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21.
Perturbative solution of the RPA equation. An application to the calculation of rotational strengths
The RPA equation is solved by perturbation in Møller-Plesset (MP) and Epstein-Nesbet (EN) partitions, which are first compared on a specific example. To still accelerate the faster one (EN), a third scheme is proposed, which involves preliminary diagonalization within a limited subset
, followed by usual EN perturbation between
and the rest of the whole configuration space. Criteria for the choice of
are given. 相似文献
22.
Malassene R Vanquelef E Toupet L Hurvois JP Moinet C 《Organic & biomolecular chemistry》2003,1(3):547-551
The anodic cyanation of methanolic solutions of the 2-alkyl-N-phenylpiperidines 6b-d was performed in a flow cell equipped with a graphite felt anode. The reaction led to the formation of the 2-cyano-6-alkyl-N-phenylpiperidines 2b-d and proceeded with a high degree of regioselectivity. The 1H NMR spectra of the aminonitriles 2b-d showed an epimeric mixture at C-6. The major isomer has a trans configuration in which the cyano group is axial and the alkyl substituent is equatorial. Conversely, electrochemical oxidation of the 4-methyl-6-pentyl-N-phenylpiperidine 6e afforded the trisubstituted aminonitrile 2e as a single diastereomer (> 98% de). The 4-cyanobutyl side chain was incorporated in a two-step procedure to yield dinitrile 4e. This latter compound was directly converted into spiropiperidine 5e by using the Thorpe-Ziegler annulation procedure. The overall sequence (4 steps, 43%) allows the construction of the basic carbon framework of perhydrohistrionicotoxin. 相似文献
23.
Muriel Lepère Ghislain Blanquet Jacques Walrand Jean-Pierre Bouanich 《Journal of Molecular Spectroscopy》1996,180(2):218-226
Infrared absolute line intensities of the ν6band of CH3F have been measured around 8.5 μm using a diode-laser spectrometer. These line strengths were obtained by the equivalent width method and, for 13 lines, by fitting a Rautian profile to the measured shape of the lines. From these results, we have deduced the vibrational band strength to beS0v= 9.66 ± 0.13 cm−2atm−1at 296 K and the first Herman–Wallis factors. 相似文献
24.
Delangle P Dutasta JP Van Oostenryck L Tinant B Declercq JP 《The Journal of organic chemistry》1996,61(25):8904-8914
The semirigid phosphonamide ligands 1-5 have been synthesized from the macrocyclic precursors 6-9 by reaction with 1,3-propanediol ditosylate or 1,2-dichloroethane. For the thiophosphoryl compounds 1 and 2, and the phosphoryl derivative 5, the reactions were carried out in biphasic aqueous NaOH solutions. The phosphoryl derivatives 3 and 4 were better obtained from NaH in anhydrous tetrahydrofuran. The conformations of the hosts in solution were deduced from low-temperature NMR and NOE difference experiments. Conformational equilibria between exo and endo forms are observed for the 18-membered macrocycles 1 and 3. The exo conformer predominates in solution for the 21-membered macrocycle 2, whereas 4 exists as rapidly exchanging conformers. The X-ray crystal structures of macrocycles 1, 2, and 5 have been determined as well as the complexes 1.Hg(SCN)(2) and 5.LiNO(3). In the Hg(2+) complex the metal ion is located out of the macrocyclic cavity and is coordinated to the thiophosphoryl unit. In 5.LiNO(3)()()the Li(+) cation is located inside the macrocyclic cavity and is coordinated to a tetrahedral array of oxygen donors. Free energies of complexation (DeltaG degrees ) of the phosphorylated ligands 3-5 with alkali metal and ammonium cations were determined in CHCl(3) saturated with H(2)O by picrate extraction experiments. The -DeltaG degrees values are greatest for 4 complexing K(+) and NH(4)(+) (7.3 and 8.0 kcal/mol, respectively). The relationships between structure and binding are discussed. 相似文献
25.
M. Niaz Khan Jean-Pierre Fleury Philippe Baumlin Christian Hubschwerlen 《Tetrahedron》1985,41(22):5341-5345
Amides or vinylogous amides react with tosyl chloride-pyridine to form activated intermediates which condense with Fischer's base or their vinylogs to give carbocyanine structures. Under the same conditions formylated Fischer's base reacts with vinylogous Fischer's bases to give trinuclear carbocyanines in good yields. Their structure and the limitations of this route are discussed. 相似文献
26.
Yolande MespliÉ Michel Bergon Jean-Pierre Calmon 《Journal of heterocyclic chemistry》1984,21(4):985-993
The alkaline hydrolysis of propargyl 3-chlorocarbanilates was investigated kinetically using uv spectropotometry. The cyclization to 4-methoylene-2-oxazolisinones proceeds via the numcleophilic attack of the substrate anion concomitantly with that of the hydroxide ion on the triple bond. The nucleophilic attack leads directly to the heterocycle whereas the hydroxide ion attack gives rise to a ketocarbamate which is then cyclized to the oxazolidione. 相似文献
27.
Birck C Cha JY Cross J Schulze-Briese C Meroueh SO Schlegel HB Mobashery S Samama JP 《Journal of the American Chemical Society》2004,126(43):13945-13947
28.
A sensor for measuring adsorption on a substrate has been designed including a contactless detection scheme, called supercapacitive admittance tomoscopy (SCAT). The sensor comprises a thin dielectric layer with two parallel band electrodes on the one side and a chemically modified surface on the other onto which the adsorption of molecules occurs. Upon application of a high frequency ac voltage between the two electrodes, a capacitive coupling is established across the dielectric layer, and the admittance measured depends on the surface state of the chemically modified interface. On the basis of this principle, a flow sensor has been developed to measure sensorgrams to follow the dynamics of the adsorption and has been tested for the adsorption of IgG on the modified surface. 相似文献
29.
The cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)-cyclopentane-[PdCl(eta3-C3H5)]2 system catalyses the coupling of aryl halides with alkynes with very high ratios of substrates-catalyst in good yields; a turnover number of 2600000 can be obtained for the reaction of 4-trifluoromethylbromobenzene with phenylacetylene in the presence of this catalyst. 相似文献
30.
Chin W Dognon JP Piuzzi F Tardivel B Dimicoli I Mons M 《Journal of the American Chemical Society》2005,127(2):707-712
Laser desorption of model peptides coupled to laser spectroscopic techniques enables the gas-phase observation of genuine secondary structures of biology. Spectroscopic evidence for the formation of beta-turns in gas-phase peptide chains containing glycine and phenylalanine residues establishes the intrinsic stability of these forms and their ability to compete with other stable structures. The precise characterization of local minima on the potential energy surface from IR spectroscopy constitutes an acute assessment for the state-of-the-art quantum mechanical calculations also presented. The observation of different types of beta-turns depending upon the residue order within the sequence is found to be consistent with the residue propensities in beta-turns of proteins, which suggests that the prevalence of glycine in type II and II' turns stems essentially from an energetic origin, already at play under isolated conditions. 相似文献