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排序方式: 共有147条查询结果,搜索用时 31 毫秒
1.
Nis Halland Tore Hansen Karl Anker Jrgensen 《Angewandte Chemie (International ed. in English)》2003,42(40):4837-4837
2.
One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
3.
Tore Berggren 《Hyperfine Interactions》1992,75(1-4):401-408
Starting from the formalism for alpha decay presented by Jackson and Rhoades-Brown /4/ and adapted for the decay of deformed
nuclei by Berggren and Olanders /3/, we calculate half-lives and anisotropies in the alpha decay of oriented odd-mass At isotopes.
The earlier results for harmonic oscillator models are compared to results for a Woods-Saxon model. 相似文献
4.
When α-halo sulfides are reacted with ambident 2-pyrimidinones, the major product is due to N-alkylation, the minor product to O-alkylation. N-Alkylation is favoured by the presence of a tertiary amine in a solvent of low dielectric constant and also by a change of the α-halo sulfide substituent from chlorine to iodine. Complete selectivity can be achieved. The course of the reaction is rationalized in terms of the HSAB-principle. 相似文献
5.
Silvestrini E Michelozzi M Skroppa T Brancaleoni E Ciccioli P 《Journal of chromatography. A》2004,1034(1-2):183-189
Head-space sampling (HS) has been combined with enantioselective gas chromatography (GC) for the analysis of chiral and non-chiral monoterpenes present in the cortical tissues of five different Norway spruce clones. (1S)-(-)-alpha-Pinene, (1S,5S)-(-)sabinene, (1S)-(-)-beta-pinene, and (4S)-(-)limonene dominated over (1R)-(+)-alpha-pinene, (1R,5R)-(+)-sabinene, (1R)-(+)-beta-pinene, and (4R)-(+)-limonene. Results showed a large variation in the enantiomeric composition of cortical tissues between different clones. The development of HS-GC greatly increased the speed of precise analyses of chiral monoterpenes in small samples and therefore offer excellent opportunities in studies on the ecophysiological and chemotaxomic roles of these chiral components. 相似文献
6.
7.
Two compounds, the (Z)- and (E)-isomers of 2,4-dibromo-1-p-tolyl-1-butene 2a and 3a, respectively, were isolated in 65% total yield when 1-(1-bromo-1-p-tolylmethyl)cyclopropyl bromide (1a) was heated at 150 degrees C for 1 h. 1,1-Dibromo-2-p-tolylcyclobutane (4a), previously reported to be the only product in this reaction, was not detected. The phenyl analogue of 1a reacted similarly and gave the (Z)- and (E)-isomers of 2,4-dibromo-1-phenyl-1-butene 2b and 3b, respectively, in 60% yield. A rationale for the reaction is presented. 相似文献
8.
Woldegiorgis A von Kieseritzky F Dahlstedt E Hellberg J Brinck T Roeraade J 《Rapid communications in mass spectrometry : RCM》2004,18(8):841-852
The use of non-polar, small polymers as matrices for the analysis of low molecular weight compounds in polymer-assisted laser desorption/ionization mass spectrometry (PALDI-MS) is demonstrated. The matrices evaluated were either based on an oligothiophene or a benzodioxin backbone. Metallocenes, polycyclic hydrocarbons, a fluorosurfactant, and a subset of small organic compounds with various functionalities, served as model analytes. The mechanism of ionization charge transfer is discussed and ionization potentials for the matrices in the study have been estimated using density functional theory (DFT) calculations. Some of the results are possibly contradictory to the generally accepted limiting conditions for gas-phase charge-transfer reactions. These results are interpreted in the light of energy pooling. Also a new mass calibration procedure for the low-mass region in positive ion mode is presented, and some aspects of the ionization/desorption process leading to radical cations are studied. 相似文献
9.