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Cecchi L De Sarlo F Machetti F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(26):7903-7912
A new procedure for the synthesis of 4.5-dihydroisoxazoles by condensation of primary nitro compounds with olefins by using a copper/base catalytic system is described. The catalytic effect of copper(II) salts is evidenced by comparison of the reaction rates. Thus, activated nitro compounds react faster than with organic catalysis by tertiary amines, whereas nitroalkanes, unable to condense with dipolarophiles in the presence of the base alone, undergo the reaction on addition of a copper(II) catalyst. The observed occurrence of induction periods in most reactions is ascribed to an equilibrium preceding the rate-determining step, and gives a hint as to the proposed reaction mechanism. The results indicate that this method might be of practical and general utility for synthetic practice. 相似文献
75.
Giovanni Buffa Dr. Luca Dore Prof. Francesca Tinti Dr. Markus Meuwly Prof. 《Chemphyschem》2008,9(15):2237-2244
An experimental and theoretical study of pressure broadening and pressure shift of HCO+ rotational lines perturbed by collisions with He is presented. Results are reported from measurements at 88 K for the lines j=4←3, 5←4 and 6←5 with frequencies ranging from 0.35 to 0.54 THz. Using a new CCSD(T)/aug‐cc‐pVQZ potential energy surface for the He–HCO+ interaction, the collisional line shape parameters are studied from fully quantum and semiclassical calculations. Results from the quantum treatment are in satisfactory agreement with experiments whereas the semiclassical approach can lead to appreciable differences. A study of the dependence of line width Γ and shift s as a function of the translational energy shows the presence of quantum oscillations. Calculations on a previous Hartree–Fock‐based potential energy surface lead to quite similar results for the collisional line shape parameters. Using a simplified version of the potential morphing method it is found that the line width Γ is particularly sensitive to the long‐range part of the potential energy surface. This also explains the success of the first line‐broadening calculations which date back to the 1950s. 相似文献
76.
Grazia Cafeo Dr. Franz H. Kohnke Prof. Luca Valenti Andrew J. P. White Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(36):11593-11600
10α,20α‐Bis(4‐nitrophenyl)calix[4]pyrrole ( 1 ) forms 1:1 complexes with anions of selected aromatic hydroxy acids in which the host orientation within the guest is controlled by a change in the pH value. Some bis‐anionic guests, including those obtained from 4‐hydroxybenzoic acid, 1,4‐ and 1,3‐benzenedicarboxylic acids, induce the self‐assembly of molecular capsules involving two molecules of the receptor. 1H NMR data and solid‐state structures of the 1:1 complex of 1 with p‐C6H4(COOH)(COO?)+NMe4 and the 2:1 capsule [( 1 )2m‐C6H4(COO?)2(+NMe4)2] provide structural details in solution and in the solid state. 相似文献
77.
Liquid densities (pvT), vapor pressures (VLE), and mean ionic activity coefficients (MIAC) at 25 °C of 115 single-salt electrolyte solutions containing univalent up to trivalent ions are modeled with the ePC-SAFT equation of state proposed by Cameretti et al. [L.F. Cameretti, G. Sadowski, J.M. Mollerup, Ind. Eng. Chem. Res. 44 (2005) 3355–3362; ibid., 8944]. For each ion, only two model parameters were adjusted to experimental density and MIAC data. Without using any additional binary parameters, ePC-SAFT is able to reproduce experimental data of the respective salt solutions up to high electrolyte molalities. Moreover, it is even able to describe the reversed MIAC series for alkali hydroxides and fluorides. 相似文献
78.
A 4-component Ugi reaction with a suitable isocyanide, followed by a novel secondary transformation involving a Pd(II)-mediated (R5 = H) or a Pd(0)-mediated (R5 = CO2Me) SN2' cyclization to give highly functionalized N-acyl-2-vinylpyrrolidines, is reported. The overall yields are usually good and in most cases the Pd(0)-catalyzed reaction gave the final product in almost quantitative yield. 相似文献
79.
Pellegrino T Fiore A Carlino E Giannini C Cozzoli PD Ciccarella G Respaud M Palmirotta L Cingolani R Manna L 《Journal of the American Chemical Society》2006,128(20):6690-6698
We describe an approach to synthesize colloidal nanocrystal heterodimers composed of CoPt(3) and Au. The growth is based on the nucleation of gold domains on preformed CoPt(3) nanocrystals. It is a highly versatile methodology which allows us to tune independently the size of the two domains in each dimer by varying several reaction parameters. The statistical analysis of the distribution of the domain sizes in the dimers and the compositional mapping achieved by dark field imaging and energy dispersive spectroscopy confirm that the two domains in each dimer are indeed made of CoPt(3) and Au, respectively. Structural characterization by high-resolution transmission electron microscopy shows that the two domains, both having cubic fcc Bravais lattice, can share a common {111}, {100}, or {110} facet, depending on the size of the initial CoPt(3) seeds. The magnetization measurements evidence a ferromagnetic CoPt(3) phase with a relatively low anisotropy as a consequence of their disordered crystalline structure, regardless of the presence of a Au tip. We believe that this prototype of nanocrystal dimer, which can be manipulated under air, can find several applications in nanoscience, as the Au section can be exploited as the preferential anchor point for various molecules, while the CoPt(3) domain can be used for magnetic detection. 相似文献