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501.
Miyoko Kamigauchi Yuko Miyamoto Kinuko Iwasa Makiko Sugiura Zjujiro Nishijo Narao Takao Toshimasa Ishida Yasuko In Masatoshi Inoue 《Helvetica chimica acta》1990,73(8):2171-2178
The solid-state and solution conformations of (+)-chelidonine ( 1 ), a biologically active alkaloid, were determined by X-ray diffraction and 1H-NMR spectroscopy, X-Ray diffraction analysis revealed a conformer with B/C ‘anti-type’ cis conjunction, a half-chair of ring B , and a twist half-chair of ring C. One H2O molecule per one alkaloid molecule was cocrystallized and stabilized by H-bonding with OH? C(11). Analysis of the thermal behavior of the crystal showed more thermal stability in the monohydrate than the anhydrate. The NMR measurement of concentration and temperature dependences in CDCl3 and in (CD3)2SO suggested that the OH group of 1 was intramolecularly H -bonded to N(5) in (CD3)2SO and intermolecularly H-bonded to the solvent in CDCl3. Conformational-energy calculations by the MNDO method showed that the intramolecular H -bond was little affected by the conformational stabilization of 1 . 相似文献
502.
[reaction: see text] A novel synthetic approach to N-alkyl-N'-arylimidazolium salts has been developed on the basis of addition of imidazoles to arynes. A variety of N-alkyl-N'-arylimidazolium salts can be synthesized straightforwardly in modest to good yields. Furthermore, utility of the resulting imidazolium salts has been demonstrated by the palladium-catalyzed Suzuki-Miyaura coupling of aryl chlorides. 相似文献
503.
The [2,3]-Wittig rearrangement of properly designated (E)- and (Z)-crotyl propargyl ether system has been shown to exhibit a remarkably high degree of threo- and erythro -selection, respectively, and the stereochemical outcomes are discussed on mechanistic grounds. Some useful transformations of the rearrangement product are also described within the context of the formal total synthesis of (±)-oudemansin. Further, the high level of diastereoselection is maintained in the reaction of the α-methylcrotyl counterparts, together with the exclusive formation of the (E)-olefinic bond. 相似文献
504.
Crotyltrichlorosilanes reacted with ketone-derived N-benzoylhydrazones in DMF without any catalyst. This is the first example of highly stereospecific crotylation of ketimine analogues leading to both syn- and anti-N'-tert-alkyl-N-benzoylhydrazines. Different reactivities between (Z)- and (E)-crotylsilanes in terms of yields and selectivities were observed. A kinetic study with both geometrically pure (Z)- and (E)-crotylsilanes was performed. These reactions are most likely to proceed via a cyclic chairlike transition state where the aromatic group of hydrazones takes an axial position. Both diastereomers of allylation products can be converted to the corresponding alpha,alpha-disubstituted homoallylic amines without epimerization. 相似文献
505.
Hirokazu Shimooka Ken-Ichi Yamada Seiji Takahashi Makoto Kuwabara 《Journal of Sol-Gel Science and Technology》1998,13(1-3):873-876
Transparent, partially-crystallized nanostructured barium titanate (BaTiO3) monolithic xerogels (dried at 90°C) have been successfully synthesized via hydrolysis of Ba, Ti alkoxide precursor solutions in a concentration range of 1.0 mol/l with addition of water with a molar ratio of H2O/Ba 6.3. Transparent monolithic xerogels obtained from a precursor solution of 1.0 mol/l remained transparent even after firing at 500°C in oxygen, although the degree of their transparency was considerably decreased. Firing at temperatures above 500°C yielded translucent ceramics of BaTiO3, and ultimately, firing above 600°C resulted in normal opaque ceramic bodies. Those obtained from a more concentrated precursor solution of 1.2 mol/l were, on the other hand, still transparent after firing at 600°C in oxygen, and turned opaque at 700°C. The results demonstrate that the materials retained their transparency even after pyrolysis of organic compounds involving exothermic oxidation at temperatures in the range of 200 to 400°C. The densification behavior of transparent BaTiO3 monolithic xerogels obtained was found to be excellent; for example, those derived from a 1.0 mol/l precursor solution could be sintered to form monolithic BaTiO3 ceramics with a relative sintered density of about 94% and an average grain size of 1 m by firing at 1100°C for 2 h in oxygen. 相似文献
506.
[reaction: see text] The product distribution of the three-component reaction of aldehydes, arylamines, and THF was dependent on a radical initiator, preferentially giving the corresponding THF adducts of imines with dimethylzinc and adducts of aldehyde with triethylborane. 相似文献
507.
Takenobu T Chi DH Margadonna S Prassides K Kubozono Y Fitch AN Kato K Iwasa Y 《Journal of the American Chemical Society》2003,125(7):1897-1904
Intercalation of C(70) with europium affords two kinds of magnetic compounds, a canted antiferromagnet Eu(x)C(70) (x approximately 3) and a ferromagnet Eu(x)C(70) (x approximately 9) with transition temperatures (T(C)) of 5 and 38 K, respectively. The Curie constants in the paramagnetic phase and the saturation moment in the ferromagnetic phase are both understood by the full moment of Eu(2+) for both systems. The structure of Eu(3)(-)(delta)C(70) (delta approximately 0.27) is pseudo-monoclinic, derived by a simple deformation of the parent face-centered cubic (fcc) structure. Eu(9)(-)(delta)C(70) (delta approximately 0.2) forms an fcc structure, in which cuboctahedral clustering of Eu(2+) ions is observed in the enhanced size octahedral holes. The observed T(C) of the Eu(9)(-)(delta)C(70) ferromagnet is comparable to or larger than those of simple binary Eu-based ferromagnets, such as Eu chalcogenides or carbides, despite the low atomic ratio of Eu in the chemical formulas. This can be understood by the short Eu(2+)-Eu(2+) distances and high coordination numbers permitted by the multiple occupation by Eu(2+) ions of the expanded octahedral interstitial sites in higher fullerene-based solids. 相似文献
508.
Saha S Koner S Tuchagues JP Boudalis AK Okamoto K Banerjee S Mal D 《Inorganic chemistry》2005,44(18):6379-6385
Mono-, di-, and trinuclear copper-azido moieties have been synthesized by varying the size of the countercations. [Bu4N]+ yielded a [Cu2(N3)6]2- copper-azido moiety in [Bu4N]2[Cu2(mu(1,1)-N3)2(N3)4], 1, and [Pr4N]+ yielded a [Cu3(N3)8]2- moiety in {[Pr4N]2[Cu3(mu(1,1)-N3)4(N3)4]}n, 2, in which symmetry-related [Cu3(N3)8]2- moieties are doubly mu(1,1)-azido bridged to form unprecedented infinite zigzag chains parallel to the crystallographic a-axis. In the case of [Et4N]+, the mononuclear species [Et4N]2[Cu(N3)4], 3, has been formed. All complexes have been characterized structurally by single-crystal X-ray analysis: 1, C32H72N20Cu2, triclinic, space group P, a = 10.671(9) A, b = 12.239(9) A, c = 10.591(5) A, alpha = 110.01(4) degrees , beta = 93.91(5) degrees , gamma = 113.28(5) degrees , V = 1160.0(1) A3; 2, C24H56N26Cu3, monoclinic, space group P2(1)/n, a = 8.811(2) A, b = 37.266(3) A, c = 13.796(1) A, beta = 107.05(1) degrees , V = 4330.8(10) A(3); 3, C16H40N14Cu, tetragonal, space group I4/m, a = b = 10.487(1) A, c = 12.084(2) A, V = 1328.9(3) A3. The variable-temperature magnetic susceptibility measurements showed that although the magnetic interaction in [Bu4N]2[Cu2(mu(1,1)-N3)2(N3)4], 1, is antiferromagnetic (J = -36 cm(-1)), it is ferromagnetic in {[Pr4N]2[Cu3(mu(1,1)-N3)4(N3)4]}n, 2 (J = 7 cm(-1)). As expected, the [Et4N]2[Cu(N3)4] complex, 3, is paramagnetic. 相似文献
509.
Y Naito M Sugiura Y Yamaura C Fukaya K Yokoyama Y Nakagawa T Ikeda M Senda T Fujita 《Chemical & pharmaceutical bulletin》1991,39(7):1736-1745
Various catechol derivatives (beta-substituted 3,4-dihydroxystyrenes, 1-substituted 3,4-dihydroxybenzenes, and 6-substituted 2,3-dihydroxynaphthalenes) were synthesized and their inhibition of 5-lipoxygenase was assayed. Their structure-activity relationships were examined quantitatively with substituent and structural parameters and regression analysis. The variations in the inhibitory activity were explained in bilinear hydrophobic parameter (log P) terms, and steric (molecular thickness) and electronic (proton nuclear magnetic resonance (1H-NMR) chemical shift of the proton adjacent to the catechol group) parameter terms. The hydrophobicity of the inhibitor molecule was important, and the optimum value of logP was about 4.3-4.6, beyond which inhibition did not increase further. A lower electron density of the aromatic ring containing the catechol group and the greater thickness of the lipophilic side chains were unfavorable to the activity. The results added a physicochemical basis for the selection of candidate compounds for developmental studies. 相似文献
510.
The chiral ligand controlled asymmetric conjugate addition reaction of lithium N-allyl-N-(tert-butyldimethylsilyl)amide to alkenoates proceeded smoothly to give, after protodesilylation, the corresponding 3-allylaminoalkanoates with high enantioselectivities in high yields. The allyl group on the nitrogen atom was easily removable to afford 3-aminoalkanoates. 相似文献