全文获取类型
收费全文 | 53198篇 |
免费 | 1827篇 |
国内免费 | 197篇 |
专业分类
化学 | 35007篇 |
晶体学 | 348篇 |
力学 | 1152篇 |
综合类 | 2篇 |
数学 | 9222篇 |
物理学 | 9491篇 |
出版年
2023年 | 369篇 |
2022年 | 620篇 |
2021年 | 886篇 |
2020年 | 920篇 |
2019年 | 883篇 |
2018年 | 1400篇 |
2017年 | 1175篇 |
2016年 | 1874篇 |
2015年 | 1503篇 |
2014年 | 1588篇 |
2013年 | 3271篇 |
2012年 | 3429篇 |
2011年 | 3752篇 |
2010年 | 2284篇 |
2009年 | 2061篇 |
2008年 | 3257篇 |
2007年 | 3164篇 |
2006年 | 2868篇 |
2005年 | 2585篇 |
2004年 | 2116篇 |
2003年 | 1715篇 |
2002年 | 1548篇 |
2001年 | 1067篇 |
2000年 | 976篇 |
1999年 | 708篇 |
1998年 | 547篇 |
1997年 | 493篇 |
1996年 | 631篇 |
1995年 | 434篇 |
1994年 | 455篇 |
1993年 | 457篇 |
1992年 | 423篇 |
1991年 | 320篇 |
1990年 | 317篇 |
1989年 | 280篇 |
1988年 | 244篇 |
1987年 | 249篇 |
1986年 | 236篇 |
1985年 | 324篇 |
1984年 | 322篇 |
1983年 | 249篇 |
1982年 | 246篇 |
1981年 | 230篇 |
1980年 | 190篇 |
1979年 | 179篇 |
1978年 | 184篇 |
1977年 | 162篇 |
1976年 | 151篇 |
1975年 | 139篇 |
1973年 | 140篇 |
排序方式: 共有10000条查询结果,搜索用时 171 毫秒
991.
992.
Chiral 1,3-perhydrobenzoxazines 1, 2, and 9-14, prepared by condensation of 8-(benzylamino)menthol with different aldehydes, react with alkylmagnesium bromides and trimethylaluminum leading to the open amino alcohols 3a-d, 4a-d, and 15-20 in excellent chemical yields and good to excellent diastereomeric excess. The sequential elimination of the menthol appendage by heating with P(2)O(5) and the benzyl group by hydrogenolysis lead to primary amines 7a-d, 8a-d, and 27-30 in excellent chemical yields and ee. The addition of the alkyl group from the Grignard derivatives and the methyl group from the trimethylaluminum occurs from opposite sides of the heterocycle, yielding the final primary amines with the same stereochemistry. 相似文献
993.
Treatment of secondary aliphatic 2-bromoallylamines with an excess of an organolithium compound led to saturated amines in which the organic group of the organolithium compound is incorporated at the alpha carbon. On the other hand, the successive reaction of the former amines with BuLi and t-BuLi between -80 degrees C and rt gave 1,3-diamines or hexahydropyrimidines depending on the reaction time. The formation of these unexpected products involves initial generation of lithium propargylamides, which subsequently undergo cleavage of the C propargylic-C acetylenic bond induced by the organolithium present in each case in the reaction medium. A mechanism which takes into account all the different reaction products has been proposed and additionally supported by successful trapping of dilithium acetylide. 相似文献
994.
995.
Fustero S Navarro A Díaz D de La Torre MG Asensio A Sanz F González ML 《The Journal of organic chemistry》1996,61(25):8849-8859
Reaction of azaenolates of 2-alkyl-oxa(thia)zolines 6 with imidoyl chlorides 7 as electrophiles to furnish masked N-substituted beta-enamino acid derivatives 1-2 in 70-90% yield is described. Alternative routes are discussed. Compounds 1-2 generally appear in one tautomeric form, imino or enamino, depending on the nature of the imidoyl chloride. The configuration of the enamino moiety (Z) and the conformation (s-cis) of compounds 1-2 obtained were established by an NMR study and unequivocally set by nuclear Overhauser effect difference experiments. An X-ray structure of compound 1e is also reported, showing a strong intramolecular NH.N hydrogen bond. Ab initio calculations (HF/3-21G and HF/3-21+G) have been carried out on several representative examples (1e, 1p, and 1l) in an attempt to support and provide the correct geometry of these derivatives. Structural considerations among the possible isomers of compounds 1 are discussed. From these studies it was concluded that the theoretical calculations agree with the experimental results. In addition, a very simple one-pot procedure for the preparation of masked N-substituted alpha-alkylated beta-enamino acid derivatives 2 from 6, 7, and different alkyl halides (R(3)Y) is described. 相似文献
996.
To develop solid-phase synthesis of phosphinic peptides, different FmocXaaPsi{PO(OAd)CH(2)}XaaOH building blocks have been prepared, where Fmoc is (fluorenylmethoxy)carbonyl. In this respect, the protection of the hydroxyphosphinyl function in these phosphinic dipeptides by the adamantyl group turns out to be convenient. The phosphinic adamantyl esters are completely stable in basic conditions and can be removed under relatively mild acidic conditions. Using these building blocks, despite the bulkiness of the adamantyl group, no particular problem of coupling was observed during the solid-phase synthesis of phosphinic peptides by the Fmoc strategy. The developed methodology is of particular interest to facilitate the development of potent inhibitors of zinc-metalloproteases. 相似文献
997.
Junquera E Laynez J Menéndez M Sharma S Penadés S 《The Journal of organic chemistry》1996,61(20):6790-6798
Thermodynamic studies of the binding of a series of p-nitrophenyl glycosides (PNPGly) of varying stereochemistry to alpha-cyclodextrin (alpha-CD) were performed at three different temperatures (25, 35, and 42 degrees C) using a microcalorimetric technique. The system p-nitrophenol (PNP) at pH = 3 and alpha-CD was also studied for the sake of comparison. All these complexes were found to be enthalpy driven with a favorable enthalpic term clearly dominant over an unfavorable entropic term. A clear enthalpy-entropy compensation effect was observed at all the temperatures, with a slope close to unity (alpha = 1.02) and an intercept TDeltaS degrees (o) = 2.91 kcal mol(-)(1). This thermodynamic pattern is in agreement with those usually found for lectin-carbohydrate associations and for the binding processes of several host-guest systems. This pattern is explained in terms of the contribution of primarily two driving forces: the van der Waals interactions between the host and the guest, and the solvation/desolvation processes which accompany the association reaction. The presence of the carbohydrate molecule in the PNP ring causes a slight destabilization of the complex at 25 degrees C with respect to the alpha-CD-PNP (pH = 3) complex, although a different behavior has been observed depending on the axial/equatorial configuration of the glycoside and the temperature. This behavior is modulated by the stereochemistry of the glycoside. Differences were observed between the deoxy-derivatives (LAra and LFuc) and those derivatives with a hydroxymethyl group (Glc, Gal, Man). DeltaC(p) degrees values were obtained from the dependency of DeltaH degrees on temperature (=( partial differentialDeltaH degrees / partial differentialT)(p)). These values are small and negative except for alphaMan complex. For the latter complex, discrepancy between the calorimetric and the calculated van't Hoff enthalpies was observed. Parallels are drawn between the thermodynamics of our model and those proposed for carbohydrate-protein associations. 相似文献
998.
The synthesis of tetracyclic polyhydroxyquinones 5a and 5b was achieved through a sequence involving two Diels-Alder reactions with 1-methoxy-1,3-cyclohexadiene: the first with 2-(p-tolylthio)naphthazarin and the second on the resulting tricyclic derivative previously transformed into a (p-tolylsulfinyl)naphthazarin. The success of this strategy stemmed from the efficient remote regiocontrol exerted by the thioether substituent in the first step. 相似文献
999.
1000.
Extending previous work on the geometric characterization of separability in the autonomous case, necessary and sufficient conditions are established for the complete separability of a system of time-dependent second-order ordinary differential equations. In deriving this result, extensive use is made of the theory of derivations of scalar and vector-valued forms along the projection :J
1
EE of the first jet bundle of a fibre bundleE . Two illustrative examples are discussed, which fully demonstrate all aspects of the constructive nature of the theory. 相似文献