全文获取类型
收费全文 | 3960篇 |
免费 | 126篇 |
国内免费 | 34篇 |
专业分类
化学 | 2951篇 |
晶体学 | 33篇 |
力学 | 85篇 |
综合类 | 1篇 |
数学 | 536篇 |
物理学 | 514篇 |
出版年
2023年 | 15篇 |
2022年 | 24篇 |
2021年 | 31篇 |
2020年 | 55篇 |
2019年 | 54篇 |
2018年 | 33篇 |
2017年 | 39篇 |
2016年 | 89篇 |
2015年 | 90篇 |
2014年 | 99篇 |
2013年 | 212篇 |
2012年 | 206篇 |
2011年 | 321篇 |
2010年 | 120篇 |
2009年 | 126篇 |
2008年 | 256篇 |
2007年 | 259篇 |
2006年 | 257篇 |
2005年 | 251篇 |
2004年 | 224篇 |
2003年 | 162篇 |
2002年 | 158篇 |
2001年 | 41篇 |
2000年 | 48篇 |
1999年 | 40篇 |
1998年 | 37篇 |
1997年 | 42篇 |
1996年 | 60篇 |
1995年 | 35篇 |
1994年 | 43篇 |
1993年 | 45篇 |
1992年 | 35篇 |
1991年 | 36篇 |
1990年 | 24篇 |
1989年 | 22篇 |
1988年 | 24篇 |
1987年 | 16篇 |
1986年 | 18篇 |
1985年 | 46篇 |
1984年 | 39篇 |
1983年 | 30篇 |
1982年 | 54篇 |
1981年 | 43篇 |
1980年 | 41篇 |
1979年 | 32篇 |
1978年 | 40篇 |
1977年 | 32篇 |
1976年 | 24篇 |
1975年 | 31篇 |
1974年 | 19篇 |
排序方式: 共有4120条查询结果,搜索用时 15 毫秒
31.
The use of allyl protecting group mediated intramolecular aglycon delivery (IAD) as a strategy for intramolecular glycosylation has been extended to allow the stereoselective synthesis of α-glucofuranosides and β-rhamnopyranosides, in a totally stereoselective fashion. The efficiency of intramolecular glycosylation is dependent on the protecting group pattern of the glycosyl donor, and on the steric bulk of the glycosyl acceptor. 相似文献
32.
Stephen G. Davies Ian A. Hunter Rebecca L. Nicholson Paul.M. Roberts Edward D. Savory Andrew D. Smith 《Tetrahedron》2004,60(35):7553-7577
α-Dibenzylamino- and α-benzyloxy- derivatives of N-acetyl-(S)-4-benzyl-5,5-dimethyloxazolidin-2-one readily undergo highly stereoselective boron mediated syn-aldol reactions with a range of aromatic and aliphatic aldehydes, generating the syn-aldol products in good to excellent yields as single diastereoisomers after purification. In the α-dibenzylamino series, deprotection of the functionalised aldol fragments to the corresponding α-amino-β-hydroxy methyl ester or α-amino-β-hydroxyaldehyde proved problematic, with a range of N- and O-protecting groups giving mixtures of products arising from endocyclic and exocyclic cleavage pathways. However, in the α-benzyloxy series, O-silyl protection of the aldol products, and subsequent DIBAL reduction gives stereoselectively the corresponding N-1′-hydroxyalkyloxazolidin-2-ones, which undergo base promoted fragmentation to the desired highly functionalised and differentially protected α,β-dihydroxyaldehydes in good yields and without loss of stereochemical integrity. 相似文献
33.
Appleby I Boulton LT Cobley CJ Hill C Hughes ML de Koning PD Lennon IC Praquin C Ramsden JA Samuel HJ Willis N 《Organic letters》2005,7(10):1931-1934
Two methods to produce (2S)-5-amino-2-(1-n-propyl-1H-imidazol-4-ylmethyl)-pentanoic acid were investigated. Diastereoisomeric salt resolution, using the quinidine salt, gave the desired intermediate in 98% ee and 33% yield. Asymmetric hydrogenation of various substrates gave high conversions, with up to 83% ee. Integration of these two approaches via asymmetric hydrogenation of a quinidine salt substrate followed by crystallization provided the desired intermediate in 94% ee and 76% yield. 相似文献
34.
Using flow microcalorimetry, the ion association reaction M2+(aq)+Fe(CN)
6
4–
(aq)=MFe(CN)
6
2–
(aq) (M=Ca, Mg) has been studied at 25°C over the ionic strength range 0.02 to 0.08 mol-dm–3. Analyses of the data to obtain Ho, the enthalpy change at infinite dilution, are described. The value obtained for Ho is sensitive to the kind of functions used to correct for non-ideal behavior. 相似文献
35.
Ian K. Boddy J. Boniface Richard C. Cambie Peter A. Craw David S. Larsen Hamish McDonald Peter S. Rutledge Paul D. Woodgate 《Tetrahedron letters》1982,23(42):4407-4408
Gentle heating of allyloxyanthraquinones with sodium dithionite in dimethylformanide - water effects a rapid and controlled rearrangement to give high yields of 2-allyanthraquinones. 相似文献
36.
Daniel E. Lynch Gillian E. Spicer Ian Mcclenaghan 《Journal of heterocyclic chemistry》2005,42(7):1363-1368
Three α‐phenylmalonamides have been prepared by the selective nucleophilic cleavage of 5,7‐dimethyl‐2‐phenyl‐1‐oxo‐1H‐pyrazolo[1,2‐a]pyrazol‐4‐ylium‐3‐olate in solventless microwave syntheses. The three weak nucleophiles employed were aniline, p‐chloroaniline and m‐toluidine. The α‐phenylmalonamides of these three aniline derivatives could not be prepared using the previously reported solvent syntheses via 3‐oxopyrazolo[1,2‐a]pyrazol‐8‐ylium‐1‐olates. All products were characterised using, infrared spectroscopy, 1H nmr and electrospray mass spectrometry. The single crystal X‐ray structures of the starting pyrazolo‐[1,2‐a]pyrazole and α‐phenylmalon‐m‐toluidide are also reported. 相似文献
37.
38.
Summary Under suitable conditions, we prove the convergence of the Bateman method for integral equations defined over bounded domains inR
d
,d1. The proof makes use of Hilbert space methods, and requires the integral operator to be non-negative definite. For one-dimensional integral equations over finite intervals, estimated rates of convergence are obtained which depend on the smoothness of the kernel, but are independent of the inhomogeneous term. In particular, for aC
kernel andn reasonably spaced Bateman points, the convergence is shown to be faster than any power of 1/n. Numerical calculations support this result. 相似文献
39.
N-Alkoxycarbonyl- and N-carboxamido-oxaziridines are shown to react with aromatic alkenes to give epoxide, aziridine or hydro-oxidation products, in ratios depending on the oxaziridine structure. Chiral oxaziridines can effect epoxidation and hydro-oxidation with promising levels of asymmetric induction. 相似文献
40.
Treatment of [Ti(O-i-Pr)(2)Cl(2)] with NaL(OEt) (L(OEt)(-) = [CpCo[P(O)(OEt)(2)](3)](-), Cp = eta(5)-C(5)H(5)) afforded [L(OEt)Ti(O-i-Pr)(2)Cl] that reacted with HCl in ether to give [L(OEt)TiCl(3)] (1). The average Ti-O and Ti-Cl distances in 1 are 1.975 and 2.293 A, respectively. Reaction of titanyl sulfate with NaL(OEt) in water followed by addition of HBF(4) afforded [L(OEt)TiF(3)] (2), the Ti-O and Ti-F distances of which are 2.020(2) and 1.792(2) A, respectively. The Zr(IV) analogue [L(OEt)ZrF(3)] (3) was prepared similarly from zirconyl nitrate, NaL(Oet), and HBF(4) in water. The Zr-O and average Zr-F distances in 3 are 2.139(2) and 1.938(2) A, respectively. Treatment of 1 with tetrachlorocatechol (H(2)Cl(4)cat) afforded [L(OEt)Ti(Cl(4)cat)Cl] (4). The average Ti-O(P), Ti-O(C), and Ti-Cl distances in 4 are 1.972, 1.926, and 2.334 A, respectively. Hydrolysis of 4 in the presence of Et(3)N yielded the mu-oxo dimer [(L(OEt))(2)Ti(2)(Cl(4)cat)(2)(mu-O)] (5). The average Ti-O(P), Ti-O(C), and Ti-O(Ti) distances in 5 are 2.027, 1.926, and 1.7977(9) A. Treatment of 1 with 1,1'-binaphthol (BINOLH(2)) in the presence of Et(3)N afforded [(L(OEt))(2)Ti(2)(mu-O)(2)(mu-BINOL)] x 2BINOLH(2) (6.2BINOLH(2)). Complex 1 is capable of catalyzing ring opening of epoxides with Me(3)SiN(3) under solvent-free conditions presumably via a Ti-azide intermediate. 相似文献