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101.
Substituent effects on the SmI2/Pd(0)-promoted carbohydrate ring-contraction of 5-alkynylpyranosides
The effect of substituents on the reactivity and stereoselectivity of the SmI2/Pd(0)-promoted ring-contraction of 5-alkynylpyranosides has been examined using substrates substituted only at selected positions. While formation of 2-ethynylcyclopentanols takes place efficiently, an internal alkyne did not afford the expected product. The presence of peripheral alkoxy substituents leads to variable stereoselectivities that depend on the number and orientation of such groups. Thus, an isolated OBn substituent at C(3) (carbohydrate numbering) exerts a significant stereochemical control while additional substitution with the same group at C(4) either enhances or drastically reduces stereoselectivity depending on its orientation (α or β, respectively). 相似文献
102.
Chen S. Yang X. Gao Sh. Hu R. Shi Q. 《Journal of Thermal Analysis and Calorimetry》2004,76(1):265-274
The solid complexes of Cr(NO3)3 with L-α-amino acids (AA=Val, Leu, Thr, Arg, Phe and Try) have been prepared in 95% alcoholic, the compositions of which were identified as the general
formula Cr(AA)2(NO3)3·2H2O by elemental and chemical analyses. The bonding characteristics of the title complexes were characterized by IR, indicating
that nitrogen and oxygen atoms in the ligands coordinated to Cr3+ in a bidentate fashion. With the aid of TG-DTG and IR techniques, the complexes were subjected to thermal decomposition in
an atmosphere of oxygen, presuming that the decompositions of the complexes consist of two steps and the complexes were decomposed
into chromium hemitrioxide after undergoing dehydration and skeleton splitting of the complexes. The constant volume energies
of combustion of the complexes were determined by a RBC-P type rotating-bomb calorimeter. According to Hess's law, the standard
enthalpies of formation of the complexes were calculated as (-1831.40±4.40), (-2542.03±6.13), (-1723.81±3.99), (-2224.31±3.02),
(-2911.61±6.53) and (-659.32±7.42) kJ mol-1, respectively.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
103.
Unsymmetrically 2,5-disubstituted 1,3,4-oxadiazoles were efficiently synthesized from the cyclization-oxidation reaction of acyl hydrazones. Also, the synthesis of the title compounds was achieved by the condensation of acyl hydrazides and aromatic aldehydes in the presence of ceric ammonium nitrate in dichloromethane. 相似文献
104.
Wen‐Bin Pan Li‐Mei Wei Li‐Lan Wei Chin‐Chung Wu Fang‐Rong Chang Yang‐Chang Wu 《中国化学会会志》2005,52(3):581-588
Oxidation of a series of phenols with cerium(IV) ammonium nitrate (CAN) in acetonitrile under mild conditions yields the mixture of corresponding nitrophenols. In the cases of methylphenols and hydroxy ‐carboxylic acids, the steric effect may reduce the nitration reaction. Compounds 3a and 4b showed selective activities to Hep 3B and Hep G2 cancer cell lines, respectively. Compound 2c showed selective activities to Hep G2 and MDA‐MB‐231 cancer cell lines. Furthermore, compound 10b showed selective activities to Hep G2, Hep 3B, MCF‐7 and MDA‐MB‐231 cancer cell lines. 相似文献
105.
S. Kittaka N. Uchida M. Katayama A. Doi M. Fukuhara 《Colloid and polymer science》1991,269(8):835-842
The colloidal stability of V2O5
nH2O was studied on the basis of the measurements of critical flocculation concentration (CFC) by metal ions, amount of ions exchanged (or intercalated), and -potential. In total, the CFC values obeyed the Schulze Hardy law and strong Hofmeister's series was found in the systems including alkaline ions. The sequence of colloidal stability of V2O5
nH2O in the electrolyte solutions was related to the intercalation of metal ions in the interlayer spaces of the solid. The largest CFC value for Li+ (87 mmol dm–3) was explained by smaller affinity of Li+ to be intercalated in V2O5
nH2O as well as smaller Hamaker constant of the intercalated solid compared to the other systems.Effect of intercalation of metal ions on the crystalline properties of the materials was measured by use of XRD and electron microscope. Under highly dehydrated condition the ions whose radii are smaller than 0.1 nm are captured in the structure of V2O5
nH2O without changing interlayer distances, while those larger than 0.1 nm increase the interlayer distance. In a saturated H2O vapor interlayer distances increased with increasing charge of intercalated ions. However, when intercalated with ions carrying the same valency the interlayer distances of the sample decreased with decrease in the hydration property of ions. Hydrolyzable Cr3+ gave exceptionally larger interlayer distances, both in a vacuum and in H2O vapor. 相似文献
106.
用密度泛函B3LYP方法研究了过渡金属钐类卡宾与乙烯的环丙烷化反应的机理. 对钐类卡宾试剂CH3SmCH2I和CH2CH2反应的反应物、中间体、过渡态和产物构型的全部结构几何参数进行了优化, 并计算了THF溶液的溶剂化效应, 用内禀反应坐标(IRC)计算和频率分析方法, 对过渡态进行了验证. 结果表明: CH3SmCH2I与CH2CH2环丙烷化反应按亚甲基转移机理(通道A)和卡宾金属化机理(通道B)都可以进行, 与锂类卡宾的反应机理相同, 通道A比通道B反应的势垒降低了14.65 kJ/mol. 溶剂化效应使通道B比通道A的反应势垒大幅度提高, 更有利于反应沿通道A进行, 而不利于通道B. 相似文献
107.
V. L. Novikov N. N. Balaneva A. M. Moiseenkov G. B. Elyakov 《Russian Chemical Bulletin》1992,41(8):1485-1494
A successful total synthesis of a biologically active pigment from plants of the Boraginaceae family was carried out with naphthazarine as the starting material, and using the 1,4,5,8-tetramethoxynaphthalene, the corresponding 2-vinyl derivative and its epoxide or a cyclopropane adduct with diazoacetic ester at the key stages. In the course of developing the scheme of the synthesis of shikalkin, its three analogs were obtained, differing in the nature of the monoterpenoid side chain.For preliminary report, see [1].Pacific Ocean Institute of Bioorganic Chemistry, Far East Branch of the Russian Academy of Sciences, 690022 Vladivostok. N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1901–1910, August, 1992. 相似文献
108.
The reactions of 2-(1-hydropolyfluoro-1-alkenyl)-4H-3,1-benzoxin-4-ones (2) with hydrazine hydrate and phenyl hydrazine were investigated. The reaction of 2 with hydrazine hydrate in ethanol under reflux condition readily gave 2-fluoroalkyl-4H-pyrazolo[5,1-b]quinazolin-9-ones (3) in high yields. The reaction of 2 with phenyl hydrazine, however, resulted in the formation of 2-(2-phenyl-5-fluoroalkyl-2H-pyrazol-3-yl) benzoic acids (7). Further treatment of 7 with PPA gave 1-phenyl-4,9-dihydro-3-fluoroalkyl-1H-pyrozolo[3,4-b]quinolin-4-ones (4) in 65-80% overall yields. 相似文献
109.
The complexes Ln(NO3)3(OPCy3)3(EtOH)x (Cy = cyclohexyl, C6H11x = 0 for Ln = Eu, Er, x = 0.5 for Ln = La, Nd and x = 1 for Ln = Tm, Yb) have been prepared by reaction of lanthanide nitrates with Cy3PO in ethanol. The single crystal X-ray structures for Ln = La, Nd, Eu, Er, Tm and Yb are reported. The structures for Ln = La–Eu have two molecules in the unit cell in which the nitrates are all bound as bidentate ligands. The unit cell for Ln = Er contains two distinct molecules; one with three bidentate nitrates and one with two bidentate and one monodentate nitrate. The Tm and Yb complexes have one molecule in the unit cell with two bidentate and one monodentate nitrate ligands. The monodentate nitrates are hydrogen bonded to ethanol in the Tm and Yb structures but not in the Er complex. The infrared spectra of the three classes of complex do not readily permit identification of the monodentate nitrate groups. Electrospray mass spectrometry indicates that redistribution/ionisation reactions occur in solution. Ions formed by solvolysis reactions are attributed to gas phase processes associated with the electrospray technique. Tandem mass spectrometry for the La, Ho and Yb complexes shows that in the gas phase loss of Cy3PO is the sole fragmentation pathway for all but the Yb complex where the higher energy required for initial fragmentation leads to a more complex fragmentation pattern. 相似文献
110.
利用改进的半微量相平衡方法研究了Y(NO3)3·3H2O-18C6-C2H5NH(18C6为18-冠-6)体系在25℃时溶解度,测定了各流相的折光率。结果指出只有一种化学计量的配合物[Y(NO3)3·18C6·3H2O·C2H5OH]生成。考查了在相平衡过程中水的行为。经分离、洗涤、浓硫酸干燥器中恒重后,通过化学分析,确定了配合物的组成为:Y(NO3)3·18C6·3H2O。用红外光谱、差热-热重分析研究了配合物的性质。并在常量情况下,研究了配合物的热失重情况。 相似文献