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1.
X-ray diffraction has been used to study the nematic phases of the cis and trans isomers of an elongated molecule containing the cyclobutane group. It has been shown that these nematic phases consist of a mixture of single molecules and overlapping core dimers. It has been found that increasing the temperature of the cis isomer rapidly reduces the dimer population, whereas increasing the temperature of the trans isomer enhances the dimer population. This provides an explanation of the relatively high clearing temperature of the trans isomer. The different temperature dependences of the dimer population in the cis and trans isomers has been explained by a model involving inversion of the cylobutane group.  相似文献   

2.
Monte Carlo (MC) simulations have been carried out for mixtures of Lennard–Jones (LJ) fluids near or in the supercritical region. Excess molar enthalpy at equimolar concentration, Hp,x=0.5E, has been obtained for four kinds of model mixtures each having different combining rule for unlike interactions. The pressure and temperature dependencies of Hp,x=0.5E are investigated. The unique pressure and temperature dependencies of Hp,x=0.5E for real systems such as (ethane+ethene) in the supercritical condition have been reproduced by the present simple model systems. Excess molar internal energies at constant volumes, UV,x=0.5E, are also evaluated. They are compared with Hp,x=0.5E to investigate the volumetric contributions to Hp,x=0.5E or excess molar internal energies at constant pressure, UV,x=0.5E. Calculated UV,x=0.5E for the present model systems are quite simple compared to the excess molar internal energy at constant pressure, UV,x=0.5E. They are very small in magnitude and show linear dependencies on the density of mixtures.  相似文献   

3.
Racemic 1,1′-methylene[(1RS,1′RS,3RS,3′RS,5RS,5′RS)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] ((±)-6) derived from 2,2′-methylenedifuran has been resolved kinetically with Candida cyclindracea lipase-catalysed transesterification giving 1,1′-methylenedi[(1R,1′R,3R,3′R,5R,5′R)-8-oxabicyclo[3.2.1]oct-6-en-3-ol] (−)-6 (30% yield, 98% ee) and 1,1′-methylenedi[(1S,1′S,3S,3′S,5S,5′S)-8-oxabicyclo[3.2.1]oct-6-en-3-yl] diacetate (+)-8, (40% yield, 98% ee). These compounds have been converted into 1,1′-methylenedi[(4S,4′S,6S,6′S)- and (4R,4′R,6R,6′R)-cyclohept-1-en-4,6-diyl] derivatives.  相似文献   

4.
The 6S,7S,10R-, 6S,7S,10S-, 6R,7R,10S-, and 6R,7R,10R-stereoisomers of the juvenile hormone III bisepoxide from higher Dipteran insects have been synthesised in high stereoisomeric purity. The route involves Sharpless epoxidation of geraniol to enantiomeric epoxyalcohols, which are each elaborated via separable diastereomeric bromohydrins.  相似文献   

5.
Y. Ogata  T. Akada 《Tetrahedron》1970,26(24):5945-5951
Oxidation of phenol by aqueous alkaline peroxydisulfate to form o and p-dihydroxybenzenes has been studied. The rate is expressed as: v = k[s2O8=[PhOH], where the k value tends to increase with an increase of the concentration of alkali and a plot of log k vs pH at pH 9·5-10 is a straight line with a slope of ca unity. The effects of ionic strength, concentration of alkali and temperature on the o/p ratio has been determined. In view of these facts a probable mechanism involving a nucleophilic attack of a C atom of phenoxide ion on the peroxide oxygen of the peroxydisulfate ion has been postulated and discussed.  相似文献   

6.
Fully optimized geometries have been calculated for the title compounds at the Hartree—Fock SCF level and compared with existing experimental data. A basis set of double zeta quality has been employed. For hydrazoic acid, a calculation with a larger basis set, expected to give results near the Hartree—Fock limit, has also been performed. All of the calculations show the azide group to be slightly bent with a trans configuration around the central NN bond. Azidoethane is predicted to exist in two conformations, gauche (71°) and anti, with a negligible energy difference of 0.26 kJ mol−1 between them. Azidoethene and azidomethanal both prefer the syn orientation of the azide group with respect to the C---C or C---O bonds, the computed energy difference between the anti and syn conformations being 3.31 and 30.3 kJ mol−1 respectively.

The barrier to rotation around the C---N bond has been calculated to be 3.75 kJ mol−1 in azidomethane while in azidoethane it was 3.30 and 9.40 kJ mol−1 in the eclipsed anti-clinal (120°) and syn positions, respectively.

Complete harmonic force fields and dipole moment derivatives have been calculated for hydrazoic acid, azidomethane and for the two stable conformations of azidoethane. For azidoethane and azidomethanal only the azide part of the harmonic force field has been calculated. The theoretical harmonic force fields have been modified through scaling by a least squares refinement to the observed wavenumbers of hydrazoic acid, azidomethane and azidoethane (anti and gauche). Infrared vapour phase intensities have been calculated and theoretical spectra are presented for azidomethane and azidoethane.  相似文献   


7.
This paper presents the phosphorescence characterization of polycyclic aromatic hydrocarbons (PAHs) on solid-surface for obtaining new flow-through phosphorescence optosensors for PAHs-based on-line, immobilized onto a non-ionic resin solid support coupled to a continuous flow system and the applications for the selective determination of benzo(a)pyrene (BaP). The phosphorescent characterization of 15 PAHs, described as major pollutants by the Environmental Protection Agency (EPA) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene and dibenzo(a,h)anthracene) has been carried out. The experimental variables (heavy atom, deoxygenation and organic solvent in samples) for obtaining different possibilities for developing mono and multi-parameter PAH sensors and the conditions for PAH screening have been carefully studied and the experimental conditions to determination of BaP in presence of other PAHs in water samples have been optimized.  相似文献   

8.
A method to evaluate empirical values of L3 magnetic sub-state photoionisation cross-sections has been reported. Preliminarily, the method requires scanning of the existing experimental data on L X-ray fluorescence (XRF) cross-sections for energy dependence of L/Lℓ cross-section ratio. After assuring the energy dependence of L/Lℓ cross-section ratio, the ratio is used for the determination of the alignment parameter A2. Thus, the determined A2 value, along with the available data on the sub-shell photoionisation cross-sections σLi and the Coster–Kronig transition probabilities fij, is used to evaluate magnetic sub-state photoionisation cross-sections σLi(m) for and . The method has been used to evaluate L3 magnetic sub-state photoionisation cross-sections for four elements with Z82, from the measured L XRF cross-sections. To the best of our knowledge, until this date neither theoretical nor semi-empirical data on magnetic sub-state photoionisation cross-sections for these elements has been available, for comparison with such cross-section values and to establish the superiority of one data set over the others.  相似文献   

9.
The microwave spectra of cyclohexylphosphine have been recorded in the 18.0–26.5 GHz region. A-type rotational transitions have been assigned. The ground state rotational constants were determined to be A = 4153.75 ± 0.23, B = 1362.31 ± 0.01 and C = 1104.14 ± 0.01 MHz for C6H11PH2, and A = 4030.03 ± 0.25, B = 1312.72 ± 0.01 and C = 1072.33 ± 0.01 MHz for C6H11PD2. From the experimental rotational constants, it is suggested that the assigned spectra have resulted from the chair conformation with the gauche phosphine group in an equatorial position (CESG). This form is believed to be the most populated conformational isomer in the gas phase.  相似文献   

10.
Structures of AgAF6 (A=Sb, Ta) have been determined by X-ray single crystal studies at ambient temperatures. AgSbF6 crystallizes in space group Ia with a=979.85(4) pm, V=9.4076(12)×108 pm3, z=8, and AgTaF6 crystallizes in space group P42/mcm with a=499.49(4) pm, c=960.51(8) pm, V=2.3964(6)×108 pm3, z=2. Only the crystal system and cell parameters were obtained for the isomorphic AgNbF6; primitive tetragonal, a=497.80(10) pm, b=960.40(10) pm, V=2.3799(12)×108 pm3, z=2. The results of the Raman spectroscopy of AgAF6 support the obtained structures. The structures are discussed by comparing with that of AgPF6 and AgAsF6 which have recently been determined in a series of our study.  相似文献   

11.
Physico-chemical properties of the binary system NaHSO4–KHSO4 were studied by calorimetry and conductivity. The enthalpy of mixing has been measured at 505 K in the full composition range and the phase diagram calculated. The phase diagram has also been constructed from phase transition temperatures obtained by conductivity for 10 different compositions and by differential thermal analysis. The phase diagram is of the simple eutectic type, where the eutectic is found to have the composition X(KHSO4) = 0.44 (melting point ≈ 406 K). The conductivities in the liquid region have been fitted to polynomials of the form κ(X) = A(X) + B(X)(T − Tm) + C(X)(T − Tm)2, where Tm is the intermediate temperature of the measured temperature range and X, the mole fraction of KHSO4. The possible role of this binary system as a catalyst solvent is also discussed.  相似文献   

12.
The preverecynarmin(12), (+)-(1E,3E,7E,11E)-cembra-3,7,11-tetraen-6yl acetate,was first isolated in 1990 from both Armina maculata and its prey,the pennatulacean coral Veretillum cynomorium with other there briarane diferpenoids and cembene-C((1E,3E,7E,11E)-cembra-l,3,7,11-tetraen1. As far as we known, the bioactive test and total synthesis of 12 have not been reported yet. Herein we wish to describe the first total synthesis of (±)-preverecynarmin (12).  相似文献   

13.
An enantiodivergent preparation of (+)-(R)- and (−)-(S)-3-amino-4,4-dimethyl-1-phenylpyrrolidin-2-one, (R)- and (S)-9, and several derivatives, from 4,4-dimethyl-1-phenylpyrrolidin-2,3-dione, 4, and (R)- or (S)-1-phenylethylamine, (R)- or (S)-5, as the chirality transfer agents, is described. Amine (S)-9 has also been used as a chiral auxiliary in a diastereoselective Michael reaction.  相似文献   

14.
(13S)-hydroxyneocembrene(18), a cembranoid which was isolated in 1988 from soft coral Sarcophyton trocheliophorum1, has been shown to be an effective inductor of the release of labeled glucose from the lecithincholesterol liposomes and have cytostatic activities2. The geometrical structure and absolute configuration of 18 have been defined to be 1S, 2E, 7E, 11E, 13S. Herein, we report the total synthesis of (±)-13hydroxyneocembrene(18).  相似文献   

15.
A computer programme for determination of equilibrium constant (K) and enantiomer ratio (E) in biocatalytic resolutions has been developed. The programme utilises experimental data, ees and eep measured at more than one conversion, and determines both K and E no matter whether the reaction is irreversible (K=0) or reversible (K>0). An estimation of errors in the calculations indicates that errors in E does not show a Gaussian distribution, while errors in K does. The usefulness of the programme has been tested in a lipase-catalysed transesterification of 1-phenoxy-2-propanol at various concentrations of acyl donor, with different solvents and at different water activities.  相似文献   

16.
1,2:5,6:9,10:13,14-Tetrabenzo-3,7,11,15-tetradehydro[16]annulene, or tetrabenzocyclyne (QBC) and 1,2:5,6:9,10:13,14:17,18:21,22-hexabenzo-3,7,11,15,19,23-hexadehydro[24]annulene (HBC) have been structurally characterized by X-ray. crystallography. QBC crystallizes in two different space groups; P21/c with a = 10.652(3) Å, b = 10.624(2) Å, c = 19.549(4) Å, β = 93.83(2)°, V = 2207.4(8) Å3, and Z = 4 and P41212 with a = 9.330(1) Å, c = 25.497(8) Å, V = 2219.6(12) Å, and Z = 4. HBC crystallizes in monoclinic P21/n with a = 14.763(3) Å, b = 10.296(2) Å, c = 22.057(4) Å, β = 108.61(3), V = 3177.4(11) Å3, T = 133 K, and Z = 4. Reaction of QBC with dicobaltoctacarbonyl has produced a tetracobalt complex which has been characterized by X-ray crystallography. This complex crystallizes in monoclinic P21/c with a = 14.699(3) Å, b = 17.188(3) Å, c = 17.254(3) Å, β = 112.63(3)°, V = 4023.5(13) Å3, and Z = 4. Only two of the four C---C triple bonds of QBC bind to dicobalthexacarbonyl moieties even when excess dicobaltoctacarbonyl is used.  相似文献   

17.
The 1H and 13C NMR chemical shifts for six toxaphene congeners: 2-exo,3-endo,6-exo,8,9,10-hexachloro- (1), 2-exo,3-endo,5-exo,9,9,10,10-heptachloro- (2), 2-exo,3-endo,6-exo,8,9,10,10-heptachloro- (3), 2-exo,3-endo,5-exo,6-endo,8,9,10-heptachloro- (4), 2-exo,3-endo,5-exo,6-endo,8,9,9,10-octachlorobornane (5) and 2,5-endo,6-exo,8,9,9,10,10-octachloro-2-bornene (6) are reported. Their chemical shift assignments have been obtained by means of Pulsed Field Gradient (PFG) Double Quantum Filtered (DQF) 1H,1H correlation spectroscopy (COSY), PFG 1H,13C Heteronuclear Multiple Quantum Coherence (HMQC) and PFG 1H,13C Heteronuclear Multiple Bond Correlation (HMBC) experiments. A single crystal X-ray structural analysis was made for compounds 1, 3, 4 and 6. The prevalences of two octachlorobornene rotamers (6a,6b) were elucidated by ab initio MO method and single point DFT/GIAO calculations for 13C chemical shifts. Theoretical calculations proved that the single crystal structure of 6 corresponds its most stable conformer in solution.  相似文献   

18.
A number of isomeric N-benzylbenzalimine palladium(II) complexes of the type [P ·CH2Ph]2 (with C=N endo to the palladocycle) and [P =C(CH3Ph]2 (with C=N exo to the palladocycle), have been prepared and charcterised by 1H and 13C NMR methods. The crystal structures of two analogous monomeric acac complexes, synthesized independently by oxidative addition of o-BrC6H4CH2N=CH · Ph to Ph to Pd(dibenzylideneacetone)2 have also been determined. These are [P · CH2Ph)] (15a) and [P =CHPh)] (20a). Crystals of 15a are monoclinic, space group P21/a with Z = 4 in a cell of dimensions a 10.286(2), b 11.902(3), c 13.895(5) Å, β 93.52(2)° while 20a is monoclinic, space group P21/c with Z = 8 and a 10.353(3), b 20.600(5), c 16.545(7) Å, β 92.14(3)°. The structures 15a and 20a were refined to residuals R = 0.041 and 0.055 for 1661 and 2525 observed reflections respectively.  相似文献   

19.
Multifunctional macrocyclic initiators for the atom transfer radical polymerization (ATRP) based on different resorcin[4]- and pyrogallol[4]arenes have been synthesized. The initiators with 8, 12 and 16 tertiary -bromoesters on the core were received by complete esterification of all phenolic groups with 2-bromo-isobutyryl bromide. The calixarene derivatives with aliphatic chains on the bridging methine carbon were obtained as their rccc (all cis) isomers, while the corresponding calixarenes with aromatic substituents gave mixtures of their rccc and rctt (cis, cis, trans, trans) isomers.  相似文献   

20.
The chiral ligands, 4,4′-bis{(1S,2R,4S)-(−)-bornyloxy}-2,2′-bipyridine, (1S,2R,4S)-1, and 4,4′-bis{(1R,2S,4R)-(+)-bornyloxy}-2,2′-bipyridine, (1R,2S,4R)-1, have been prepared and characterized by spectroscopic techniques and, for (1S,2R,4S)-1, by single crystal X-ray diffraction. Despite the use of enantiomerically pure ligands, the formation of the complexes [Fe((1S,2R,4S)-1)3]2+, [Ru((1S,2R,4S)-1)3]2+, [Ru((1S,2R,4S)-1)(bpy)2]2+ and [Ru((1R,2S,4R)-1)(bpy)2]2+ proceeds without preference for either the Δ or Λ-diastereoisomers.  相似文献   

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