全文获取类型
收费全文 | 591篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 466篇 |
晶体学 | 2篇 |
力学 | 12篇 |
数学 | 28篇 |
物理学 | 108篇 |
出版年
2024年 | 2篇 |
2023年 | 3篇 |
2022年 | 16篇 |
2021年 | 32篇 |
2020年 | 22篇 |
2019年 | 24篇 |
2018年 | 20篇 |
2017年 | 21篇 |
2016年 | 26篇 |
2015年 | 11篇 |
2014年 | 22篇 |
2013年 | 31篇 |
2012年 | 52篇 |
2011年 | 56篇 |
2010年 | 37篇 |
2009年 | 28篇 |
2008年 | 40篇 |
2007年 | 35篇 |
2006年 | 35篇 |
2005年 | 23篇 |
2004年 | 22篇 |
2003年 | 5篇 |
2002年 | 9篇 |
2001年 | 3篇 |
2000年 | 3篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1996年 | 1篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有616条查询结果,搜索用时 390 毫秒
21.
Palladium catalyzed domino C-H functionalization reaction of arylaldehyde with dihaloarene has been developed to access 9-flourenone molecules. Bidentate ligand assisted strategy, single step reaction, high yield and excellent functional group tolerance make this method concise and effective for the synthesis of 9-flourenone. In addition, proposed method has been successfully employed to synthesise Tilorone in gram scale. 相似文献
22.
Patel Anuj P. Shaikh Mohammedumar M. Gurjar Kamlesh K. Chikhalia Kishor H. 《Research on Chemical Intermediates》2021,47(5):2049-2061
Research on Chemical Intermediates - Indenoquinolinones have been synthesized from 2-haloquinoline-3-carbaldehyde through Pd-mediated simultaneous C–H (aldehyde) and C–X bond... 相似文献
23.
An efficient and convenient conversion of oximes to corresponding carbonyl compounds with sodium perborate in glacial acetic acid is reported. 相似文献
24.
A series of donor–acceptor compounds 2–6 have been synthesized, via Knoevenagel condensation reaction (using conventional method, as well as microwave method). The ferrocene unit acts as a donor, conjugated phenyl–acetylene linker act as a π-electron relay unit, and malononitrile, cyanoacetic acid, and indanone groups act as acceptor. The electronic absorption spectra displayed a broad intramolecular charge transfer (CT) band in the visible region (450–650 nm). The electrochemical studies suggest considerable donor–acceptor interaction. The single crystal X-ray structure of 2, and 3 are reported, the structure reveals that 2 is nearly planar compared to 3. The supramolecular structure of 2 exhibits intramolecular C–H–π, and C–H–N interaction, which leads to formation of 2D network, whereas compound 3 shows head to tail dimer formation through C–H–π, and π–π interaction. 相似文献
25.
26.
Pradep Mathur Anjan K. Bhunia Ch. Srinivasu Shaikh Md. Mobin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(4-5):899-901
Group 16 elements serve as useful bridging and stabilising single atom ligands in mixed-metal carbonyl complexes and impart unusual reactivity on coordinated acetylenic moieties. Reactions of [Fe 3 (CO) 9 (μ 3 -E) 2 ] (E = S, or Se) with mononuclear acetylide complexes, [CpM(CO)_3-x(CCR)] (M = Mo or W, x = 0, R = Ph; M = Fe, x = 1, R = Ph or ferrocenyl) under facile conditions yield complexes featuring acetylide coupling, acetylide-flip and formation of oxo and acetylide-bridged complexes. In presence of free acetylenes, unusual ligand systems arising from C─S bond formation are observed and under certain conditions, formation of quinones by coupling of acetylenes with carbon monoxide is facilitated. 相似文献
27.
Sitaram Pal Sukumar Ghosh Bimal K. Banik Shaikh Khairul Alam Usha Ranjan Ghatak 《合成通讯》2013,43(14):2203-2216
The bridged-ethers, (±)-2-methoxy-9a-carbamorphinan (1b) and (±)-2-methoxy-9a-carba-14α-morphinan(2b) have been synthesized. The acid-catalyzed cyclizations of 1-m-methoxy benzyloctalone 3b and 1-m-methoxybenzyloctalins 4b proceed with high regio-and stereoselectivities leading mostly to the bridged-ketone 14 and ether 1b respectively, along with o-methoxy-tetracyclic ketone 15 and the ether 17, in addition to other minor products. 相似文献
28.
Dr. Dipanwita Das Hemlata Agarwala Dr. Abhishek Dutta Chowdhury Tuhin Patra Dr. Shaikh M. Mobin Prof. Dr. Biprajit Sarkar Prof. Dr. Wolfgang Kaim Prof. Dr. Goutam Kumar Lahiri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7384-7394
The complex series [Ru(pap)(Q)2]n ([ 1 ]n–[ 4 ]n; n=+2, +1, 0, ?1, ?2) contains four redox non‐innocent entities: one ruthenium ion, 2‐phenylazopyridine (pap), and two o‐iminoquinone moieties, Q=3,5‐di‐tert‐butyl‐N‐aryl‐1,2‐benzoquinonemonoimine (aryl=C6H5 ( 1+ ); m‐(Cl)2C6H3 ( 2+ ); m‐(OCH3)2C6H3 ( 3+ ); m‐(tBu)2C6H3 ( 4 +)). A crystal structure determination of the representative compound, [ 1 ]ClO4, established the crystallization of the ctt‐isomeric form, that is, cis and trans with respect to the mutual orientations of O and N donors of two Q ligands, and the coordinating azo N atom trans to the O donor of Q. The sensitive C? O (average: 1.299(3) Å), C? N (average: 1.346(4) Å) and intra‐ring C? C (meta; average: 1.373(4) Å) bond lengths of the coordinated iminoquinone moieties in corroboration with the N?N length (1.292(3) Å) of pap in 1 + establish [RuIII(pap0)(Q.?)2]+ as the most appropriate electronic structural form. The coupling of three spins from one low‐spin ruthenium(III) (t2g5) and two Q.? radicals in 1 +– 4 + gives a ground state with one unpaired electron on Q.?, as evident from g=1.995 radical‐type EPR signals for 1 +– 4 +. Accordingly, the DFT‐calculated Mulliken spin densities of 1 + (1.152 for two Q, Ru: ?0.179, pap: 0.031) confirm Q‐based spin. Complex ions 1 +– 4 + exhibit two near‐IR absorption bands at about λ=2000 and 920 nm in addition to intense multiple transitions covering the visible to UV regions; compounds [ 1 ]ClO4–[ 4 ]ClO4 undergo one oxidation and three separate reduction processes within ±2.0 V versus SCE. The crystal structure of the neutral (one‐electron reduced) state ( 2 ) was determined to show metal‐based reduction and an EPR signal at g=1.996. The electronic transitions of the complexes 1 n– 4 n (n=+2, +1, 0, ?1, ?2) in the UV, visible, and NIR regions, as determined by using spectroelectrochemistry, have been analyzed by TD‐DFT calculations and reveal significant low‐energy absorbance (λmax>1000 nm) for cations, anions, and neutral forms. The experimental studies in combination with DFT calculations suggest the dominant valence configurations of 1 n– 4 n in the accessible redox states to be [RuIII(pap0)(Q.?)(Q0)]2+ ( 1 2+– 4 2+)→[RuIII(pap0)(Q.?)2]+ ( 1 +– 4 +)→[RuII(pap0)(Q.?)2] ( 1 – 4 )→[RuII(pap.?)(Q.?)2]? ( 1 ?– 4 ?)→[RuIII(pap.?)(Q2?)2]2? ( 1 2?– 4 2?). 相似文献
29.
Nam T. Nguyen Edward Greenhalgh Mohd J. Kamaruddin Jaouad El harfi Kim Carmichael Georgios Dimitrakis Samuel W. Kingman John P. Robinson Derek J. Irvine 《Tetrahedron》2014
This paper reports the first detailed study focussed upon identifying the influence that microwave heating (MWH) has upon the mechanic steps involved in the tin catalysed ring-opening of lactones such as ?-caprolactone (CL). Direct comparison of conventional (CH) and microwave (MWH) heated kinetic studies showed that a key factor in the reduction of the polymerisation cycle time with MWH was the elimination of the induction period associated with in situ catalyst manufacture and initiation. NMR studies demonstrated that the most significant mechanistic change contributing to the observed induction time reduction/elimination was faster initiation (i.e., reaction of the initiatior/catalyst complex with the first monomer unit). Consequently, analysis of the dielectric properties of the reaction components predicted that this MWH induced change was related to the selective volumetric heating of both the catalyst and the monomer. Furthermore, this indication of the greater significance of the initiation step in defining the length of the induction period suggests that this is the rate determining step of the process, whether conducted by CH or MWH. Increasing the catalyst concentration was demonstrated to produce significant reductions in reaction heat-up time and to induce a significant (up to 30 °C) overshoot in reaction mixture bulk temperature in with MWH only. Thus supporting the conclusion that selective heating of the organometallic species in the system contributes directly to differences in the reaction conditions and which need to be taken into account when drawing comparisons with CH systems. Consequently, both effects were concluded to be thermally generated from selective volumetric heating. 相似文献
30.