全文获取类型
收费全文 | 10356篇 |
免费 | 1109篇 |
国内免费 | 204篇 |
专业分类
化学 | 8851篇 |
晶体学 | 12篇 |
力学 | 28篇 |
综合类 | 5篇 |
数学 | 27篇 |
物理学 | 2746篇 |
出版年
2023年 | 73篇 |
2022年 | 121篇 |
2021年 | 209篇 |
2020年 | 360篇 |
2019年 | 270篇 |
2018年 | 242篇 |
2017年 | 181篇 |
2016年 | 373篇 |
2015年 | 359篇 |
2014年 | 454篇 |
2013年 | 682篇 |
2012年 | 416篇 |
2011年 | 485篇 |
2010年 | 387篇 |
2009年 | 453篇 |
2008年 | 435篇 |
2007年 | 492篇 |
2006年 | 435篇 |
2005年 | 370篇 |
2004年 | 324篇 |
2003年 | 342篇 |
2002年 | 1213篇 |
2001年 | 199篇 |
2000年 | 150篇 |
1999年 | 164篇 |
1998年 | 160篇 |
1997年 | 93篇 |
1996年 | 103篇 |
1995年 | 116篇 |
1994年 | 56篇 |
1993年 | 54篇 |
1992年 | 42篇 |
1991年 | 41篇 |
1990年 | 29篇 |
1988年 | 24篇 |
1987年 | 24篇 |
1985年 | 92篇 |
1984年 | 117篇 |
1983年 | 106篇 |
1982年 | 149篇 |
1981年 | 113篇 |
1980年 | 97篇 |
1979年 | 100篇 |
1978年 | 106篇 |
1977年 | 144篇 |
1976年 | 118篇 |
1975年 | 129篇 |
1974年 | 165篇 |
1973年 | 133篇 |
1972年 | 82篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
91.
Sandrine LangleFranck David-Quillot Mohamed AbarbriAlain Duchêne 《Tetrahedron letters》2003,44(8):1647-1649
Using double Stille cross-coupling reaction bromo (or chloro)benzylbromide is easily transformed into substituted styrene monomers bearing a wide range of substituents in para position 相似文献
92.
A polystyrene-bonded stannic chloride catalyst was synthesized by the method of lithium polystyryl combined with stannic chloride. This catalyst is a polymeric organometallic compound containing 0.25 mmol Sn (Ⅳ)/g catalyst. The catalyst showed sufficient stability and catalytic activity in organic reaction such as esterification, acetalation and ketal formation, and it could be reused many times without losing its catalytic activity. 相似文献
93.
Xiu Yang LU Qi JING Zhun LI Lei YUAN Fei GAO Xin LIU 《中国化学快报》2006,17(6):841-844
High temperature liquid water (HTLW), as an environmentally benign medium, has drawn increasing attention for organic chemical reactions and biomass conversion1-3. HTLW has a strong tendency to ionize and can act as an acid and/or base catalyst. In addition, HTLW can dissolve organic compounds to some extent allowing for a homogenous reaction within an aqueous phase. Extensive researches4-10 have been pursued on acid/base-catalysis reactions in HTLW without addition of acid or base. Howe… 相似文献
94.
A comprehensive B3LYP/6-31+G∗ study of the influence of BF3 on the [4+2] cycloaddition of vinylketene with formaldimine was conducted. For this purpose, the complete pathway was determined and changes in different magnetic properties (magnetic susceptibility, χ, magnetic susceptibility anisotropy, χanis, and the nucleus-independent chemical shifts, NICS) were monitored along the reaction profile with a view to estimate the aromatization associated to the process. We have also applied the ACID (anisotropy of the current-induced density) method with the same intention. 相似文献
95.
Einar Uggerud 《Theoretical chemistry accounts》1997,97(1-4):313-316
The potential energy hypersurface of protonated glycine, GH+, has been investigated. The calculated G2(MP2) value for the proton affinity (PA) of glycine, PA
calc=895kJ mol−1, is in good agreement with the experimental value which has been estimated to lie in the range 864kJ mol−1 < PA
exp
<891kJ mol−1. Ab initio quantum chemical calculations of relevant parts of the potential energy surface of GH+ give a reaction model which is consistent with the observed mass spectrometric fragmentation pattern. The lowest energy unimolecular
reactions of GH+ are two distinct processes: (1) loss of CO, which has a substantial barrier for the reverse reaction, and (2) loss of CO
plus H2O, which has no barrier for the reverse reaction.
Received: 15 November 1996 / Accepted: 6 May 1997 相似文献
96.
The oxidative decomposition of various ketones (including acetone, 2-butanone, 4-heptanone, cyclopentanone and cyclohexanone) over dehydrated TiO(2) (P25) powder is investigated by electron paramagnetic resonance (EPR) spectroscopy. For the first time, a series of thermally unstable radical intermediates are observed both on the activated and reduced TiO(2) surface, depending on the adopted experimental conditions. These radical intermediates are identified as organoperoxy-based species of general formula ROO(.-) and RCO(3) (.-). They are formed by reaction of photogenerated charge carriers (either trapped electrons or trapped holes) with the adsorbed ketones in the presence of molecular oxygen. The organoperoxy intermediates are thermally unstable and decompose at temperatures in the region of 180-250 K. This work demonstrates that free-radical pathways involving both organoperoxy and superoxide radicals can be responsible for the thermal- and photodecomposition of ketones over polycrystalline TiO(2) (P25). 相似文献
97.
Ring‐rearrangement metathesis (RRM) refers to the combination of several metathesis transformations into a domino process, in which an endocyclic double bond of a cycloolefin reacts with an exocyclic alkene. RRM has proven to be a powerful method for the rapid construction of complex structures. The extension of the basic ring‐opening–ring‐closing metathesis process by further metathesis steps as well as an examination of the driving forces, limits, scope, recent advantages, and future perspectives of these domino sequences is presented with various examples, thus reflecting the high efficiency and utility of RRM in organic synthesis. 相似文献
98.
Rybachenko V. I. Schroeder G. Chotii K. Yu. Lenska B. Kovalenko V. V. Red'ko A. N. 《Theoretical and Experimental Chemistry》2003,39(6):359-363
We have studied the rate of 15 reactions of acyl transfer from O-acyl salts of 4-dimethylaminostyryl-4-pyridine N-oxide to 4-morpholinopyridine and 4-dimethylaminopyridine N-oxides in acetonitrile solutions. Analysis of the results based on the Shaik – Pross approach and the Marcus equation shows that if the structure of the acyl group is varied, then the reactivity is determined by such parameters as the resonance interaction in the transition state (B) or the internal barrier (G
0) of the reaction. 相似文献
99.
Simon Doherty Julian G. Knight Tom H. Scanlan Mark R. J. Elsegood William Clegg 《Journal of organometallic chemistry》2002,650(1-2):231-248
The aprotic and protic bi- and multidentate iminophosphines 2-Ph2PC6H4N=CR1R2 (R1=H, R2=Ph=2a; R1=Me R2=Ph=2b; R1=H, R2=2-thienyl=2c; R1=H, R2=C6H4-2-PPh2=2d; R1=H, R2=C6H4-2-OH=2e, R1=H, R2=C6H4-2-OH-3-But=2f; R1=H, R2=CH2C(O)Me=2g) have been prepared by the acid catalyzed condensation of 2-(diphenylphosphino)aniline with the corresponding aldehyde–ketone. Iminophosphine 2d can be reduced with sodium cyanoborohydride to give the corresponding amino-diphosphine 2-Ph2PC6H4N(H)CH2C6H4-2-PPh2 (2h). In the presence of a stoichiometric quantity of acid, 2-(diphenylphosphino)aniline reacts in an unexpected manner with benzaldehyde, salicylaldehyde, or acetophenone to give the corresponding 2,3-dihydro-1H-benzo[1,3]azaphosphol-3-ium salts and with pyridine-2-carboxaldehyde to give N-(pyridin-2-ylmethyl)-2-diphenylphosphinoylaniline, the latter of which has been characterized by single-crystal X-ray crystallography, as its palladium dichloride derivative. The attempted condensation of 2-(diphenylphosphino)aniline with pyridine-2-carboxaldehyde to give the corresponding pyridine-functionalized iminophosphine resulted in an unusual transformation involving the diastereoselective addition of two equivalents of aldehyde to give 1,2-dipyridin-2-yl-2-(o-diphenylphosphinoyl)phenylamino-ethanol, which has been characterized by a single-crystal X-ray structure determination. The bidentate iminophosphine 2-Ph2PC6H4N=C(H)Ph reacts with [(cycloocta-1,5-diene)PdClX] X=Cl, Me) to give [Pd{2-Ph2PC6H4N=C(H)Ph}ClX] and the imino-diphosphine 2-Ph2PC6H4N=C(H)C6H4-PPh2 reacts with [(cycloocta-1,5-diene)PdClMe] to give [Pd{2-Ph2PC6H4N=C(H)C6H4---PPh2}ClMe] and each has been characterized by single-crystal X-ray crystallography. The monobasic iminophosphine 2-Ph2PC6H4N=C(Me)CH2C(O)Me reacts with [Ni(PPh3)2Cl2] in the presence of NaH to give the phosphino–ketoiminate complex [Ni{2-Ph2PC6H4N=C(Me)CHC(O)Me}Cl], which has been structurally characterized. Mixtures of iminophosphines 2a–h and a palladium source catalyze the Suzuki cross coupling of 4-bromoacetophenone with phenyl boronic acid. The efficiency of these catalysts show a marked dependence on the palladium source, catalysts formed from [Pd2(OAc)6] giving consistently higher conversions than those formed from [Pd2(dba)3] and [PdCl2(MeCN)2]. Catalysts formed from neutral bi- and terdentate iminophosphines 2a–d gave significantly higher conversions than those formed from their monobasic counterparts 2e–f. Notably, under our conditions the conversions obtained with 2a–c compare favorably with those of the standards; catalysts formed from tris(2-tolyl)phosphine and tris(2,4-di-tert-butylphenyl)phosphite and a source of palladium. In addition, mixtures of [Ir(COD)Cl]2 and 2a–h are active for the hydrosilylation of acetophenone; in this case catalysts formed from monobasic iminophosphines 2e–f giving the highest conversions. 相似文献
100.
Mark J. Thompson 《Tetrahedron letters》2006,47(14):2361-2364
A convenient route to 4-phenyl-5-aminothiazoles is described, which offers control over substitution at the 2-position. 2-N-Acylglycinamides were dithionated and a subsequent TFAA-mediated cyclisation step was followed by removal of the 5-N-trifluoroacetyl group providing the free amines. Though applicable generally the method was found to be most effective when introducing aromatic substituents at the 2-position, whereupon moderate overall yields of the 5-amino compounds were obtained. 相似文献