全文获取类型
收费全文 | 1192篇 |
免费 | 33篇 |
国内免费 | 5篇 |
专业分类
化学 | 804篇 |
晶体学 | 1篇 |
力学 | 45篇 |
数学 | 214篇 |
物理学 | 166篇 |
出版年
2023年 | 6篇 |
2019年 | 11篇 |
2018年 | 14篇 |
2017年 | 11篇 |
2016年 | 24篇 |
2015年 | 27篇 |
2014年 | 26篇 |
2013年 | 61篇 |
2012年 | 49篇 |
2011年 | 42篇 |
2010年 | 27篇 |
2009年 | 31篇 |
2008年 | 46篇 |
2007年 | 46篇 |
2006年 | 40篇 |
2005年 | 38篇 |
2004年 | 40篇 |
2003年 | 36篇 |
2002年 | 52篇 |
2001年 | 14篇 |
2000年 | 17篇 |
1999年 | 16篇 |
1998年 | 15篇 |
1997年 | 13篇 |
1996年 | 13篇 |
1995年 | 13篇 |
1994年 | 11篇 |
1993年 | 15篇 |
1992年 | 20篇 |
1991年 | 12篇 |
1990年 | 20篇 |
1989年 | 7篇 |
1988年 | 21篇 |
1987年 | 13篇 |
1986年 | 12篇 |
1985年 | 27篇 |
1984年 | 23篇 |
1983年 | 29篇 |
1982年 | 21篇 |
1981年 | 16篇 |
1980年 | 28篇 |
1979年 | 21篇 |
1978年 | 24篇 |
1977年 | 21篇 |
1976年 | 32篇 |
1975年 | 13篇 |
1974年 | 13篇 |
1973年 | 10篇 |
1972年 | 9篇 |
1971年 | 7篇 |
排序方式: 共有1230条查询结果,搜索用时 15 毫秒
51.
van der Rest G Mourgues P Nedev H Audier HE 《Journal of the American Society for Mass Spectrometry》2000,11(8):705-710
The bimolecular reaction of the CH2CHOH.+ enol ion (m/z 44) with acetaldehyde gives a strongly dominant product,m/z 45, formed mainly by proton transfer from the ion to the molecule. The abundance of the product coming from a H. abstraction reaction from the neutral, albeit more exothermic, is negligible. In order to explain this result, the long lived [CH2CHOH.+, CH3CHO] solvated ion was generated by reaction of the CH2CHOH.+ enol ion with (CH3CHO) n in the cell of a Fourier transform ion cyclotron resonance mass spectrometer. The structure of this solvated ion was clearly established. Labeling indicates that [CH2CHOH.+, CH3CHO], upon low energy collisions, reacts by H. abstraction more rapidly than by H+ transfer to the neutral moiety. This shows that the entropic factors are determinant when the enol ion reacts directly with acetaldehyde. 相似文献
52.
Summary. A series of novel tridentate ligands with nitrogen and oxygen donor sites was synthesized starting from enantiomerically
pure (S)- and (R)-1-(pyridin-2-yl)ethylamine, the preparation and resolution of which was developed. The new optically active ligands were
tested as in situ catalysts together with Ru(PPh3)3Cl2 in the enantioselective transfer hydrogenation of acetophenone with isopropanol. The secondary amine ligand (S)-2,4-di-tert-butyl-6-(1-(pyridin-2-yl)ethylamino)methylphenol gave the best results with almost quantitative conversion and 47%ee.
Received August 17, 2001. Accepted August 27, 2001 相似文献
53.
Henri Patin Gerard Mignani Christian Mahe Jean-Yves Le Marouille Alain Benoit Daniel Grandjean 《Journal of organometallic chemistry》1980,193(1):93-103
103Rh Chemical shifts of a variety of mono- and di-nuclear rhodium carbonyl complexes are reported together with the modifications to the probe and decoupler unit of a JEOL PS-100 PFT spectrometer which enable these 103Rh-decoupled 13C NMR measurements to be made. These data are discussed in conjunction with 13C NMR data on other rhodium carbonyls. 相似文献
54.
Henri Brunner Manfred Muschiol Ivan Bernal George M. Reisner 《Journal of organometallic chemistry》1980,198(2):169-178
C7H7Mo(CO)(PN★)I (I) (PN★ (S)(+)-(C6H5)2PN(CH3)CH(CH3)(C6H5)) is prepared in 90% yield by reaction of C7H7Mo(CO)2I and PN★. The two diastereo-isomers Ia and Ib differing only in the Mo-configuration exhibit chemical shift differences of their C7H7 and CH3 signals. Ia and Ib can be separated by fractional crystallization. In solution Ia epimerizes with respect to the Mo configuration. The half lives in benzene for the equilibration Ia ? Ib are 5.5, 30, and 104 min at 60, 50, and 40°C, respectively. Phosphine exchange experiments show that the epimerization proceeds via PN★ dissociation.An X-ray structure analysis was carried out on a single crystal of Ia. The absolute configuration at Mo was determined to be (R). 相似文献
55.
We report here our findings on a new and highly efficient strategy for the synthesis of β-amino acids involving the addition of bis(O-silyl) ketene acetals on Mannich type iminium electrophiles. 相似文献
56.
[RhCl(C8H14)2]2 together with the optically active amidines C6H5C(=NR)NHCH(CH3) (C6H5) I–V or their Li derivatives after activation with molecular hydrogen gives catalysts which at room temperature and 1.1 bar H2-pressure hydrogenate the prochiral substrates (Z)-[N-acetylamino]-cinnamic acid, itaconic acid, -methylcinnamic acid, -methylcinnamic aldehyde, and -methylcinnamic alcohol as well as cyclohexene, benzene and toluene. Good hydrogenation activity of the new catalysts is in contrast to low optical induction which only in the hydrogenation of -methylcinnamic alcohol with 1.5 to 2% leads to values different from zero.
3. Mitt.:H. Brunner undW. Pieronczyk, J. Chem. Res., im Druck. 相似文献
57.
In order to establish the mechanism of CO loss occurring during metastable decomposition of protonated 1-indanone, fragmentations of monocyclic [C9H9O]+ isomers have been studied. These ions of known structure were prepared by CI protonation and fragmentation of the corresponding acids chlorides. It is demonstrated that the wide component of the [MH? CO]+ metastable peak induced by protonated 1-indanone fragmentation is the result of fragmentation of the [C6H5CH2CH2CO]+ isomer ion. 相似文献
58.
Imrich Gci Jn Imrich Pavol Kristian Henri Kivel Pauliina Valtamo Kalevi Pihlaja 《Journal of heterocyclic chemistry》2005,42(5):907-918
The synthesis of regioisomeric 3‐alkyl(aryl)‐2‐(acridin‐9′‐yl)imino‐1,3‐thiazolidin‐4‐ones ( 8b‐i ) and 2‐alkyl(aryl)imino‐3‐(acridin‐9′‐yl)‐1,3‐thiazolidin‐4‐ones ( 11a‐i ) was performed by the reaction of 3‐(acridin‐9‐yl)‐1‐alkyl(aryl)thioureas 5a‐i with methyl bromoacetate and bromoacetyl bromide, respectively, via the corresponding isothiourea hydrobromides with excellent regioselectivity. The structure, NMR spectra and mass spectrometric behavior of the resulting compounds are discussed. 相似文献
59.
cis,cis,cis-1,2,3,4-Tetrakis(diphenylphosphinomethyl)cyclopentane/[PdCl(C3H5)]2 efficiently catalyses the Heck reaction of β-substituted enol ethers with aryl bromides. Employing β-methoxystyrene, 3-ethoxyacrylonitrile or methyl 3-methoxyacrylate, the regioselective α-arylation of these enol ethers was observed in all cases, and mixtures of Z and E isomers were generally obtained, which in many cases yielded a single ketone product after acid treatment. The stereoselectivity of this reaction depends on steric and electronic factors, and better stereoselectivities in favour of Z isomers were observed with electron-rich or sterically congested aryl bromides. Better yields were obtained for this reaction with electron-rich or sterically congested aryl bromides than with electron-poor aryl bromides. This observation suggests that with these β-substituted enol ethers the rate-limiting step of the catalytic cycle is not the oxidative addition of the aryl bromide to the palladium complex. 相似文献
60.