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31.
Andrei V. Afonin Igor A. Ushakov Dmitry V. Pavlov Andrei V. Ivanov Al'bina I. Mikhaleva 《Magnetic resonance in chemistry : MRC》2010,48(9):685-692
The 1H, 13C and 15N NMR studies have shown that the E and Z isomers of pyrrole‐2‐carbaldehyde oxime adopt preferable conformation with the syn orientation of the oxime group with respect to the pyrrole ring. The syn conformation of E and Z isomers of pyrrole‐2‐carbaldehyde oxime is stabilized by the N? H···N and N? H···O intramolecular hydrogen bonds, respectively. The N? H···N hydrogen bond in the E isomer causes the high‐frequency shift of the bridge proton signal by about 1 ppm and increase the 1J(N, H) coupling by ~3 Hz. The bridge proton shows further deshielding and higher increase of the 1J(N, H) coupling constant due to the strengthening of the N? H···O hydrogen bond in the Z isomer. The MP2 calculations indicate that the syn conformation of E and Z isomers is by ~3.5 kcal/mol energetically less favorable than the anti conformation. The calculations of 1H shielding and 1J(N, H) coupling in the syn and anti conformations allow the contribution to these constants from the N? H···N and N? H···O hydrogen bondings to be estimated. The NBO analysis suggests that the N? H···N hydrogen bond in the E isomer is a pure electrostatic interaction while the charge transfer from the oxygen lone pair to the antibonding orbital of the N? H bond through the N? H···O hydrogen bond occurs in the Z isomer. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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Boris A. Trofimov Lyubov'' N. Sobenina Zinaida V. Stepanova Tamara I. Vakul''skaya Ol''ga N. Kazheva Grigorii G. Aleksandrov Oleg A. Dyachenko Al''bina I. Mikhaleva 《Tetrahedron》2008,64(23):5541-5544
The solvent-free interaction of 2-phenylpyrrole with bromobenzoylacetylene (room temperature) upon their grinding with solid metal oxides (MgO, CaO, ZnO, BaO, Al2O3, TiO2, ZrO2) and salts (CaCO3, ZrSiO4) leads to either the cross-coupling product or the adduct of pyrrole addition to the riple bond of acetylene. The ethynylation is accompanied by the formation of intermediate and side products: E-2-(1-bromo-2-benzoylethenyl)-5-phenylpyrrole and 1,1-di(5-phenylpyrrol-2-yl)-2-benzoylethene. The activity of the metal oxides in the ethynylation reaction falls in the order (in the brackets, the content of 2-benzoylethynyl-5-phenylpyrrole in the reaction mixture is given): ZnO (81%), BaO (73%), Al2O3 (71%), MgO (69%), CaO (50%). The oxides, SiO2, TiO2, ZrO2, and the salts, CaCO3 and ZrSiO4, are inactive in the ethynylation reaction affording only the intermediate adduct, with ZrO2 the isolated yield of the bromoethenylpyrrole reaching 60%. ESR monitoring shows the reaction to start from one electron transfer from pyrrole to acetylene mediated by the oxide surface. The adduct is readily converted on Al2O3 to 2-(benzoylethynyl)-5-phenylpyrrole crystallized mostly as cis-rotamer (X-ray data). 相似文献
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A. B. Zaitsev E. Yu. Shmidt A. M. Vasil’tsov A. I. Mikhaleva A. V. Afonin I. A. Ushakov D.-S. D. Toryashinova 《Chemistry of Heterocyclic Compounds》2005,41(4):444-448
The oxime of 2-acetylcoumarone reacts with acetylene under pressure in the system KOH-DMSO unusually readily forming 2-(2-pyrrolyl)coumarone and the corresponding O-vinyl oxime. Under more rigid conditions 2-(1-vinyl-2-pyrrolyl)coumarone is formed. The possibility of a two-stage transformation of 2-acylcoumarones into 2-pyrrolylcoumarones has therefore been demonstrated for the first time.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 524–529, April, 2005. 相似文献
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Boris A. Trofimov Tatyana E. Glotova Marina Yu. Dvorko Igor’ A. Ushakov Elena Yu. Schmidt Al’bina I. Mikhaleva 《Tetrahedron》2010,66(38):7527-3421
Triphenylphosphine catalyzes the regio- and stereospecific addition of ketoximes to acylacetylenes, whereas classical conditions using acetylene (KOH/DMSO, 70 °C) are unsuitable for this purpose. The reaction proceeds under mild conditions (CH2Cl2, rt, 7 h) to afford (E)-(O)-2-(acyl)vinylketoximes (92-98% stereoselectivity) in a yield of up to 85%. The (E)-adducts obtained are energetically less favorable than the corresponding (Z)-isomers and are gradually enriched with (Z)-isomers, thus indicating the kinetic control of (E)-stereoselectivity of the reaction. 相似文献
37.
Vasil’tsov A. M. Mikhaleva A. I. Ivanov A. V. Skital’tseva E. V. Trofimov B. A. 《Russian Chemical Bulletin》2010,59(1):302-303
Russian Chemical Bulletin - 相似文献
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