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11.
12.
Summary The simultaneous stereospecific assay of four stereoisomers of diltiazem hydrochloride in bulk drug and aqueous solution was
developed using HPLC on a Chiralcel OF column. The four isomers were quantitated with good precision by the internal standard
method. The chiral inversion of (+)-cis-diltiazem hydrochloride in vitro, stability of its (2S, 3S) configuration in the solid
and aqueous states was examined by HPLC. Chiral inversion of (+)-cis-diltiazem hydrochloride was not observed in the solid
state, and its (2S, 3S) configuration was stable to heat, humidity and light. Chiral inversion of (+)-cis-diltiazem hydrochloride
(2S, 3S) was observed in aqueous solution under UV, but not in aqueous solution stored at 80°C for 5h nor under visible light
for 10 h. The (+)-cis-diltiazem hydrochloride (2S, 3S) epimerized to (+)-trans-diltiazem hydrochloride (2R, 3S) with a half-life
of 5h in aqueous solution under UV but the reverse chiral inversion of (+)-trans-diltiazem hydrochloride (2R, 3S) to (+)-cis-diltiazem
hydrochloride (2S, 3S) was not observed. 相似文献
13.
14.
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
15.
A hybrid approach combining energy density analysis with the interaction energy decomposition method
We propose a new analysis technique for characterizing molecular interactions that combines an energy decomposition scheme, such as the Kitaura-Morokuma decomposition method, with energy density analysis, which partitions the total energy of the system into atomic contributions. The combined scheme, termed Interaction-EDA, enables us to estimate the local contribution of interaction energy components, such as electrostatic, exchange, polarization, and charge transfer. The evaluation of the local interaction energy is rather important in large systems. For a numerical assessment, the Interaction-EDA method is applied to the process of CO adsorption on Si(100) - (2 x 1) surface. 相似文献
16.
Sasaki M Kawanishi E Nakai Y Matsumoto T Yamaguchi K Takeda K 《The Journal of organic chemistry》2003,68(24):9330-9339
Metalated O-silyl cyanohydrins of beta-silyl-alpha,beta-epoxyaldehyde have been found to serve as functionalized homoenolate equivalents by a tandem sequence involving base-promoted ring opening of the epoxide, Brook rearrangement, and alkylation of the resulting allylic anion. On the basis of mechanistic studies involving competitive experiments using the diastereomeric cyanohydrins, we propose a reaction pathway involving a silicate intermediate 36 formed by a concerted process via an anti-opening of the epoxide followed by the formation of an O-Si bond. 相似文献
17.
Masahiro Manabe Asako Tokunaga Hideo Kawamura Hajime Katsuura Masaki Shiomi Koichi Hiramatsu 《Colloid and polymer science》2002,280(10):929-935
In the micellar solution of SDS, the partition coefficient (Kx) of following branched alkanols at infinite dilution was determined by applying a differential conductivity method: the alkanols used were i-CmH2m+1OH (m=4-9, i=1-5) in which the position of OH group (i) shifts from an end to the center of a hydrocarbon chain. The method provides two significant quantities, d!/dXam and dCsf/dCaf in addition to Kx. The following results have been obtained. (1) The dependence of Kx on i indicates that the hydrophobicity of alkanol is weakened with increasing i, whereas the increase in m strengthens the hydrophobicity. (2) The degree of counterion disossiation of micelles (!) is accelerated by the solubilized alkanols in micelles (mole fraction: Xam) and the acceleration rate, d!/dXam (=0.17), depends on neither m nor i. (3) In the bulk water, the monomerically dissolved alkanols (concentration: Caf) depresses the concentration of free monomer surfactant (Csf), and the depressing rate, dCsf/dCaf, in micellar solution is identical with the corresponding quantity, ((CMC/(Ca)o at CMC. 相似文献
18.
A procedure of analysis for small-angle X-ray scattering (SAXS) data has been established to obtain density fluctuation of supercritical fluids near the critical point. It is indispensable for the certain analysis to utilize both of high-quality SAXS data measured under stable thermodynamic condition and accurate P–ρ–T data in supercritical region. As a standard example, SAXS measurements have been performed for supercritical CO2, which is a suitable sample satisfying the condition for both experiment and analysis. The measurements were carried out along four isothermal conditions at reduced temperature of Tr = T/Tc = 1.020, 1.022, 1.043 and 1.064. Comparing the experimental density fluctuation with calculated one from the most reliable equation of state, the differences are within 8% at most. 相似文献
19.
Complexes of the type (n-C
n
H2n
+1NH3)2SnX6 (0n 4 and X=Cl or Br) have been investigated with a variety of physico-chemical techniques. The structural phase transitions were found in some of these complexes. The temperature dependence of the Mössbauer spectral absorption area for (C2H5NH3)2SnCl6 and (C2H5NH3)2SnBr6 changed sharply at phase transition temperatures. The temperature dependences for (n-C4H9NH3)2SnCl6 and (n-C4H9NH3)2SnBr6 decreased gradually with an increase in temperature. The correlation between the temperature dependence of the spectral absorption area and the motion of n-C
n
H2n+1NH3
+ ions is discussed. 相似文献
20.
The nature of active titanium species for epoxidation of olefins with H2O2 and t-butyl hydroperoxide has been investigated for titanium silicalite (TS-1), titania silica (TiO2/SiO2) prepared by a sol-gel method, and titanium oxide supported on silica by a CVD method (TiO2/SiO2-CVD). IR and XANES analyses suggested that Ti in TiO2/SiO2 and TiO2/SiO2-CVD has a tetrahedral configuration bonded to SiO2 and that in TS-1 has a configuration composed of >Ti=O or related to it. Their configurations are closely related to their reactivities for epoxidation of olefins in which the former works with t-butyl hydroperoxide and the latter with H2O2. 相似文献