全文获取类型
收费全文 | 428篇 |
免费 | 90篇 |
国内免费 | 156篇 |
专业分类
化学 | 664篇 |
物理学 | 10篇 |
出版年
2023年 | 1篇 |
2022年 | 7篇 |
2021年 | 16篇 |
2020年 | 32篇 |
2019年 | 24篇 |
2018年 | 19篇 |
2017年 | 8篇 |
2016年 | 37篇 |
2015年 | 29篇 |
2014年 | 30篇 |
2013年 | 46篇 |
2012年 | 29篇 |
2011年 | 24篇 |
2010年 | 31篇 |
2009年 | 27篇 |
2008年 | 17篇 |
2007年 | 20篇 |
2006年 | 17篇 |
2005年 | 23篇 |
2004年 | 26篇 |
2003年 | 39篇 |
2002年 | 54篇 |
2001年 | 25篇 |
2000年 | 29篇 |
1999年 | 20篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 11篇 |
1995年 | 6篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有674条查询结果,搜索用时 671 毫秒
1.
Fluoride effect on the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates
Michela Gasperini Fabio Ragaini Sergio Cenini Emma Gallo Simone Fantauzzi 《应用有机金属化学》2007,21(9):782-787
Fluorides promote the palladium–phenanthroline catalyzed carbonylation of nitroarenes to carbamates. The effect is more evident on the rate of the reaction at short reaction times, but a positive effect on selectivity is also observed under certain conditions. The effect is observed even under conditions under which chloride inhibits the reaction. Tetraethylammonium is a better countercation than sodium. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
2.
Tandem intramolecular silylformylation-allyl(crotyl)silylation reactions have been developed that allow the highly efficient synthesis of polyketide fragments. The substrates are subjected to Rh(I)-catalyzed silylformylation to afford β-(diallyl)silyl aldehydes which undergo spontaneous uncatalyzed allylsilylation. This unusual spontaneous allylsilylation reaction is driven by strain release Lewis acidity, which arises from the ∼95° O-Si-C bond angle in the oxasilacyclopentane product of the silylformylation reaction. The methodology has been developed both for alkene and alkyne substrates, may be used to establish as many as three stereocenters, and has been shown to be amenable to use in an iterative fashion. 相似文献
3.
A. L. Lapidus S. D. Pirozhkov A. R. Tumanova T. G. Koksharova N. V. Volkova V. A. Bakulev V. S. Mokrushin 《Russian Chemical Bulletin》1992,41(1):178-180
A new method has been developed for the synthesis of the ethyl ester of the mononitrile of malonic acid by the carbonylation of benzenesulfonyloxyacetonitrile in absolute ethanol in the presence of cobalt carbonyl. The yield of the desired product was 30% with 60–90% conversion of the starting compound. The effects of temperature, pressure, and reaction time were studied.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. S. M. Kirov Urals Polytechnical Institute, Ekaterinburg. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 215–216, January, 1992. 相似文献
4.
一种甲醇直接气相羰基化新催化剂 总被引:12,自引:0,他引:12
本世纪70年代Monsanto公司成功开发了甲醇液相羰化RhI催化体系,使甲醇羰化生产醋酸成为重要的工业过程.然而,由于此工艺产物与催化剂分离复杂、铑资源紧缺以及体系中还必须加大量的碘甲烷(或氢碘酸)作促进剂,设备腐蚀严重.80年代以来,甲醇气相羰... 相似文献
5.
A novel type of heterogenized CuCl2 catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl– while keeping the catalytic activity of the homogeneous CuCl2 catalyst, we adopted, as supports (or ligands) of CuCl2, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl2 and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl2 and Ppy-CuCl2 catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl2 catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl2 catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl2 leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system. 相似文献
6.
7.
8.
常压气相氧化羰基化合成碳酸二乙酯 总被引:3,自引:0,他引:3
碳酸二乙酯是一种重要的有机化工原料,可广泛用于合成农药如脱叶灵,医药如喹啉酮衍生物,中间体3-氧硫代羧酸酯,还可用于电子管阴极的镀层[1-3]。生产碳酸二乙酯的传统方法为:无水乙醇与光气反应生成氯甲酸乙酯,氯甲酸乙酯继续与乙醇反应生成碳酸二乙酯后经水洗蒸馏制成。使用光气为原料对设备的要求较高。我们在常压下气相羰基化合成碳酸二乙酯[4]:2NO+C2H5OH+0.5O2→2C2H5ONO+H2O(1)CO+2C2H5ONO→(C2H5O)2CO+2NO(2)产生的一氧化氮可与氧气和乙醇进行反应再生为亚硝酸乙酯,符合原子经济反应且几乎不放出对… 相似文献
9.
超强酸性室温离子液体反应介质中烷烃羰化研究 总被引:10,自引:0,他引:10
在卤化1-烷基吡啶和1-甲基-3-烷基咪唑季胺盐与无水AlCl_3组成的超强酸性 氯铝酸室温离子液中,首次实现了烷烃与CO的直接羰化反应。2,2,4-甲基戊烷可 直接与CO反应,产物为酮。 相似文献
10.