全文获取类型
收费全文 | 16516篇 |
免费 | 1319篇 |
国内免费 | 644篇 |
专业分类
化学 | 6660篇 |
晶体学 | 106篇 |
力学 | 1526篇 |
综合类 | 162篇 |
数学 | 5832篇 |
物理学 | 4193篇 |
出版年
2024年 | 10篇 |
2023年 | 218篇 |
2022年 | 257篇 |
2021年 | 484篇 |
2020年 | 613篇 |
2019年 | 536篇 |
2018年 | 493篇 |
2017年 | 619篇 |
2016年 | 611篇 |
2015年 | 548篇 |
2014年 | 879篇 |
2013年 | 1711篇 |
2012年 | 916篇 |
2011年 | 981篇 |
2010年 | 791篇 |
2009年 | 1247篇 |
2008年 | 1129篇 |
2007年 | 1040篇 |
2006年 | 834篇 |
2005年 | 752篇 |
2004年 | 639篇 |
2003年 | 495篇 |
2002年 | 431篇 |
2001年 | 266篇 |
2000年 | 267篇 |
1999年 | 241篇 |
1998年 | 183篇 |
1997年 | 169篇 |
1996年 | 160篇 |
1995年 | 141篇 |
1994年 | 130篇 |
1993年 | 98篇 |
1992年 | 87篇 |
1991年 | 53篇 |
1990年 | 41篇 |
1989年 | 39篇 |
1988年 | 42篇 |
1987年 | 31篇 |
1986年 | 21篇 |
1985年 | 46篇 |
1984年 | 53篇 |
1983年 | 23篇 |
1982年 | 30篇 |
1981年 | 31篇 |
1980年 | 18篇 |
1979年 | 18篇 |
1978年 | 14篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1974年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A Practical Synthesis of 1,4,7,10-Tetraaza-Cyclododecane,A Pivotal Precursor for MRI Contrast Agents
A practical preparation of the versatile macrocycle 1,4,7,10-tetraazacyclododecane (cyclen) was developed starting from cheap and easily available starting materials as ethylenediamine and glyoxal. 相似文献
992.
The reaction of 1H‐indol‐2,3‐diones with 1,6‐dibromohexane has resulted in the formation of new 1H‐indol‐2,3‐diones‐1,1′‐(1,6‐hexanediyl)bis in quantitative yields. These compounds have been used for the synthesis of novel [3′‐(2,3‐dimethyl‐5‐oxo‐1‐phenyl‐3‐pyrazolin‐4‐yl)spiro[3H‐indol‐3,2′‐thiazolidine]‐2,4′‐dione]‐1,1′‐(1,6‐hexanediyl)bis via bis Schiff's bases, [3‐(2,3‐dimethyl‐5‐oxo‐1‐phenyl‐3‐pyrazolin‐4‐yl) imino‐1H‐indol‐2‐one]‐1,1′‐(1,6‐hexanediyl)bis. 相似文献
993.
Synthesis of Schiff's bases in aqueous medium: a green alternative approach with effective mass yield and high reaction rates 总被引:1,自引:0,他引:1
《Green Chemistry Letters and Reviews》2013,6(3):217-223
Abstract Schiff's bases constitute a class of pharmaceutical and medicinally important molecules. The conventional methods for the synthesis of Schiff's bases require long reaction times and use of organic solvents. We report a novel and eco-friendly condensation reaction method permitting the “green synthesis” of various Schiff's bases by stirring 1,2-diaminobenzene with various aromatic aldehydes in water as solvent. This method is experimentally simple, clean, high yielding, green, and with reduced reaction times. The product is purified by simple filtration followed by washing with water and drying processes. 相似文献
994.
A. Khodairy H. Abdel-ghany 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):259-273
Abstract 3,4-Diamino-2,5-dicarbethoxythieno(2.3-b)thiophene 1 reacted with malononitrile or ethyl cyanoacetate to afford bis(thienopyrimidin-4-one) derivatives 2a.b The reaction of compound 1 with o-aminothiophenol, o-aminophenol or o-phenylenediamine gave benzothiazolyl-, benzoxazolyl-, benzoimidazolylthienothiophene 3a-c, Chloroacetylation of compound 1 and reacting the resulting compound 4 with malononitrile furnished thienopyrolopyrimidine 6. Fusion of compound 1 with formamide yielded bis(thienopyrimidine) 7 which reacted with POCI3/PCl5 to yield the corresponding chloro derivative 8 which was converted into the corresponding hydrazine derivative 9. Treatment of compound 1 with CS2, NaOH and 1,2 dibromoethane produced the corresponding 1.3 dithiolane 11 which also treated with chloroacetyl chloride or ethyl mercaptoacetate to get the corresponding β-lactame 12 or thiazolidinone 13. On reacting compound 1 with CS2, NaOH and (CH3)2S04 produced the corresponding bi(dithiocarbamate methyl ester) 14 which treated with hydrazine hydrate to yield the corresponding bis(thienopyrimidine) derivative 15. This compound reacted with Lawesson's reagent (LR) to give the desired compounds 16 and 17. While its reaction with (CH3)2 SO4 and NaOH furnished the corresponding methyl derivative 18. Fusion of compound 18 with aniline afforded compound 19. Compound 19 was allowed to react with ethyl acetoacetate, acetylacetone, α-oxoketene dithioacetal, ethoxymethylene malononitrile or LR to get the described compounds 2Oa.b-24 respectively. 相似文献
995.
Il'yas S. Nizamov Alexey E. Popovich Elvira S. Batyeva Nail M. Azancheev Vladimir A. Al'fonsov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):167-178
Abstract The reactions of tetraphosphorus decasulfide and Lawesson's reagent with tetra-, tri- and dialkoxysilanes were studied. On the basis of these reactions, new S-silyl esters of phosphorus(V) thioacids have been prepared. The prepared compounds were identified by IR, 1H, and 31P NMR and mass spectra as well as elemental analyses. 相似文献
996.
M. M. Sidky M. R. Mahran A. A. El-kateb I. T. Hennawy 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):409-412
Abstract Trialkyl phosphites react with quinisatin (1) and its monohydrate 3 to give the corresponding phosphate derivatives 2a-c. The same compounds are obtained upon reacting 1 and/or 3 with the proper dialkyl phosphite. Structural reasonings based on IR, MS and NMR spectral data, are presented. 相似文献
997.
Cheng-ye Yuan Ke Wang Jinfeng Li Zu-yi Li 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2391-2397
Bioreduction of 3-substituted-2-oxoalkanephosphonates by baker's yeast afforded corresponding 2-hydroxy-alkanephosphonates in good yields and ee value. These compounds ( 2a,b ) could serve as useful chirons for the stereoselective synthesis of phosphorus analogs of (R)-Carnitine and (R)-GABOB. 相似文献
998.
Subhash C. Jain Pankaj Khanna Sunita Bhagat Manish Jain Rajeev Sakhuja 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1829-1839
The reaction of indol-2,3-diones ( 1a–i ) with 5-aminoindazole ( 2 ) has resulted in the formation of hitherto unknown 3-(indazol-5-yl)iminoindol-2-ones ( 3a–i ) in quantitative yields which, on 1,3-dipolar cyclocondensation with mercaptoacetic acid ( 4 ), has afforded a series of new spiro heterocycles, 3′-(indazol-5-yl) spiro[3H, indol-3, 2′ -thiazolidine]-2,4′-diones* ( 5a–i ). 相似文献
999.
The Reaction Activity of Aromatic Carbonyl Compounds with Diphenylphosphine Oxide Studied by 31P NMR
Jinyun Zheng Xiangming Feng Yujian Yu Xiaomin Zhen Yufen Zhao 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1080-1087
Abstract A series of α-hydroxyphosphine oxides were prepared by the reactions of diphenylphosphine oxide and aromatic carbonyl compounds and characterized by 1H NMR, 13C NMR, 31P NMR, FT-IR, ESI-MS, and HR-MS spectra. The reaction rates and experimental conditions of aromatic aldehydes and aromatic ketones were obviously different due to the activity of their carbonyls. The different substituents of the aromatic aldehydes affected the reaction rate too, and the quantitative reactivity of their substituent conformed to the Hammett equation. The results were confirmed by 31P NMR spectroscopy. 相似文献
1000.
Davood Nori-Shargh Daryoush Tahmassebi Mahboobeh Poukalhor Mostafa Mohammadpour Amini Saeed Jameh-Bozorghi Farzad Deyhimi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(10):2419-2434
Ab initio molecular orbital and density functional theory were used to investigate energetic and structural properties of the various conformations of hexa-tertbutylbenzene (1), hexakis(trimethylsilyl)benzene (2), hexakis (trimethylgermyl)benzene (3), and hexakis(trimethylstannyl)benzene (4). HF/3-21G//HF/3-21G and B3LYP/3-21G//HF/3-21G results revealed that the Twist-Boat (TB) conformer of compound 1 is more stable than the 1-Chair (C), 1-Boat (B), and 1-Planar (P) conformers. B3LYP/3-21G//HF/3-21G results show that the 1- TB conformer is more stable than 1- C, 1- B, and 1- P conformers of about 1.13, 4.34, and 99.94 kcal mol?1 , respectively. Contrary to the stability order of compound 1 conformers, the C conformer of compounds 2–4 is more stable than TB, B, and P conformations, as calculated by B3LYP/3-21G//HF/3-21G and HF/3-21G//HF/3-21G levels of theory. The energy gap between the C and P conformers in compounds 1–4 is decreased in the following order: ΔE(4: C, P) < ΔE (3: C, P) < ΔE(2: C, P) < ΔE (1: C, P). This fact can be explained in terms of the increase of C aromatic -M (M═C, Si, Ge, and Sn) bond lengths and the decrease of steric (van der Waals) repulsions in the previously discussed compounds. For compounds 1–3, the calculations were also performed at the B3LYP/ 6-31G*//HF/3-21G level of theory. However, the comparison showed that the results at B3LYP/3-21G//HF/3-21G methods correlated well with those obtained at the B3LYP/6-31G*// HF/6-31G method. Further, NBO analysis revealed that in compounds 1–4, the resonance energy associated with the σM-C1 to σ*C2-C3 delocalization is 5.20, 9.68, 11.15, and 12.27 kcal mol?1, respectively. These resonance energy values could explain the easiness of the ring flipping processes of C, B, and TB conformers of compounds 4 to 1. Also, the NBO results showed that by an increase of the σM-C1 → σ *C2-C3 resonance energies in compounds 1–4, the σM-C1 bonding orbital occupancies decrease. This fact could fairly explain the increase of the Caryl-M bond length from compound 1 to 4. The NBO results are also in good agreement with the calculated energy barriers for the ring flipping of the chair conformations in compounds 1–4, as calculated by B3LYP and HF methods. 相似文献