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181.
Takemura H Kon N Kotoku M Nakashima S Otsuka K Yasutake M Shinmyozu T Inazu T 《The Journal of organic chemistry》2001,66(8):2778-2783
The C-F.M(+) interaction was investigated by employing a cage compound 1 that has four fluorobenzene units. The NMR ((1)H, (13)C, and (19)F) spectra and X-ray crystallographic analyses of 1 and its metal complexes showed clear evidence of the interaction. Short C-F.M(+) distances (C-F.K(+), 2.755 and 2.727 A; C-F.Cs(+), 2.944 and 2.954 A) were observed in the crystalline state of K(+) subset 1 and Cs(+) subset 1. Furthermore, the C-F bond lengths were elongated by the interaction with the metal cations. By calculating Brown's bond valence, it is shown that the contribution of the C-F unit to cation binding is comparable or greater than the ether oxygen in the crystalline state. Representative spectroscopic changes implying the C-F.M(+) interaction were observed in the NMR ((1)H, (13)C, and (19)F) spectra. In particular, (133)Cs-(19)F spin coupling (J = 54.9 Hz) was observed in the Cs(+) complex. 相似文献
182.
Excitation-energy dependence of phosphorescence quantum yield of benzaldehyde vapour at low pressure
The phosphorescence quantum yield of benzaldehyde vapour was measured at low pressure (down to 2 mtorr) as a function of excitation wavelength. The quantum yield is essentially constant in the range of excitation energy corresponding to the S1(n,π*) state, but it decreases very rapidly as the excitation energy is raised to the value corresponding to S2(π,π*), indicating that the phosphorescence property of the benzaldehyde molecule varies, depending on the nature of the singlet state to which the molecule is initially excited. 相似文献
183.
Takemura N Takahashi K Tanaka H Ihara Y Ikemoto A Fujii Y Okuyama H 《Photochemistry and photobiology》2002,76(6):657-663
Peroxidizability of fatty acids in the air is roughly proportional to the number of double bonds, but in vivo peroxidation proceeds in a more complex manner. Here, we compared the effects of dietary and topically applied oils enriched with linoleic acid (LA, 18:2n-6) or alpha-linolenic acid (ALA, 18:3n-3) on UV-induced skin injury in a strain of hairless mice. The UVB-induced erythema score was significantly lower in mice with topically applied creams containing LA and ALA than in mice with the basal cream; no significant increase in the score was detected in the ALA group compared with the LA group. However, dietary ALA inhibited the increase in erythema score after UVB irradiation compared with LA. The peroxidizability index of the skin total lipids was significantly higher, but UVB-induced prostaglandin E2 (PGE2) production was significantly lower in the group fed an ALA-rich diet compared with the group fed an LA-rich diet. The levels of thiobarbituric acid-reactive substances, estimated in the presence of butylated hydroxytoluene in the assay mixture, were not affected by UVB treatment or by the dietary fatty acids, but the severity of the skin lesion was associated with PGE2 levels. These results indicate that the type of fatty acids, n-6 or n-3, is critical for the suppression of UVB-induced skin lesion when the skin fatty acids are modified by dietary manipulation. Anti-inflammatory activity of dietary flaxseed oil with relatively high ALA and low LA contents was demonstrated in UVB-irradiated hairless mice. 相似文献
184.
Yoshihiro Sohtome Dr. Nobuko Takemura Keisuke Takada Rika Takagi Toshitsugu Iguchi Kazuo Nagasawa Prof. Dr. 《化学:亚洲杂志》2007,2(9):1150-1160
Catalytic enantio‐ and diastereoselective nitroaldol reactions were explored by using designed guanidine–thiourea bifunctional organocatalysts under mild and operationally simple biphasic conditions. These catalytic asymmetric reactions have a broad substrate generality with respect to the variety of aldehydes and nitroalkanes. Based on this catalytic nitroaldol process, straightforward syntheses of cytoxazone and 4‐epi‐cytoxazone were achieved. These catalytic nitroaldol reactions require KI as an additive for highly asymmetric induction; it operates by inhibiting the retro mode of the reaction. On the basis of studies of structure and catalytic‐activity relationships, a plausible guanidine–thiourea cooperative mechanism and a transition state of the catalytic reactions are proposed. Drastic substituent effects on the catalytic properties of this catalyst may lead to the development of new chiral surfactants. 相似文献
185.
The allylic-type diindium reagents A and B were prepared from 3-bromo-1-iodopropene (1a) and 4-bromo-2-iodobut-2-ene (1b), respectively, and their reactions with electrophiles were investigated. The diindium reagents A and B were initially reacted with imines and the resulting vinylindium compounds were then treated with organic halides in the presence of Pd(PPh(3))(4) to give linear N-aryl and N-tosyl homoallylic amines. Diindium A is stable in a small amount of water in solvent, whereas B is easily protonated to give a crotylindium reagent. The reaction of B with benzaldehyde gives mainly the 1,3- and 1,5-diols via a spontaneous coupling with two molecules of the aldehyde, in contrast to A, which reacts with one molecule of carbonyl compounds to give the vinylindium compounds. 相似文献
186.
Takushi Kurihara Hirokatsu Tanno Shigetaka Takemura Shinya Harusawa Ryuji Yoneda 《Journal of heterocyclic chemistry》1993,30(3):643-652
C-nor-4,6-Secocamptothecin 2 , 4-ethyl-4-hydroxy-6-(2-quinolinyl)-1H-pyrano[3,4-c]pyridine-3,8(4H,7H)-dione, lacking the C-ring of camptothecin 1 , and its related compounds 3 and 4 were prepared from ethyl quinoline-2-carboxylate 7 . By an analogous reaction sequences, synthesis of 6-(2-pyridinyl)-1H-pyrano[3,4-c]-pyridine-3,8(4H7H)-dione derivatives 5 and 6 , which contain the B, D, and E ring of 1 , were achieved. 相似文献
187.
Takemura H Nakashima S Kon N Yasutake M Shinmyozu T Inazu T 《Journal of the American Chemical Society》2001,123(38):9293-9298
The C-F...M(+) interaction was investigated by observation of the NMR spectroscopic changes and complexation studies between metal cations and the cage compounds 1 and 2 which have fluorobenzene units as donor atoms. As a result, the interaction was detected with all of the metal cations which form complexes with 1 and 2. The stability of the complexes of 1 and 2 was determined by the properties of the metal cations (ionic radii and degree of hydrolysis), not by the hard-soft nature of the cations. Crystallographic analyses of Tl(+) subset 1 and La(3+) subset 2 provided structural information (interatomic distances and bond angles), and the bond strengths, C-F...M(+), O...M(+), and N...M(+), were estimated by Brown's equation based on the structural data. Short C-F...Tl(+) (2.952-3.048 A) distances were observed in the complex Tl(+) subset 1. The C-F bond lengths in the complexes, Tl(+) subset 1 and La(3+) subset 2, are elongated compared to those of the metal-free compounds. Interestingly, no solvent molecules including water molecules were coordinated to La(3+) in the La(3+) subset 2. The stabilization energy of cation-dipole interaction was calculated on the basis of the data from X-ray crystallographic analysis, and it is roughly consistent with the (-)Delta H values estimated in solution. Thus, the C-F...M(+) interaction can be expressed by the cation-dipole interaction. This result explains the fact that compound 1 which has fluorine atom as hard donor strongly binds soft metals such as Ag(+) and Tl(+). Furthermore, it was concluded that the fluorobenzene unit has a poor electron-donating ability compared to that of ether oxygen or amine nitrogen, and thus the ratio of the coordination bond in C-F...M(+) is small. The specific and remarkable changes in the (1)H, (13)C, and (19)F NMR spectra were observed accompanied by the complexation between M(+) and the hosts 1 and 2. These spectral features are important tools for the investigation of the C-F...M(+) interaction. Furthermore, F.Tl(+) spin couplings were observed at room temperature in the Tl(+) subset 1, 2 (J(F-Tl) = 2914 Hz for Tl(+) subset 1 and 4558 Hz for Tl(+) subset 2), and these are clear and definitive evidence of the interaction. 相似文献
188.
Tomoyuki Ando Kazuhiro Irie Koichi Koshimizu Takeshi Takemura Hoyoku Nishino Akio Iwashima Naohito Takeda Susumu Nakajima Isao Sakata 《Photochemistry and photobiology》1993,57(4):629-633
Abstract— A new water-soluble porphyrin derivative, 2,4-bis(1-decyloxyethyl)-deuteroporphyrinyl–6,7-bisaspartic acid(C–10-DP), and its metal complexes (Ga, In, Sn, Zn, Mn, Cu, Ni and Fe) were examined for their physicochemical properties (absorption, fluorescene, triplet lifetime and partition coefficient) and photocytotoxicity on HeLa cells. The five derivatives with longer(>1ms) triplet lifetimes (free base, Zn, Ga, In and Sn complexes) exhibited remarkable photocytotoxicity, and the other derivatives (Mn, Cu, Ni and Fe), which had or were deduced to have fairly short (<0.01 ms) triplet lifetimes, manifested no photocytotoxicity, indicating that the triplet lifetime of these derivatives played a significant role in their photocytotoxicity. Cellular fluorescence due to C10-DP and its gallium complex was observed mainly on the plasma membrane at the concentrations showing significant photocytotoxicity with low (<32.6%) cytotoxicity in the dark(2–10 μM). 相似文献
189.
190.
Organo‐Iodine(III)‐Catalyzed Oxidative Phenol–Arene and Phenol–Phenol Cross‐Coupling Reaction
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Dr. Koji Morimoto Kazuma Sakamoto Takao Ohshika Dr. Toshifumi Dohi Prof. Dr. Yasuyuki Kita 《Angewandte Chemie (International ed. in English)》2016,55(11):3652-3656
The direct oxidative coupling reaction has been an attractive tool for environmentally benign chemistry. Reported herein is that the hypervalent iodine catalyzed oxidative metal‐free cross‐coupling reaction of phenols can be achieved using Oxone as a terminal oxidant in 1,1,1,3,3,3‐hexafluoropropan‐2‐ol (HFIP). This method features a high efficiency and regioselectivity, as well as functional‐group tolerance under very mild reaction conditions without using metal catalysts. 相似文献