全文获取类型
收费全文 | 1295篇 |
免费 | 133篇 |
国内免费 | 352篇 |
专业分类
化学 | 1726篇 |
晶体学 | 12篇 |
力学 | 3篇 |
综合类 | 9篇 |
物理学 | 30篇 |
出版年
2023年 | 10篇 |
2022年 | 25篇 |
2021年 | 36篇 |
2020年 | 55篇 |
2019年 | 66篇 |
2018年 | 53篇 |
2017年 | 51篇 |
2016年 | 53篇 |
2015年 | 53篇 |
2014年 | 87篇 |
2013年 | 199篇 |
2012年 | 103篇 |
2011年 | 104篇 |
2010年 | 92篇 |
2009年 | 71篇 |
2008年 | 61篇 |
2007年 | 75篇 |
2006年 | 71篇 |
2005年 | 83篇 |
2004年 | 63篇 |
2003年 | 75篇 |
2002年 | 41篇 |
2001年 | 38篇 |
2000年 | 37篇 |
1999年 | 25篇 |
1998年 | 25篇 |
1997年 | 29篇 |
1996年 | 24篇 |
1995年 | 13篇 |
1994年 | 7篇 |
1993年 | 19篇 |
1992年 | 8篇 |
1991年 | 2篇 |
1990年 | 7篇 |
1989年 | 3篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1982年 | 3篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有1780条查询结果,搜索用时 78 毫秒
21.
22.
采用密度泛函理论, 对在Ru(II)催化剂存在下, 有机叠氮化合物和末端炔的反应机理作了深入理论研究. 在B3LYP/LANL2DZ水平上, 对该反应体系中势能面各驻点的几何构型进行了全优化计算, 并经振动频率分析确定了过渡态和中间体, 通过内禀反应坐标(IRC)的计算, 确认了反应物、中间体、过渡态和产物的相关性. 对多个反应通道的协同反应以及分步反应进行了研究. 结果表明: 协同反应通道Ic和分步反应通道IIc是反应能垒较低的反应通道, 活化自由能较其它反应通道低, 有利于1,5-二取代1,2,3-三唑的生成, 具有特定的区域选择性, 与实验结果吻合. 相似文献
23.
Ilaria AdamoFabio Benedetti Federico BertiGiorgio Nardin Stefano Norbedo 《Tetrahedron letters》2003,44(51):9095-9097
4-Acyl-1H-1,2,3-triazoles are formed from diethylaluminum azide and α′-(N,N-dibenzylamino)-α,β-unsaturated ketones by [3+2] cycloaddition of azide, followed by 1,5 hydride transfer to the β carbon of the triazoline side chain and fragmentation of the tertiary amino group promoted by coordination of the latter to the Lewis acid. The structure of a triazole product is confirmed by X-ray crystallography. 相似文献
24.
Wei Wang Rongliang Wang Fan Wu Boshun Wan 《Reaction Kinetics and Catalysis Letters》2005,85(2):277-282
Summary A Ni-promoted ligand free palladium catalyst system for Suzuki coupling of aryl bromides has been developed in high efficiency under mild reaction conditions. It was obtained in situ by introducing NiCl2 to PdCl2/PVP using a parallel high-throughput screening technique. A wide range of aryl bromides bearing a variety of functional groups was evaluated. 相似文献
25.
Synthesis and characterization of new soluble poly(aryl ether nitrile)s containing phthalazinone moiety 总被引:1,自引:0,他引:1
Ming Jing Wang Cheng Liu Li Ming Dong Xi Gao Jian 《中国化学快报》2007,18(5):595-597
A series of novel poly(aryl ether nitrile)s containing phthalazinone moiety were synthesized by the nucleophilic displacement reaction of bisphenol-like monomers (I) with 2,6-difluorobenzonitrile. The inherent viscosities ranged from 0.46 to 1.07 dL g^-1. The glass transition temperatures were in the range of 277-295℃, and the temperatures for 10% weight loss in nitrogen atmosphere were found between 495 and 527 ℃. The structures of these resultant polymers were confirmed by FT-IR and 1^H NMR. Moreover, the properties of poly(aryl ether nitrile)s including solubility and crystallinity were also studied. 相似文献
26.
Cu(I)/Diamine-catalyzed Aryl-alkyne Coupling Reactions 总被引:1,自引:0,他引:1
Ye Feng WANG Wei DENG Lei LIU Qing Xiang GUO 《中国化学快报》2005,16(9):1197-1200
Arylalkynes are important building blocks for the synthesis of natural products,pharmaceuticals,and artificial molecular devices1.They are often synthesized via the Pd-catalyzed Sonogashira coupling reactions between aryl halides and terminal alkynes2,3.Unfortunately,it remains difficult to apply the Sonogashira reaction to industrial scale and/or pharmaceutical synthesis,due to the high cost of Pd and the difficulty in removing the toxic Pd residues from the reaction products.Thus it is wor… 相似文献
27.
在吡啶溶剂中氯化镍催化的溴代芳烃自身偶联反应 总被引:1,自引:0,他引:1
Pyridine was used as a solvent for homocoupling of aryl bromides catalyzed by nickel chloride/triarylphosphinein the presence of zinc and recycled easily.Triphenylphosphine was the best ligand for nickel in this coupling reac-tion. 相似文献
28.
Tandem cascade reactions of allylazides and olefinic dipolarophiles to give cis‐fused 2,3,7‐triazabicyclo [3.3.0]octenes ( 5, 6 or 7 ) are reported. Therein, an intermolecular dipolar cycloaddition of azide and alkene gave a triazoline which was followed by isomerization of the triazoline to a diazoester ( 4 ) and then an intramolecular dipolar cycloaddition from the diazo functional group and the double bond in 4 to give 5 . Compound 5 may further more undergo a Michael addition to give 7‐substituted‐ 2,3,7‐ triazabicyclo [3.3.0]oct‐2‐ene ( 6 ) or a tautomerization to give 2,3,7‐triazabicyclo[3.3.0]oct‐3‐ene ( 7 ). The reaction may be manipulated to stop at a particular stage by adopting a suit able solvent or an appropriate temperature. 相似文献
29.
J. Díaz-Ferrero M.C. Rodríguez-Larena L. Comellas B. Jiménez 《Trends in analytical chemistry : TRAC》1997,16(10):1865-573
The usual methods for determining polychlorinated dibenzo-p-dioxins (PCDD), polychlorinated dibenzofurans (PCDF) and polychlorinated biphenyls (PCB) are generally expensive and time consuming. This fact has favored the development of faster and cheaper techniques, based on immunoassays and bioassays. This paper reviews these bioanalytical methods and their analytical importance at the present moment. 相似文献
30.
A. M. Demchenko V. A. Yanchenko V. V. Kisly M. S. Lozinskii 《Chemistry of Heterocyclic Compounds》2005,41(5):668-672
We have developed a method for synthesis of aryl isothiocyanates by means of thiocarbamoylation of aromatic amines by tetramethylthiuram disulfide followed by degradation of the intermediate N(1)-aryl-N,N-dimethylthiourea by concentrated HCl. We have shown that thiocarbamoylation of 4-amino-5-ethyl-4H-1,2,4-triazole-3-thiol occurs at the 2 position of the triazole ring, while thiocarbamoylation of 4-amino-3-methyl-6-phenyl-4,5-dihydro-1,2,4-triazin-5-one leads to the dihetaryl-substituted thiourea. We consider the possibility of using N(1)-aryl-N,N-dimethylthioureas as analogs of isothiocyanates in reactions with N-nucleophiles.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 775–780, May, 2005. 相似文献