied with the B3LYP density functional method. It has been shown that the (1)A, (3)A, and (5)A states of cationic 1-oxo species are virtually degenerate, while for the neutral 2-oxo species the ground (4)A state lies 6.4 kcal/mol lower than (2)A. In the nitrido species 3, the (1)A state has been shown to be the ground state in agreement with experiment. We have investigated isomerization of 1-oxo and 2-oxo species into unusual [(OSalen)Mn(III)](+) (1-N-oxo and 1-peroxo) and [(OSalen)Mn(II)] (2-N-oxo and 2-peroxo) species, respectively. For cationic species 1, the 1-N-oxo isomers are more stable (by 10-12 kcal/mol) than the 1-oxo isomer and are separated from the latter by 21-22 kcal/mol barriers. On the other hand, 1-peroxo isomers are calculated to be 14-16 kcal/mol higher than the 1-oxo isomer. For neutral species 2, however, both 2-N-oxo and 2-peroxo isomers lie significantly higher in energy than the 2-oxo isomer. It has been shown that coordination of axial imidazole ligand alters relative energies of spin states for 1- and 2-oxo species, destabilizing low-spin states. For singlet states of H(2)Salen, 1-oxo, and 3, we have calculated (1)H, (13)C, (15)N, and (17)O NMR chemical shifts using the gauge-independent-atomic orbital (GIAO) approach. 相似文献
35.
M. Takai S. Nagatomo H. Kohda C. Yada H. Sandaiji F. Takeya 《Applied Physics A: Materials Science & Processing》1994,58(4):359-363
A laser-induced thermochemical reaction has been used to etch single crystalline magnetic ferrite for industrial application to recording-head processing. Scanning focused Ar-ion laser irradiation to ferrite in flowing aqueous solutions of KOH or H3PO4 resulted in etch rates of 350–400 m/s with aspect ratios of up to 40. Metal-In-Gap (MIG) head structures with Sendust (FeAlSi) have been successfully fabricated using laser chemical processing. The MIG head fabricated by laser chemical processing showed better performance than that by conventional mechanical machining.Presented at LASERION '93, June 21–23, 1993 München (Germany) 相似文献
36.
Yukihiro Shintani Keiji Hirako Masanori Motokawa Yoshihiko Takano Masahiro Furuno Hiroyoshi Minakuchi Mitsuyoshi Ueda 《Analytical sciences》2004,20(12):1721-1723
An interconnecting technique, the "PDMS connection method", for quartz microchips in a high-pressure system is presented. The connection between quartz microchips is an essential technology for modular microfluidic devices, such as microchip-HPLC. PDMS was applied to the seal material, being spread on the seal side of the chips, and set into the metal housing. The characteristics of the PDMS connection method concerning pressure resistance and the extension of the peak were examined. The experimental results showed a good seal at 5 MPa, which seem to be sufficient for realizing microchip-HPLC utilizing a monolithic silica capillary column as a separation medium. The influence of the extra column effect on chromatographic separation was almost the same as in the case using a commercial union fitting. In addition, the PDMS connection enabled the detachability of chip-based modules with user-friendliness. Our experimental findings suggest that the novel PDMS connection method can possibly be applied as a generic technology in high-pressure microTAS. 相似文献
37.
Shin-ichi OhsugiKiyoharu Nishide Keiji OonoKazunori Okuyama Masato FudesakaSumiaki Kodama Manabu Node 《Tetrahedron》2003,59(42):8393-8398
Development of the odorless dodecyl methyl sulfide (Dod-S-Me, 1) as an alternative for dimethyl sulfide (DMS) and new odorless methods for the Corey-Kim and Swern oxidations are described. These reactions have been developed with a view toward green chemistry, utilizing Dod-S-Me (1) and common solvents instead of dichloromethane. 相似文献
38.
A direct preparative route to benzoyltrimethylsilane has been found by the reaction of benzoyl chloride with hexamethyldisilane in the presence of a specified palladium(II) complex as catalyst. 相似文献
39.
Bendazzoli Gianni L. Raimondi Mario Garetz Bruce A. George Thomas F. Morokuma Keiji 《Theoretical chemistry accounts》1977,44(4):341-350
Semiclassical calculations are carried out by two methods for the problem of collision-induced predissociation of electronically excited I2. The first method is that of surface-hopping with the Landau-Zener model. The second method is similar to surface-hopping, except that analytic continuation of the adiabatic potential energy surfaces replaces the Landau-Zener model. Results of the calculations by the two methods compare favorably with each other and with experiment. The possible advantages of the second method are discussed.Camille and Henry Dreyfus Teacher-Scholar, Alfred P. Sloan Research Fellow. 相似文献
40.
The partial molar free energy, enthalpy, and entropy of oxygen in niobium oxides with ratios from 2.47 to 2.50 were measured with a galvanic cell in the temperature range from 1084 to 1325 K. The partial molar enthalpies of oxygen of the Nb2O5?x and V phases were observed to be nearly independent of composition, indicating the presence of only weak interactions between defects. The value of the slope for the plots of log x in Nb2O5?x against log PO2 was observed to be which is interpreted in terms of a defect structure involving both singly ionized and doubly ionized oxygen vacancies. The previously proposed phase diagram in the vicinity of Nb2O5?x was confirmed by the present emf measurements. 相似文献