全文获取类型
收费全文 | 15331篇 |
免费 | 641篇 |
国内免费 | 45篇 |
专业分类
化学 | 10408篇 |
晶体学 | 237篇 |
力学 | 479篇 |
综合类 | 2篇 |
数学 | 1172篇 |
物理学 | 3719篇 |
出版年
2024年 | 48篇 |
2023年 | 169篇 |
2022年 | 402篇 |
2021年 | 453篇 |
2020年 | 480篇 |
2019年 | 543篇 |
2018年 | 509篇 |
2017年 | 480篇 |
2016年 | 694篇 |
2015年 | 484篇 |
2014年 | 776篇 |
2013年 | 1295篇 |
2012年 | 1160篇 |
2011年 | 1217篇 |
2010年 | 795篇 |
2009年 | 623篇 |
2008年 | 765篇 |
2007年 | 750篇 |
2006年 | 597篇 |
2005年 | 526篇 |
2004年 | 402篇 |
2003年 | 334篇 |
2002年 | 273篇 |
2001年 | 166篇 |
2000年 | 142篇 |
1999年 | 111篇 |
1998年 | 77篇 |
1997年 | 103篇 |
1996年 | 98篇 |
1995年 | 79篇 |
1994年 | 75篇 |
1993年 | 107篇 |
1992年 | 102篇 |
1991年 | 83篇 |
1990年 | 69篇 |
1989年 | 74篇 |
1988年 | 51篇 |
1987年 | 51篇 |
1986年 | 47篇 |
1985年 | 70篇 |
1984年 | 69篇 |
1983年 | 58篇 |
1982年 | 52篇 |
1981年 | 44篇 |
1980年 | 48篇 |
1979年 | 66篇 |
1978年 | 52篇 |
1977年 | 59篇 |
1976年 | 47篇 |
1975年 | 36篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
151.
Density functional calculations have been carried out on a series of linearly annelated acenes and their BN analogues. Even though borazine shows aromatic and reactivity behavior parallel with that of benzene, its condensed derivatives show patterns different from those of their hydrocarbon analogues. Nucleus independent chemical shift (NICS) values in acenes suggest that the aromaticity of the inner rings is more than that of benzene, whereas in BN-acenes there is no substantial change in the aromaticity of the individual rings. Molecular electrostatic potential (MESP) is employed to obtain further insights into the bonding and reactivity trends for these systems. The MESP topography patterns of acenes and BN-acenes are substantially different, with BN-acenes showing more localized pi electron features compared to those of acenes. The MESP values at the critical points (CPs) indicate overall lowering of aromaticity in these annelated systems. However, this change is gradual among the BN-acenes. 相似文献
152.
Synthesis of phthalide derivatives using nickel-catalyzed cyclization of o-haloesters with aldehydes
Rayabarapu DK Chang HT Cheng CH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(12):2991-2996
The reaction of o-bromobenzoate (1 b) with benzaldehyde (2 a) in the presence of [NiBr(2)(dppe)] (dppe=1,2-bis(diphenylphosphino)ethane) and zinc powder in THF (24 hours, reflux temperature), afforded 3-phenyl-3H-isobenzofuran-1-one (3 a) in an 86 % yield. Similarly, o-iodobenzoate reacts with 2 a to give 3 a, but in a lower yield (50 %). A series of substituted aromatic and aliphatic aldehydes (2 b, 4-MeC(6)H(4)CHO; 2 c, 4-MeOC(6)H(4)CHO; 2 d, 3-MeOC(6)H(4)CHO; 2 e, 2-MeOC(6)H(4)CHO; 2 f, 4-CNC(6)H(4)CHO; 2 g, 4-(Me)(3)CC(6)H(4)CHO; 2 h, 4-C(6)H(5)C(6)H(4)CHO; 2 i, 4-ClC(6)H(4)CHO; 2 j, 4-CF(3)C(6)H(4)CHO; 2 k, CH(3)(CH(2))(5)CHO; 2 l, CH(3)(CH(2))(2)CHO) also underwent cyclization with o-bromobenzoate (1 b) producing the corresponding phthalide derivatives in moderate to excellent yields and with high chemoselectivity. Like 1 b, methyl 2-bromo-4,5-dimethoxybenzoate (1 c) reacts with tolualdehyde (2 b) to give the corresponding substituted phthalide 3 m in a 71 % yield. The methodology can be further applied to the synthesis of six-membered lactones. The reaction of methyl 2-(2-bromophenyl)acetate (1 d) with benzaldehyde under similar reaction conditions afforded six-membered lactone 3 o in a 68 % yield. A possible catalytic mechanism for this cyclization is also proposed. 相似文献
153.
New secondary and tertiary amine borane derivatives were prepared in a one-pot reaction starting from primary amine boranes. The reaction involves treatment of an amine borane with 2 equivalents of s-BuLi at −78 °C. In general, mixtures of mono and di metallated products were obtained. Alkyl iodides and benzyl chloride reacted with the lithiated amine, but aldehydes and ketones were reduced. Conversion was high as determined by NMR, but moderate to low yields were obtained after chromatography, possibly due to decomposition on silica. Crystal structures were obtained for the compounds 3a, 3b and 3c. 相似文献
154.
A new Schiff base has been synthesized from 4-aminoantipyrine and 3-formylsalicylic acid. The ligand has a dianionic tetradentate compartmental OONO donor system. The cobalt(II), nickel(II), copper(II) and dioxouranium(VI) complexes exist in phenolato-bridged dinuclear species, while palladium(II) gives a mononuclear complex with free –COOH groups. The complexes have been characterized by elemental analyses, i.r., u.v.-vis, thermal and magnetic measurements. 相似文献
155.
Summary New dioxomolybdenum(VI) complexes MoO2L · H2O (LH2=Schiff base) derived from Salicylhydrazide and salicylaldehyde, 5-chloro-, 5-bromo-, 5-nitro-, 3-methoxy, 3-ethoxy-, 3,5-dichlorosalicylaldehyde and 2-hydroxy-1-naphthaldehyde have been synthesized and characterized, together with the MoO2L · THF adducts. The complexes are monomers, nonelectrolytes and diamagnetic, and contain acis O=Mo=O 相似文献
156.
Chloride1), borohydrides2) and hydrides3) of dicyclopentadienyl thallium (III) and diindenyl thallium (III) have already been reported. The present communication deals with a study on the preparation and characterization of difluorenyl thallium (III) chloride, -hydride and -borohydride. 相似文献
157.
An efficient route for the regio- and stereoselective ring opening of N-tosylaziridines with zinc dihalides (ZnX2, X = Cl, Br, I) is described. Depending on the solvent and Zn(II) halide, β-halo amines or imidazolines are obtained selectively in good to excellent yields. 相似文献
158.
Akhilesh K. Verma Rupesh Kumar Amit Saxena Subho Mozumdar 《Tetrahedron letters》2005,46(31):5229-5232
A novel method for effecting the aza-Michael reactions of N-alkyl- and N-arylpiperazines with acrylonitrile using Cu-nanoparticles is described. The method features the use of 10 mol % Cu (14-17 nm) nanoparticles under mild reaction conditions to afford the addition products in good to excellent yields. The Cu-nanoparticles selectively catalysed the aza-Michael reaction of N-alkyl- and N-arylpiperazines in the presence of aromatic amino or aliphatic hydroxy groups. 相似文献
159.
J.S. Yadav B.V. Subba Reddy K.V. Raghavendra Rao G.G.K.S. Narayana Kumar 《Tetrahedron letters》2007,48(31):5573-5576
Indoles undergo smooth alkylation with propargylic alcohols in the presence of 10 mol % of scandium triflate under mild conditions to produce 3-propargylated indoles in excellent yields with high selectivity. 相似文献
160.
An efficient and mild method for the reduction of aromatic nitro and azido groups on solid support using Al/NiCl2·6H2O and Al/NH4Cl is described. This solid phase reduction technique has been applied towards the synthesis of DNA binding pyrrolo[2,1-c][1,4]benzodiazepine antitumour antibiotics. 相似文献