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991.
The chemical shifts of the N-methyl protons of a number of N-methylated-1,2,4-triazoles were studied. Substitution of methyl and methylthio groups in position 3 causes upfield shifts of the N-methyl signals, while substitution of α-pyridyl, γ-pyridyl, and phenyl groups causes downfield shifts. In 3,5-disubstituted 1,2,4-triazoles, substituents in positions 3 and 5 have additive effects on the chemical shifts of N-methyl groups, so that the chemical shifts of the N-methyl groups of such compounds can be calculated. In this way, it was possible to assign the peaks of mixtures of N-monomethylated derivatives obtained by methylation of 1,2,4-triazoles. 相似文献
992.
Tsugio Hamada Kei-ichi Iida Kenji Mitsuda 《Journal of Thermal Analysis and Calorimetry》1997,48(5):981-988
The YBCO superconductor was synthesized with BaF2. The synthesis temperature of the specimen with BaF2 was to be considerably lower than that for the unused one. The BaF2 decomposes during the heat treatment, and does not influence the structure and critical temperature. The critical current density,J c, in the specimen is 1×108 A/m2 at 77 K and 0.5T. However,J c is actually lower for the QMG specimen because the Y2BaCuO5 particles are larger than those of the QMG specimen. 相似文献
993.
Masayuki Yamane 《Journal of Sol-Gel Science and Technology》2006,40(2-3):273-279
Two unique commercial applications of the sol-gel process in Japan are presented. One application involves alkoxide-derived
nanometer-sized silica particles used in the final polishing of silicon wafers for the fabrication of integrated circuits.
The particles are cocoon-like in shape and have almost replaced conventional abrasives because of the advantages over spherical
particles of similar size in terms of obtaining high polishing efficiency for good surface finish. The other application concerns
the treatment of paper with an alkoxide solution for water repellent and oil resistance properties, which leads to new products
for disposable tableware or cooking ware for microwave oven use. 相似文献
994.
This paper describes a data processing system of monitors with a personal computer for a radioisotope laboratory. A monitoring system includes 6 area, 6 dust, and 3 gas monitors. Monitor signals through a multiplexer were fed to the personal computer which has analogue ports. Processed data were displayed on a color CRT, stored on a 5 inch mini floppy disk, and printed out as a report. We developed a data processing program with BASIC language. This system largely reduced manpower required to estimate radiation levels in the laboratory. The personal computer has sufficiently enough ability to construct a digital monitoring system for a small radioisotope laboratory. 相似文献
995.
Cai X Sakamoto M Hara M Tojo S Ouchi A Sugimoto A Kawai K Endo M Fujitsuka M Majima T 《The journal of physical chemistry. A》2005,109(17):3797-3802
Stepwise photocleavage of naphthylmethyl-oxygen (C-O) bonds of mono(substituted-methyl)naphthalenes [1- and 2-ROCH2Np, R = 4-benzoylphenyl (BP), phenyl (Ph), and methyl (CH3)] and bis(substituted-methyl)naphthalenes [1,8-(ROCH2)2Np and 1,4-(ROCH2)2Np, R = BP and Ph] was observed to give the naphthylmethyl radicals (NpCH2* or ROCH2NpCH2*) in almost 100% yield with two-step or three-step excitation by the two-color two-laser or three-color three-laser irradiation, respectively, at room temperature. The C-O bond cleavage quantum yields of 1-PhOCH2Np, 2-PhOCH2Np, 1,8-(PhOCH2)2Np, and 1,4-(PhOCH2)2Np were higher than those of 1-BPOCH2Np, 2-BPOCH2Np, 1,8-(BPOCH2)2Np, and 1,4-(BPOCH2)2Np. No C-O bond cleavage occurred from 1,8-(HOCH2)2Np and 2-CH3OCH2Np in the higher triplet excited state (T(n)). The experimental results show that the C-O bond cleavage was determined not only by the position of the substituents on Np but also by the type of the substituents. The C-O bond cleavage of 1-ROCH2Np was more efficient than that of 2-ROCH2Np. In the case of 1,8-(ROCH2)2Np and 1,4-(ROCH2)2Np (R = BP and Ph), the first C-O bond cleavage from the T(n) states occurred to give ROCH2-substituted naphthylmethyl radicals (1,8- and 1,4-ROCH2NpCH2*) when the T1 states, generated with the 308-nm first laser irradiation, were excited using the 430-nm second laser. The second C-O bond cleavage occurred when 1,8- and 1,4-ROCH2NpCH2* in the ground state [1,8- and 1,4-ROCH2NpCH2*(D0)] were excited to the excited states [1,8- and 1,4-ROCH2NpCH2*(D(n))] using the third 355-nm laser during the three-color three-laser flash photolysis at room temperature. It was revealed that acenaphthene was produced as the final product during the stepwise C-O bond cleavages of 1,8-(BPOCH2)2Np and 1,8-(PhOCH2)2Np. This is a successful example of stepwise cleavage of two equivalent C-O bonds in a molecule using the three-color three-laser photolysis method. 相似文献
996.
Masayuki Enomoto Yoshio Ito Tsutomu Katsuki Masaru Yamaguchi 《Tetrahedron letters》1985,26(10):1343-1344
Alkylation of lithiated -(benzyloxyacetyl)--2,5-bis(mehtoxyymethoxymethyl)- pyrrolidine proceeded with high stereoselectivity (≥96% de) and subsequent transformations of the alkylated products gave synthetically useful α-benzyloxy acids or α-hydroxy acids of high enantiomeric purity. 相似文献
997.
Inoue M Yamashita S Tatami A Miyazaki K Hirama M 《The Journal of organic chemistry》2004,69(8):2797-2804
The right wings (13 and 14) of ciguatoxins were synthesized highly stereoselectively. Key transformations in the synthesis are (i) an oxiranyl anion strategy to attach the H ring, (ii) intramolecular carbonyl olefination to cyclize the J ring, (iii) regio- and stereoselective reduction of the epoxyacetal to install the C42-stereocenter, and (iv) stereoselective reductive etherification to construct the K ring. The present procedure greatly improved the stereoselectivity and efficiency in comparison to a previous synthesis. Remarkably, only 23 steps were required from monocyclic I ring 5 to construct the ciguatoxin right wings. The high practicality of the present synthesis ensures a sufficient supply of these complex fragments for total syntheses and biomedical applications. 相似文献
998.
Keijiro Taga Shigetaka Hamada Hideto Fukui Hiroshi Yoshida Keiichi Ohno Hiroatsu Matsuura 《Journal of Molecular Structure》2002,610(1-3):85-97
Raman and infrared spectra of propylgermane, CH3CH2CH2GeH3, and its Ge-deuterated analog, CH3CH2CH2GeD3, were investigated in their gaseous, liquid and solid states. The normal coordinate treatment was carried out by density functional theory (DFT) calculation, using B3LYP/6-31G* and 6-311++G** basis sets, and the corresponding fundamental vibrations were assigned. The trans (T) and gauche (G) forms around the central C–C bond coexisted in the gaseous and liquid states and only the T form existed in the solid state. From the temperature dependent measurements of the Raman spectra in the liquid state, the enthalpy difference was found to be ΔH(T−G)=−0.36±0.02 kcalmol−1 with the T form being more stable. The energy differences between the isomers obtained by DFT calculations were ΔE(T−G)=−0.46 kcalmol−1 and ΔE(T−G)=−0.87 kcalmol−1 by the 6-31G* basis set and 6-311++G** basis set, respectively. 相似文献
999.
Samori S Hara M Ho TI Tojo S Kawai K Endo M Fujitsuka M Majima T 《The Journal of organic chemistry》2005,70(7):2708-2712
[structure: see text] Photoreaction of trans-4'-benzyl-5-styrylfuran (trans-BSF) has been studied by the 355-nm laser flash photolysis (LFP) in CH2Cl2 using a Nd3+:YAG laser (30 ps, 5 mJ pulse(-1) or 5 ns, 30 mJ pulse(-1)). Transient fluorescence and absorption spectra assigned to the singlet excited trans-BSF were observed during the 30-ps LFP, whereas a transient absorption spectrum with two peaks at 400 and 510 nm, assigned to the trans-fused dihydrophenanthrene (DHP)-type intermediate (DP1), was observed during the 5-ns LFP. It is clearly suggested that a two-photon absorption process is involved in the formation of DP1. The first photoreaction is the photoisomerization of trans-BSF, which occurs to give cis-BSF. The second photoreaction process is photocyclization of cis-BSF, which occurs to give DP1 decaying with the half lifetime (tau1/2) of 2.8-4.0 micros to produce another DHP-type intermediate (DP2) with an absorption peak at 400 nm in the absence of O2, through [1,9]-hydrogen shift. DP2 decayed with tau1/2 > 500 micros to give the product through aromatization. In O2-saturated CH2Cl2, DP1 decayed with tau1/2 = 250 ns to give a radical intermediate (X) with two peaks at 410 and 510 nm, through hydrogen abstraction of DP1 by O2. X decayed with tau1/2 = 150 micros to give the product through successive hydrogen abstraction. 相似文献
1000.
Tadano-Aritomi K Hikita T Kubota M Kasama T Toma K Hakomori SI Ishizuka I 《Journal of mass spectrometry : JMS》2003,38(7):715-722
A novel plasmal conjugate of galactosylsphingosine (psychosine), Gro1(3)-O-plasmal-O-6Galbeta-sphingosine (glyceroplasmalopsychosine), was analyzed by electrospray ionization and liquid secondary ion mass spectrometry with low- or high-energy collision-induced dissociation (CID). In the product ion spectra of the [M + H](+) ions, [M + H - glycerol](+) ions arising from the loss of a glycerol were predominant. Unexpectedly, CID of the [M + H - glycerol](+) ion produced an outstanding ion, [(M + H - glycerol) - Hex](+), which required the loss of the galactose from inside the molecule. This ion was greatly reduced in the spectra of N,N-dimethyl derivatives, indicating that the [(M + H - glycerol) - Hex](+) ion is formed from an intramolecular rearrangement with migration of the plasmal residue to the free amino group of sphingosine. It would be expected that the rearrangement occurs simultaneously with the elimination of glycerol or a rearranged [M + H](+) ion leads to the elimination of glycerol, to form a Schiff base-type [M + H - glycerol](+) ion, from which the terminal galactose could be removed by the normal mechanism of glycosidic cleavage. On the other hand, the [M + Na - glycerol](+) ion derived from the sodiated molecule did not produce an ion corresponding to the rearrangement reaction, possibly owing to a higher stability of the sodiated ions against conformational changes. 相似文献