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91.
Nirmaljeet Kaur 《合成通讯》2018,48(1):26-31
(S,R)-Noscapine, a phthalideisoquinoline alkaloid has been used as precursor for the synthesis of chiral ionic liquids (CILs). Noscapine based CILs have been synthesized from reaction between (S,R)-noscapine and methyl iodide in acetonitrile at room temperature. The synthesized CILs have been characterized by 1H NMR, 13C NMR, EI-MS, and polarimetry techniques. These CILs have been used as organocatalysts in the enantioselective reduction of prochiral ketones to produce optically active secondary alcohols. The optically active secondary alcohols have been obtained with excellent yields and low to moderate enantiomeric excess (ee); also the complete enantiomeric excess (100% ee) has been achieved in some cases. 相似文献
92.
Abstract The IR spectra of the linkage isomers [Pd(bipy)(SCN)2] and [Pd(bipy)(NCS)2] have been determined in the C≡N stretching region (2200–2000 cm?1) and below 500 cm?1. The band shifts resulting from deuteration of the 2,2′-bipyridine (bipy) ring and 15NCS-labelling are shown to provide a ready means for distinguishing between the internal ligand modes, the μPd-N(bipy) and μPd-SCN/μPd-NCS vibrations. The assignment technique has been further extended to the complexes [Pt(bipy)(SCN)2] and [Pd(phen)(SCN)2] (phen = 1,10-phenanthroline). Finally, a comparison between the IR spectra of [Pd(bipy)(NCO)2], [Pd(bipy)(NCS)2] and [Pd(bipy)(SCN)2] reveals that the frequencies μM-NCO, μM-NCS and μM-SCN decrease in the sequence NCO > NCS > SCN. 相似文献
93.
Excess enthalpies (H
E
) for mixtures of cyclohexanone with propan-1-ol. propan-2-ol, butan-1-ol, butan-2-ol and 2-methyl propan-1-ol at 298.15 K
have been measured over the entire composition range. All mixed endothermically with the maximum values ofH
E
occurring at equimole fraction. Comments about the molecular interactions contributing to the excess enthalpies of a cyclic
ketone + an alcohol are made on the basis of these results. 相似文献
94.
John T. W. Lai Frankie W. Lau Damon Robb Peter Westh Gerda Nielsen Christa Trandum Aase Hvidt Yoshikata Koga 《Journal of solution chemistry》1995,24(1):89-102
The excess partial molar enthalpies, the vapor pressures, and the densities of dimethylsulfoxide (DMSO)–H2O mixtures were measured and the excess partial molar Gibbs energies and the partial molar volumes were calculated for DMSO and for H2O. The values of the excess partial molar Gibbs energies for both DMSO and H2O are negative over the entire composition range. The results for the water-rich region indicated that the presence of DMSO enhances the hydrogen bond network of H2O. Unlike monohydric alcohols, however, the solute-solute interaction is repulsive in terms of the Gibbs energy. This was a result of the fact that the repulsion among solutes in terms of enthalpy surpassed the attraction in terms of entropy. The data in the DMSO-rich region suggest that DMSO molecules form clusters which protect H2O molecules from exposure to the nonpolar alkyl groups of DMSO. 相似文献
95.
96.
Pietro Baraldi Gian Carlo Franchini Andrea Marchetti Gavino Sanna Lorenzo Tassi Alessandro Ulrici Giulia Vaccari 《Journal of solution chemistry》2000,29(5):489-504
Thermodynamic interactions in the ethane-1,2-diol (1) + 1,2-dimethoxyethane(2) + water (3) ternary system have been investigated in terms of the excessmolar volume, derived from density measurements at 19 different temperaturesfrom –10;dg to 80;dgC. Fourteen three-component mixtures have been considered,covering the entire composition range. The excess molar volumes are discussedin terms of conformational changes induced in each component by the presenceof another one. The results obtained support the hypothesis of the absence of anythree-component complex adducts under all experimental conditions investigated. 相似文献
97.
P. M. Carreira D. Nunes P. Valério M. F. Araújo 《Journal of Radioanalytical and Nuclear Chemistry》2009,281(1):153-156
The Nuclear and Technological Institute (Instituto Tecnológico e Nuclear—ITN) in cooperation with the International Atomic
Energy Agency (IAEA) has been conducting a nationwide survey of hydrogen (2H/1H) and oxygen (18O/16O) isotopic composition of monthly precipitation since 1988. This paper focuses on basic features of spatial and temporal
distribution of δ18O and δ2H in the precipitation over Continental Portugal derived from ITN database. Phenomenological relationships between stable
isotopes composition of precipitation and various climate-related parameters (local air temperature, distance to the Atlantic
coast, altitude, amount of precipitation) are established and discussed. 相似文献
98.
Volker Schurig 《Journal of chromatography. A》2009,1216(10):1723-1736
The retention increment approach is described which quantifies the association equilibria of a selectand and a selector in complexation and inclusion chromatography. A thermodynamic treatment of enantioselectivity based on retention phenomena in chromatography including entropy/enthalpy compensation and the isoenantioselective temperature is advanced. Kinetic parameters of enantiomerization are discussed. Non-linear effects, both existent and elusive, are described and proposed, respectively. The enantioselectivity pertaining to catalysis vs. chromatography is compared and a unified nomenclature is proposed. Through an educational effort, this account is aimed at providing a deeper insight into chemoselective aspects of chromatography thereby stimulating further research of both established and speculative phenomena of the most intriguing manifestation of chemoselectivity, that is, of enantioselectivity. 相似文献
99.
Let Y
i
, 1 ≤ i ≤ n be i.i.d. random variables with the generalized Pareto distribution W
γ,σ
with γ < 0. We define the empirical mean excess process with respect to {Y
i
, 1 ≤ i ≤ n} as in Eq. 2.1 (see below) and investigate its weak convergence. As an application, two new estimators of the negative tail
index γ are constructed based on the linear regression to the empirical mean excess function and their consistency and asymptotic
normality are obtained.
相似文献
100.
Paul Kosma Martina Strobl Andreas Hofinger Jens Ø. Duus Bent O. Petersen Klaus Bock Helmut Brade 《Monatshefte für Chemie / Chemical Monthly》2002,133(4):561-570
Summary. Methyl glycosides of Kdo and a (2→8)-linked Kdo disaccharide were prepared which contain a deuterium label at C-8 of the reducing unit. The label was introduced in fair
diastereoselectivity upon reduction of an aldehyde group using a chiral borane complex derived from N-benzyloxycarbonyl-(S)-proline which produced the 8-(S)-deuterated derivative as the major isomer. Further coupling with a Kdo bromide gave the α-(2→8)-linked disaccharide in good yield. The deprotected disaccharide serves as a model for NMR spectroscopic
studies on the side chain conformation of a carbohydrate epitope from the bacterial pathogen Chlamydia.
Received September 17, 2001. Accepted October 17, 2001 相似文献