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排序方式: 共有73条查询结果,搜索用时 31 毫秒
1.
Hidetake Sakuraba Yoshio Tananaka Fujio Toda 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(2):195-204
The asymmetric Michael addition of aromatic thiols to 2-cyclohexenone and maleic acid esters has been carried out by utilizing their crystalline cyclodextrin complexes suspended in water. The best chiral induction, 30% enantiomeric excess (ee), was achieved in combinations of 2-cyclohexenone and octyl maleate with the crystalline -cyclodextrin complex of benzenethiol (method A) to afford (S)-3-phenylthiocyclohexanone and (S)-octyl-2-phenylthiosuccinate, respectively, whereas the reaction of benzenethiol with 2-cyclohexenone included in -cyclodextrin (method B) inversely induced the chiral recognition to give the (R)-adduct with 4–9% ee. 相似文献
2.
Hidetake Sakuraba Toshimori Nakai Yoshio Tanaka 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):829-839
Asymmetric halogenation and hydrohalogenation oftrans-cinnamic acid have been achieved in the microcrystals of cyclodextrin complexes. The bromination of the organic acid in the cavity of -cyclodextrin gave theerythro-dibromide in 40 % optical yield which was much larger than that from the resolution treatment of the racemic dibromide with -cyclodextrin and the absolute configuration was opposite in sign. The asymmetric induction in the gas-solid reaction was not due to optical resolution but to the reaction itself which was influenced by the chiral frame of cyclodextrin. The reaction shows the molecular size effect that the acid in the cavity of -cyclodextrin reacted with smaller hydrogen bromide but did not with larger bromine and chlorine. In contrast, the guest molecule in the wider cavity of -cyclodextrin reacted with bromine and chlorine as well as hydrogen bromide. The stereospecificities of the gas-solid halogenations of the acid in -cyclodextrin were similar to those of the both reactions in the solid state and in carbon tetrachloride solution without -cyclodextrin: bromination of the acid yieldederythro-2, 3-dibromo-3-phenylpropionic acid stereospecifically in 100 % in three different conditions, but chlorination gave an excess ofthreo-2, 3-dichloro-3-phenylpropionic acid to theerythro-isomer in 7287 % yields. 相似文献
3.
Kashiwagi T Ohkoshi S Seino H Mizobe Y Hashimoto K 《Journal of the American Chemical Society》2004,126(16):5024-5025
We have prepared a pillared layer magnetic material containing a noncoordinated aromatic molecule, [{MnII(pyrimidine)(H2O)}2{MnII(H2O)2}{WV(CN)8}2](pyrimidine)2.2H2O. This compound has one-dimensional channels (6.2 x 2.1 A) that are occupied by noncoordinated pyrimidine. The magnetization versus temperature plots showed the magnetic phased transition temperature (TC) was 47 K. The magnetization versus external magnetic field plots showed that the saturation magnetization (MS) value was 13.0 muB at 2 K. This MS value indicates that an antiferromagnetic interaction operates between the WV (S = 1/2) and MnII (S = 5/2) ions. The magnetic hysteresis loop showed that the coercive field (HC) was 17 G at 2 K. 相似文献
4.
Tatsuro Ouchi Hidetake Miyazaki Hidetoshi Arimura Fumitaka Tasaka Atsushi Hamada Yuichi Ohya 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1426-1432
Amphiphilic AB‐type diblock copolymers composed of hydrophobic poly(L ‐lactide) (PLA) segments and hydrophilic poly(glycolic acid lysine) [poly(Glc‐Lys)] segments with amino side‐chain groups self‐associated to form PLA‐based polymeric micelles with amino surfaces in an aqueous solution. The average diameter of the loose core–shell polymeric micelles for poly(Glc‐Lys) [number‐average molecular weight (Mn) = 1240]‐b‐PLA (Mn = 7000) obtained by a dimethyl sulfoxide/water dialysis method was estimated to be about 50 nm in water by dynamic light scattering measurements. The size and shape of the obtained polymeric micelles were further observed with transmission electron microscopy and atomic force microscopy. To investigate the possibility of applying the obtained PLA‐based polymeric micelles as bioabsorbable vehicles for hydrophobic drugs, we tested the entrapment of drugs in poly(Glc‐Lys) (Mn = 1240)‐b‐PLA (Mn = 7000) micelles and their release with doxorubicin as a hydrophobic drug. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1426–1432, 2002 相似文献
5.
Hidetake Sakuraba Hiroshi Maekawa 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):41-45
The two modified β-cyclodextrin (β-CD) derivatives having catechol-type ligand (2,3- and 3,4-dihydroxy groups on the benzoate
ring) were synthesized. The chiral catalytic activity of their MoV and CuII complexes was examined in the asymmetric oxidation of aromatic sulfides using hydrogen peroxide in water (pH 6.0). The oxidation
with the MoV complexes of two β-CD derivatives were more accelerated than that with the CuII complexes. The sign of the optical rotation of the sulfoxides obtained in the above two cases showed the opposite configuration
in the oxidation of the same sulfide. The difference of the enantioselectivity appeared also between the two complexes of
the 2,3- and 3,4-dihydroxybenzoate derivatives with the same metal ion. While the use of the MoV complexes with the catechol derivatives yielded the sulfoxides with 35–65% ee, the use of the CuII complexes gave the products with the␣opposite configuration at 26–52% ee. The chiral induction in the oxidation, observed
conversely between the␣catalysts, was reflected on the chiral conformation of the respective metal catalysts, showed in Induced
Circular Dichroism (ICD) spectra. The highest optical yield, 65%, was observed in the oxidation of butyl phenyl sulfide using
the catalytic amount (0.1 equiv) of the MoV complex with mono-6-O-(3,4-dihydroxybenzoyl)-β-CD. The reaction gave predominantly the (S)-sulfoxide in 95% chemical yield. 相似文献
6.
The generation of heterobimetallic complexes with two or three bridging sulfido ligands from mononuclear tris(sulfido) complex of tungsten [Et(4)N][(Me(2)Tp)WS(3)] (1; Me(2)Tp = hydridotris(3,5-dimethylpyrazol-1-yl)borate) and organometallic precursors is reported. Treatment of 1 with stoichiometric amounts of metal complexes such as [M(PPh(3))(4)] (M = Pt, Pd), [(PtMe(3))(4)(micro(3)-I)(4)], [M(cod)(PPh(3))(2)][PF(6)] (M = Ir, Rh; cod = 1,5-cyclooctadiene), [Rh(cod)(dppe)][PF(6)] (dppe = Ph(2)PCH(2)CH(2)PPh(2)), [CpIr(MeCN)(3)][PF(6)](2) (Cp = eta(5)-C(5)Me(5)), [CpRu(MeCN)(3)][PF(6)], and [M(CO)(3)(MeCN)(3)] (M = Mo, W) in MeCN or MeCN-THF at room temperature afforded either the doubly bridged complexes [Et(4)N][(Me(2)Tp)W(=S)(micro-S)(2)M(PPh(3))] (M = Pt (3), Pd (4)), [(Me(2)Tp)W(=S)(micro-S)(2)M(cod)] (M = Ir, Rh (7)), [(Me(2)Tp)W(=S)(micro-S)(2)Rh(dppe)], [(Me(2)Tp)W(=S)(micro-S)(2)RuCp] (10), and [Et(4)N][(Me(2)Tp)W(=S)(micro-S)(2)W(CO)(3)] (12) or the triply bridged complexes including [(Me(2)Tp)W(micro-S)(3)PtMe(3)] (5), [(Me(2)Tp)W(micro-S)(3)IrCp][PF(6)] (9), and [Et(4)N][(Me(2)Tp)W(micro-S)(3)Mo(CO)(3)] (11), depending on the nature of the incorporated metal fragment. The X-ray analyses have been undertaken to clarify the detailed structures of 3-5, 7, and 9-12. 相似文献
7.
Isao Yamaguchi Hidetake Ishii Tatsuaki Sakano Kohtaro Osakada Takakazu Yamamoto 《应用有机金属化学》2001,15(3):197-203
1,1′‐Ferrocenedithiol reacts with di(4‐methoxyphenyl)silane, diphenylsilane, and di(4‐fluorophenyl)silane in the presence of RhCl(PPh3)3 catalyst to give mixtures of 2,2‐diaryl‐1,3‐dithia‐2‐sila[3]ferrocenophanes (1a–3a) and ? (Fc? S? SiAr2? S) n? (Fc = 1,1′‐ferrocenylene; 1b: Ar = C6H4OMe‐4; 2b: Ar = Ph; 3b: Ar = C6H4F‐4). The products are isolated and characterized by NMR spectroscopy and elemental analyses. The polymers 1b–3b, obtained from a toluene‐soluble fraction of the products, show GPC elution patterns corresponding to Mn values of 2700–4600 (polystyrene standards). The UV–vis spectra of the ferrocenophanes and polymers exhibit a d–d transition peak at about 440 nm, while the polymers show a π–π* transition peak at 320–330 nm. The cyclic voltammograms of 3a (Ar = C6H4F ? 4) and 3b show a reversible redox of the iron center at 0.27 V and 0.35 V (Ag+/Ag) respectively. Reaction of 1,1′‐ferrocenedimethanol with diphenylsilane in the presence of RuCl2(PPh3)3 catalyst results in selective formation of 3,3‐diphenyl‐2,4‐dioxa‐3‐sila[5]ferrocenophane ( 4 ), whose structure was determined by X‐ray crystallography. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
8.
T. Honda T. Oi T. Ossaka T. Nozaki H. Kakihana 《Journal of Radioanalytical and Nuclear Chemistry》1989,130(1):81-97
Hot spring water and crater lake water samples were analyzed for their rare earth elements: (REE's) by neutron activation method, which, in the irradiation, sample preparation, incorporated a coprecipitation process in which aluminium was used as a collector. Ten REE's, La, Ce, Sm, Eu, Gd, Tb, Dy, Tm, Yb and Lu, were consequently detected and determined at the ppb level with satisfactory precision. It was shown that the aluminium coprecipitation is effective in enhancing concentrations of the REE's and reducing the amounts of interfering nuclides before neutron irradiation. 相似文献
9.
10.
Microwave-assisted synthesis method enabled the preparation of the (tris-acetylacetonate)(2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolinate) terbium(III) (Tb(acac)3(dmdpphen)) complex with outstanding high green luminescence. This method is appropriate for green chemistry and energy-saving processes. The Tb(acac)3(dmdpphen) complex has good thermal stability. Emission peaks are assigned to the f-f transitions of the Tb3+. The Tb(acac)3(dmdpphen) complex is expected to be used in functional materials of electronic products. 相似文献