全文获取类型
收费全文 | 1004篇 |
免费 | 41篇 |
国内免费 | 45篇 |
专业分类
化学 | 1083篇 |
晶体学 | 4篇 |
物理学 | 3篇 |
出版年
2023年 | 23篇 |
2022年 | 9篇 |
2021年 | 13篇 |
2020年 | 18篇 |
2019年 | 33篇 |
2018年 | 46篇 |
2017年 | 40篇 |
2016年 | 19篇 |
2015年 | 24篇 |
2014年 | 82篇 |
2013年 | 142篇 |
2012年 | 39篇 |
2011年 | 66篇 |
2010年 | 37篇 |
2009年 | 55篇 |
2008年 | 69篇 |
2007年 | 58篇 |
2006年 | 42篇 |
2005年 | 51篇 |
2004年 | 59篇 |
2003年 | 29篇 |
2002年 | 51篇 |
2001年 | 17篇 |
2000年 | 11篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 5篇 |
1995年 | 8篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1985年 | 1篇 |
1982年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有1090条查询结果,搜索用时 15 毫秒
21.
Mhamed Lemhadri Touriya Zair Maurice Santelli 《Journal of organometallic chemistry》2007,692(11):2270-2281
The Heck reaction of aryl halides with functionalised alk-1-enes should be a powerful method for the synthesis of functionalised (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl chain when there are no substituents on the C3 carbon of the alk-1-enes. We observed that for the arylation of ethyl pent-4-enoate, ethyl 2-methylpent-4-enoate or dimethyl allylmalonate this migration could be partially or completely controlled using appropriate reaction conditions. The ramification on the alkyl chain and the substituents on the aryl halide have also an important influence on this migration. Moreover, the cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane/1/2[PdCl(C3H5)]2 system catalyses this reaction with a wide range of aryl bromides using very high ratio substrate/catalyst in good yields. 相似文献
22.
A highly efficient Suzuki cross-coupling reaction between benzylic halides and aryl boronic acids using palladium chloride as catalyst in acetone:water (3:1) as the solvent system has been developed. High yields of products, mild reaction conditions and short reaction times in the absence of ligand are important features of this method. 相似文献
23.
Matthias D’hooghe 《Tetrahedron letters》2007,48(10):1771-1774
1-Arylmethyl-2-(cyanomethyl)aziridines were transformed into novel N-arylmethyl-N-(2-chloro-3-cyanopropyl)amides as the major reaction products upon treatment with acid chlorides in CH2Cl2 through the ring opening of intermediate aziridinium salts. Subsequently, N-arylmethyl-N-(2-chloro-3-cyanopropyl)amides were converted into stable N-arylmethyl-N-(3-cyano-2-propenyl)amides for the first time by means of a dehydrochlorination mediated by Et3N in CH2Cl2. 相似文献
24.
A. V. Makarycheva-Mikhailova S. I. Selivanov N. A. Bokach V. Yu. Kukushkin P. F. Kelly A. J. L Pombeiro 《Russian Chemical Bulletin》2004,53(8):1681-1685
Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN)2] (R = Me, CH2Ph, Ph) with 1,2- and 1,4-PhS(=NH)C6H4SPh in CH2Cl2 afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The latter were isolated in 75—90% yields and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and 1H and 13C1H NMR spectroscopy. The temperature dependence of the 1H NMR spectra of the model [PtCl4{NH=C(R)N=SPh2}2] complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to -70 °C demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40 to -10 °C. The activation free energy of this process was calculated.Published in Russian in Izvestiya Akademii Nauk.
Seriya Khimicheskaya, No. 8, pp. 1618–1622, August, 2004. 相似文献
25.
Thomas Schareina 《Journal of organometallic chemistry》2004,689(24):4576-4583
Benzonitriles are easily accessible via palladium-catalyzed cyanation of aryl halides using potassium hexacyanoferrate(II) as cyanide source. This method is applicable on both activated and deactivated aryl and heteroaryl bromides and activated chlorides giving the corresponding benzonitriles in good to excellent yield. Advantageously, the used cyanating agent is non-toxic and cheap. The presented catalyst system is rather simple and it is not necessary to add expensive phosphines, making the novel method also attractive for industrial applications. 相似文献
26.
Anna Maria Zawisza 《Tetrahedron letters》2007,48(38):6738-6742
The Pd-catalyzed homocoupling of aryl halides in a basic DMF solution is often accompanied by the dehalogenation of the substrate as side reaction. When an inorganic base such as sodium bicarbonate is used, the reducing role of the solvent has been demonstrated using DMF-d7 and GC/MS analysis. 相似文献
27.
HuaRongZHAO XiaoFengLI XinJianZHAO YangPingNIU 《中国化学快报》2004,15(11):1292-1294
Aryl selenoamides react smoothly with a-haloacetic acid in various alcohol to givecorresponding bis(carboxyalkylmethyl) diselenides in good yields. 相似文献
28.
2,2-Dimethyl-3-(2-methyl-3-indolyl)cyclopropylacetic acid, its amide and esters, and the corresponding alcohol, viz., the product of ester reduction by LiAlH4, were synthesized. The chemoselectivity of N- and O-alkylation of these compounds was studied. Selective monoalkylation at the nitrogen atom of the heterocycle, O-alkylation to the side chain, or dialkylation at both nucleophilic sites can be carried out under conditions of phase-transfer catalysis. The N-acylation at the indole fragment of nitrile of this acid occurs only under the Vilsmeier—Haak formylation conditions. 相似文献
29.
Zvjezdana Lazarević Jasna Vorkapić-Furač Jasenka Mühl 《Monatshefte für Chemie / Chemical Monthly》1992,123(12):1175-1179
Summary Stable enolic isomers of 2-aroyl-4-aracyl-1,3-cyclopentanediones such as3 and4 were prepared by condensation of aryl methyl ketones and diethyl maleate using an excess of sodium ethoxide (Aryl=C6H5, 4-C6H4CH3, 4-C6H4Br and 4-C6H4Cl).
-Tricarbonyl Verbindungen. I. 2,4-Disubstituierte 1,3-Cyclopentandione
Zusammenfassung Stabile Enol-Isomere von 2-Aroyl-4-aracyl-1,3-cyclopentandionen wie3 und4 wurden durch Kondensation von Arylmethylketonen und Diethylmaleat mit einem Überschuß von Natriumethoxid dargestellt (Aryl=C6H5, 4-C6H4CH3, 4-C6H4Br und 4-C6H4Cl).相似文献
30.
Zhibo Ma 《Tetrahedron letters》2006,47(27):4721-4724
One-step and highly efficient syntheses of 2-aryl-1-benzazocines via Beckmann rearrangement of 5H-benzocyclohepten-5-one oxime mesylates in dry toluene was described, in which aryl Grignard reagents were used for the first time to induce Beckmann rearrangement directly without any additional protic agents. Iodotrimethylsilane was also employed to promote Beckmann rearrangement of the mesylates, followed by the treatment of the intermediate imidoyl iodide with phenylmagnesium bromide to complete the synthesis of benzazocines. 相似文献