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The existence and multiplicity of positive solutions to a periodic boundary value problem for nonlinear third-order ordinary differential equation are established, based on the zero point theorem concerning cone expansion and compression of order type. Our main approach is different from the previous papers on the existence of multiple positive solutions to the similar problem. 相似文献
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9-Methylideneflourene (IIa) reacts rapidly with HCo(CO)4 at -67° C to give a quantitative yield of 9-methylfluorene (IIIa); k2 (13.4 ± 0.5) × 10-2 l mol-1S-1. Although the internal olefin, 9-ethylidenefluorene (IIb) reacts more slowly than IIa, it is hydrogenated about 2.5 times as fast as the terminal olefin, 1,1-diphenylethylene (I). Measurement of the rate of the reaction of IIb with DCo(CO)4 and comparison with HCo(CO)4 shows a very large inverse isotope effect kH/kD of 0.43. 相似文献
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The proton NMR spectra of N-[2-pyridyl-N-oxide]-derivatives of primary and secondary ethylamines, containing a substituent R on the C atom bearing the amino function, have been completely analysed in terms of the fundamental NMR parameters. The preferred conformations of the compounds investigated were established by the indications from NOE experiments as well as: (1) the long range coupling across the five bond between the aminic hydrogen and the proton in 4-position of the pyridine-N-oxide ring (5JmH,NH ~ 0·5 c/s), (2) the value of the vicinal coupling constant in the fragment CHNH (3JNHCH ~ 7–9 c/s), (3) the large deshielding (Δτ ~ 1–1·5 ppm) observed for the resonance position of the proton on the asymmetric C atom in secondary amine derivatives with respect to the corresponding primary ones, and (4) the diamagnetic shielding produced on protons in position 3 and 4 of the pyridine-N-oxide ring by different aromatic groups introduced in the R substituent.The NMR data confirmed the preferred rotamers previously suggested on the basis of ORD and CD measurements. 相似文献
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Reaction of the isodicyclopentadienide anion and its dehydro congener with Fe(II) leads to a stereochemically homogeneous ferrocene derivative in each instance. Through chemical correlation and X-ray analysis, above-plane complexation is established for both halves within the two sandwich compounds. 相似文献
5.
The heat capacities of potassium, rubidium, cesium, and thallium azides were determined from 5 to 350 K by adiabatic calorimetry. Although the alkali-metal azides studied in this work exhibited no thermal anomalies over the temperature range studied, thallium azide has a bifurcated anomaly with two maxima at (233.0±0.1) K and (242.04±0.02) K. The associated excess entropy was 0.90 calth K?1 mol?1. The thermal properties of the azides and the corresponding structurally similar hydrogen difluorides are nearly identical. Both have linear symmetrical anions. However, thallium azide shows a solid-solid phase transition not exhibited by thallium hydrogen difluoride. At 298.15 K the values of Cpo, So, and , respectively, are 18.38, 24.86, and 12.676 calth K?1 mol?1 for potassium azide; 19.09, 28.78, and 15.58 calth K?1 mol?1 for rubidium azide; 19.89, 32.11, and 18.17 calth K?1 mol?1 for cesium azide; and 19.26, 32.09, and 18.69 calth K?1 mol?1 for thallium azide. Heat capacities at constant volume for KN3 were deduced from infrared and Raman data. 相似文献
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X-ray diffraction studies of glasses in the following ternary systems have been made: Na2OMgOSiO2, Na2OZnOSiO2, Na2OCaOSiO2 and Na2OBaOSiO2. The following heavy atom substitutions have been used: Ag for Na and Ge for Si. The changes in the electron radial distribution curves resulting from AgNa replacement can be explained as amplifications of relatively well-defined NaSi distances, which are nearly the same in all the glasses investigated. The GeSi substitution causes changes which can be explained on the basis of isostructural GeSi substitutions. 相似文献
8.
The lithium enolate derived from methyl 2-methylpropanoate reacts stereoselectively with 2-phenylpropanal and 2-(cyclohexyl)propanal, affording mainly the β-hydroxy ester in both cases. With 2-ethylhexanal, no selectivity was observed. 相似文献
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The kinetics of the stoichiometric hydrogenation of 1,1-diphenylethylene with HCo(CO)4 is cleanly second order, permitting a determination of the activation parameters. The rate is unaffected by the atmosphere over the reaction and is enhanced by substituting DCo(CO)4 for HCo(CO)4. These results contrast sharply with those secured in the hydroformylation of 1-alkenes and thus dual mechanistic pathways are available for the reaction of HCo(CO)4 with unsaturated systems. It is very possible that the stoichiometric hydrogenation of 1,1-diphenylethylene involves a geminate free radical pair but definitive proof is still lacking. 相似文献