全文获取类型
收费全文 | 17963篇 |
免费 | 568篇 |
国内免费 | 3421篇 |
专业分类
化学 | 14569篇 |
晶体学 | 54篇 |
力学 | 735篇 |
综合类 | 85篇 |
数学 | 4038篇 |
物理学 | 2471篇 |
出版年
2024年 | 140篇 |
2023年 | 799篇 |
2022年 | 646篇 |
2021年 | 652篇 |
2020年 | 1770篇 |
2019年 | 1423篇 |
2018年 | 1237篇 |
2017年 | 1050篇 |
2016年 | 1040篇 |
2015年 | 858篇 |
2014年 | 1154篇 |
2013年 | 3410篇 |
2012年 | 890篇 |
2011年 | 502篇 |
2010年 | 415篇 |
2009年 | 376篇 |
2008年 | 477篇 |
2007年 | 474篇 |
2006年 | 429篇 |
2005年 | 484篇 |
2004年 | 523篇 |
2003年 | 416篇 |
2002年 | 309篇 |
2001年 | 308篇 |
2000年 | 306篇 |
1999年 | 240篇 |
1998年 | 240篇 |
1997年 | 249篇 |
1996年 | 191篇 |
1995年 | 190篇 |
1994年 | 153篇 |
1993年 | 196篇 |
1992年 | 115篇 |
1991年 | 62篇 |
1990年 | 64篇 |
1989年 | 42篇 |
1988年 | 28篇 |
1987年 | 16篇 |
1986年 | 7篇 |
1985年 | 10篇 |
1984年 | 10篇 |
1983年 | 8篇 |
1982年 | 6篇 |
1981年 | 11篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1974年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 8 毫秒
991.
手性钯络合物催化下2-硝基环酮的不对称烯丙基化反应 总被引:2,自引:0,他引:2
在用氮杂冠醚改良的手性二茂铁膦与钯的络合物催化下, 2-硝基环酮可进行不对称烯丙基化反应. 讨论了配位基的形状, 反应物的构造, 碱的类型以及反应时间对反应速率和立体选择性的影响. 通过增加反应的空间位阻改进了反应的立体选择性 . 相似文献
992.
Qian Lei Yawen Wei Dinesh Talwar Prof. Chao Wang Prof. Dong Xue Prof. Jianliang Xiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(12):4021-4029
Reductive amination of various ketones and aldehydes by transfer hydrogenation under aqueous conditions has been developed, by using cyclometallated iridium complexes as catalysts and formate as hydrogen source. The pH value of the solution is shown to be critical for a high catalytic chemoselectivity and activity, with the best pH value being 4.8. In comparison with that in organic solvents, the reductive amination in an aqueous phase is faster, and the molar ratio of the substrate to the catalyst (S/C) can be set as high as 1×105, the highest S/C value ever reported in reductive amination reactions. The catalyst is easy to access and the reaction is operationally simple, allowing a wide range of ketones and aldehydes to react with various amines in high yields. The protocol provides a practical and environmental friendly new method for the synthesis of amine compounds. 相似文献
993.
Liang‐Hua Zou Dr. Adam Johannes Johansson Dr. Erik Zuidema Prof. Dr. Carsten Bolm 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(25):8144-8152
An efficient catalytic system for Sonogashira–Hagihara‐type reactions displaying ligand acceleration in the copper‐catalyzed formation of C(sp2)? C(sp) bonds is described. The structure of the ligand plays a key role for the coupling efficiency. Various copper sources show excellent catalytic activity, even in sub‐mol % quantities. A wide variety of substituents is tolerated in the substrates. Mechanistic details have been revealed by kinetic measurements and DFT calculations. 相似文献
994.
Majid M. Heravi Fatemeh Nahavandi Samaheh Sadjadi Hossein A. Oskooie Fatemeh F. Bamoharram 《合成通讯》2013,43(4):498-503
Reaction of aldehydes and 4-hydroxycoumarin in the presence of catalytic amount of silica-supported Preyssler nanoparticles led to synthesis of bis-coumarins in excellent yields. 相似文献
995.
The [3 + 2] cycloaddition reaction between sodium azide and various organic nitriles proceeds smoothly in the presence of amine salts as catalyst in dimethylformamide. The corresponding 5-substituted 1-H tetrazoles were obtained under mild condition in good to excellent yields. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
996.
Baylis–Hillman adducts 3-hydroxyl-2-methylene alkanoates have been converted in one pot into the corresponding (Z)-allyl phosphonates by treatment with FeCl3 and trialkyl phosphites in toluene under reflux. The products are formed in excellent yields (88–98%) within 1–1.5 h. The process is highly convenient and efficient, cost-effective, and remarkably stereoselective. 相似文献
997.
The activity of the [Pd{C6H4(CH2N(CH2Ph)2)}(µ-Br)]2 complex was investigated in the synthesis of symmetrical biaryls under both conventional and microwave irradiation conditions, and their results were compared. This complex is efficient, stable, and not sensitive to air or moisture and is a catalyst for the homo-coupling reaction of aryl iodides, bromides, and even chlorides. The products were produced in excellent yields in short reaction times using a catalytic amount of [Pd{C6H4(CH2N(CH2Ph)2)(µ-Br)]2 complex in N-methylpyrolidine (NMP) at 130 °C. In comparison to conventional heating conditions, the reactions under microwave irradiation gave better yields in shorter reaction times. 相似文献
998.
Direct condensation of carboxylic acids and alcohols with electronic, steric, and functional group variations was carried out using the environmentally benign, moisture-stable, inexpensive, and recoverable iron(III) acetylacetonate [Fe(acac)3] as catalyst (5 mol%). This iron salt efficiently catalyzed the esterification of several primary and secondary alcohols in refluxing xylene, without the need for a dehydration reagent. The chemoselectivity of the proposed protocol was demonstrated by the selective esterification of primary alcohol functionality in racemic 1-phenylethane-1,2-diol with benzoic acid. The esterification was also applicable to unmasked α -hydroxyacid, guasiaromatic, heterocyclic, and N-protected amino acids. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications® to view the free supplemental file. 相似文献
999.
Abdelbasset A. Farahat 《合成通讯》2013,43(2):245-252
Copper(I) 3-methylsalicylate (CuMeSal) mediates N-arylation reactions between aryl boronic acids and aromatic heterocycles (Chan–Lam coupling) under moderate reaction conditions (K2CO3, methanol, 65 °C, in air, 3–5 h). Both electron-rich and electron-deficient aryl boronic acids and a diverse set of N-heterocycles were allowed to react and gave N-arylation products in reasonable yields, which demonstrate the utility of this catalyst. 相似文献
1000.
Leonid Kikot Alexander Lyapunov Tatiana Bogaschenko Sergey Smola Catherine Kulygina 《合成通讯》2013,43(4):478-484
A new facile synthetic route to benzils containing fragments of 12-crown-4, 15-crown-5, and 18-crown-6 by oxidation of corresponding stilbenes was developed. The first representative of a new family of fluorescent sensors was obtained by reaction of bis(15-crown-5)benzil with o-phenylenediamine. The latter exhibits great fluorescence enhancement upon association with K+ and Rb+ compared to Na+ and Cs+. 相似文献