全文获取类型
收费全文 | 1759篇 |
免费 | 64篇 |
国内免费 | 3篇 |
专业分类
化学 | 1437篇 |
晶体学 | 11篇 |
力学 | 21篇 |
数学 | 179篇 |
物理学 | 178篇 |
出版年
2023年 | 15篇 |
2022年 | 9篇 |
2021年 | 44篇 |
2020年 | 35篇 |
2019年 | 40篇 |
2018年 | 21篇 |
2017年 | 26篇 |
2016年 | 55篇 |
2015年 | 44篇 |
2014年 | 44篇 |
2013年 | 110篇 |
2012年 | 115篇 |
2011年 | 138篇 |
2010年 | 96篇 |
2009年 | 71篇 |
2008年 | 128篇 |
2007年 | 126篇 |
2006年 | 105篇 |
2005年 | 94篇 |
2004年 | 99篇 |
2003年 | 56篇 |
2002年 | 61篇 |
2001年 | 18篇 |
2000年 | 25篇 |
1999年 | 15篇 |
1998年 | 18篇 |
1997年 | 10篇 |
1996年 | 9篇 |
1995年 | 11篇 |
1994年 | 6篇 |
1993年 | 12篇 |
1992年 | 15篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 8篇 |
1988年 | 10篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 13篇 |
1984年 | 13篇 |
1983年 | 12篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 11篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1973年 | 4篇 |
1972年 | 5篇 |
1956年 | 3篇 |
排序方式: 共有1826条查询结果,搜索用时 640 毫秒
81.
The synthesis of some novel bakkenolides and their epi-spiro analogues was achieved by a new approach. Photolysis of allyl 1-(phenylseleno)-2-oxocyclopentanecarboxylates 7-9 afforded the corresponding spiro lactones 10-12 by radical cyclization via group transfer of the phenylseleno group. Selenoxide elimination of 11 and 12 produced the corresponding beta-methylene lactones 14 and 15. Diels-Alder cycloaddition of lactone11 with piperylene failed at ambient pressure, but proceeded in generally good yield in the presence of various Lewis acids at pressures of ca. 16 kbar, to give mixtures of beta-exo, alpha-endo, and beta-endo cycloadducts 19, 21, and 23, respectively. The preponderance of endo products 21 and 23, formed via highly hindered, but more compact, transition states was attributed to the high pressure and resulted in trans-dimethyl configurations of the products. The facial selectivity was dependent upon the Lewis acids, and the greatest alpha:beta ratio was observed with catalysts of the type TiCl(2)(OR)(2). Epimerization of the C-4 methyl group in 21 and 23 to furnish the corresponding cis-dimethyl analogues was achieved via exo-epoxidation, regioselective reduction, oxidation to the corresponding 3-keto derivatives, and base-catalyzed equilibration, thereby affording (+/-)-3,6-dioxobakkenolide-A (39) and its epi-spiro derivative 28, respectively. When the radical cyclization step was performed subsequent to the Diels-Alder cycloaddition by photolysis of perhydrindane 43, only the epi-spiro product 44 was obtained. 相似文献
82.
Narayan G. Bhat Patricia Wawroski Gonzalo Perez-Garcia Mayra Elizondo 《Tetrahedron letters》2005,46(31):5153-5155
A convenient, novel diastereoselective synthesis of 1-trimethylsilyl-(E)-1,3-alkenynes and a convenient synthesis of alkyl trimethylsilylethynyl ketones based on Z-1-bromo-1-alkenylboronate esters are developed. α-Bromo-(Z)-1-alkenylboronate esters readily available using literature procedures smoothly undergo a reaction with trimethylsilylethynyllithium (derived from the deprotonation of trimethylsilylethyne with n-butyllithium) in tetrahydrofuran to provide the corresponding ‘ate’ complexes. These ‘ate’ complexes undergo intramolecular nucleophilic substitution reactions to afford the corresponding (E)-1-alkenylboronate esters containing trimethylsilylethynyl moiety which upon protonolysis with acetic acid provide the corresponding 1-trimethylsilyl-(E)-1,3-alkenynes in good yields (70-82%) and in high stereochemical purities (>98%). These intermediates upon oxidation with hydrogen peroxide and sodium acetate afford the corresponding alkyl trimethylsilylethynyl ketones in good yields (66-78%). 相似文献
83.
84.
85.
86.
87.
Emilio J. González Patricia F. Requejo Ángeles Domínguez Eugénia A. Macedo 《Journal of solution chemistry》2013,42(4):746-763
In this study, densities and speeds of sound were measured over the whole composition range, at T = (298.15, 303.15 and 308.15) K and p = 0.1 MPa, for the binary systems of ethanol, or 1-propanol, or 2-propanol and 1-butyl-3-methylpyridinium bis(trifluoromethylsulfonyl)imide, or 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide. The density and speed of sound data were used to calculate the corresponding excess molar volumes and excess molar isentropic compressions, which were fitted with the Redlich–Kister equation. From the obtained results, a discussion was carried out in terms of interactions and structure factors in these binary mixtures. 相似文献
88.
89.