全文获取类型
收费全文 | 602篇 |
免费 | 11篇 |
国内免费 | 1篇 |
专业分类
化学 | 404篇 |
晶体学 | 7篇 |
力学 | 13篇 |
数学 | 68篇 |
物理学 | 122篇 |
出版年
2021年 | 5篇 |
2020年 | 4篇 |
2017年 | 5篇 |
2016年 | 5篇 |
2015年 | 9篇 |
2014年 | 11篇 |
2013年 | 15篇 |
2012年 | 17篇 |
2011年 | 18篇 |
2010年 | 12篇 |
2009年 | 10篇 |
2008年 | 18篇 |
2007年 | 30篇 |
2006年 | 24篇 |
2005年 | 22篇 |
2004年 | 23篇 |
2003年 | 15篇 |
2002年 | 23篇 |
2001年 | 10篇 |
2000年 | 8篇 |
1999年 | 14篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 6篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 10篇 |
1989年 | 7篇 |
1988年 | 4篇 |
1987年 | 7篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 18篇 |
1980年 | 9篇 |
1979年 | 16篇 |
1978年 | 13篇 |
1977年 | 16篇 |
1976年 | 13篇 |
1975年 | 16篇 |
1974年 | 21篇 |
1973年 | 12篇 |
1971年 | 5篇 |
1970年 | 8篇 |
1955年 | 4篇 |
1925年 | 4篇 |
排序方式: 共有614条查询结果,搜索用时 31 毫秒
11.
Alain Merschaert Laurent DelhayeJean-Paul Kestemont Willy BrionePieter Delbeke Vincent MancusoFreddy Napora Khalid DikerDaniel Giraud Michel Vanmarsenille 《Tetrahedron letters》2003,44(24):4531-4534
A stereoselective approach has been developed for the synthesis of cis- and trans-2-methyl-4-arylpiperidines from a common intermediate. The Ni-catalyzed hydrogenolysis of N-Boc-2-methyl-4-aryl-4-piperidinols, obtained by addition of organometallic reagents on N-Boc-2-methyl-4-piperidone, afforded the trans derivatives with up to 95% selectivity whereas the corresponding cis isomers were obtained in the presence of palladium catalysts. 相似文献
12.
Xiongyu Wu Xiaohong Liu Guangce Jiang Yongcheng Lin Willy Chan L. L. P. Vrijmoed 《Chemistry of Natural Compounds》2005,41(1):27-29
A novel metabolite 1, named xyloketal G, was isolated from cultures of marine derived mangrove fungus Xylaria sp. 2508. Its structure was elucidated by analysis of spectroscopic data.__________Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 22–23, January–February, 2005. 相似文献
13.
Reduction of 2 cyclopropenyl esters and alcohols with lithium aluminium hydride is selective; at low temperatures (0°) the double bond is not reduced, but at higher temperatures (65°) the reduction is complete and only the cyclopropylmethanol is obtained. The reduction of the double bond is regioselective (the most stable carbanion is formed) and stereospecific (the hydride attack on the double bond occurs cis to the functional group). This stereospecificity can be explained through the initial formation of an alkoxylaluminium hydride followed by an intramolecular reduction of the double bond. Similar results have been obtained in the reduction of functionalised methylenecyclopropanes. 相似文献
14.
15.
Epoxides are stereoselectively prepared in one step from β-hydroxy selenides and β-hydroxy sulfides in a process which involves dichlorocarbene 相似文献
16.
17.
Mechanistic studies on the photoisomerization of 2-alkyl-indazoles into 1-alkyl-benzimidazoles. I. Structure and reactivity of an intermediate. 2-Alkyl-indazoles ( 1 ) undergo photochemical isomerization to 1-alkyl-benzimidazole via previously unknown intermediates 3 (Scheme 1). In the present paper the structure and reactivity of these intermediates are discussed. Low-temperature irradiation (?60°) of 1 b with 300 nm light gives 3 b in quantitative yield. 3 b is transformed during warm-up to 1 b and 2 b (UV.-evidence). The formations of 1 and 2 show the same temperature dependence but their ratio is found to be temperature-independent. In contrast to the above behaviour, low-temperature irradiation with 250 nm light of 3 b yields 1 b only (no 2 b ). These findings are consistent with the proposed reaction mechanism 2 c in Scheme 2. On the basis of spectroscopic properties and the described reaction pathways, it appears that the most suitable structure for intermediate 3 is a 7,8-diaza-tricyclo[4.3.0.07,9]nona-2,4,6(10)-trien ( 9 ). In Scheme 4 the reaction pathway for the iudazole-benzimidazole-rearrangement is summarized. 相似文献
18.
Mechanistic studies on the photochemistry of 2-alkylindazoles in aqueous solutions. The photochemistry of 2-alkylindazoles 1 in aqueous solutions is rather complex, the relative yields of different products being dependent on the pH-value of the irradiated solution: In neutral or basic solutions (pH > 7) as well as in most of the organic solvents isomerization to 1-alkyl-benzimidazoles 2 takes place. In dilute sulfuric acid (pH 2–4) this reaction is suppressed and the dihydro-azepinones 3 and 4 are formed. Irradiation in strongly acid solutions (pH < 1) yields the o-amino-acetophenones 5 (Scheme 1). The relative quantum yields of the photoproducts 2–5 have been measured as a function of the pH-value of the irradiated solution (Fig. 1). A comparison of these yields with the protonation equilibrium of the indazole in its first excited singlet state (pK = 2.8) suggests that 2 and 3 are both photoproducts of the neutral indazole molecule, whereas 4 as well as 5 are formed from the protonated indazole. The rearrangement of the indazole 1 to the benzimidazole 2 proceeds via an intermediate 6 , which can be produced in high concentrations by monochromatic irradiation of 1 at low temperatures. The thermal reactivity of this intermediate in dilute sulfuric acid could be investigated: At pH 8 the only product is the benzimidazole 2 . With decreasing pH-value increasing amounts of 3 are formed and at pH < 4 the formation of 2 is completely suppressed, the only product being the azepinone 3 . Thus, 3 is a solvolysis product of the intermediate 6 (Scheme 2). The most probable primary product of singlet indazolium is the nitrenium ion 7 . From this intermediate the formation of 5 can proceed in well-known thermal reactions. The formation of 4 is possibly due to a further protonation equilibrium nitrenium-nitrene. The nitrene 7 can be converted into the azepinone 4 via the azirine 8 (Scheme 3). The pK-values of different indazoles and intermediates are listed in the Table. 相似文献
19.
A new chemiluminescence (CL) flow-injection method is proposed for the determination of 1,3-dichloro-5,5-dimethylhydantoin (DDH). The method is based on the chemiluminescent reaction of DDH and luminol-H(2)O(2) in an alkaline medium (pH 12.0-12.5). The concentration of the analyte shows a good linear relationship with the produced luminescence intensity in the range of 3.0x10(-8) to 8.0x10(-6) mol l(-1). The detection limit of the proposed method is 1.0x10(-8) mol l(-1) and the relative standard deviation (R.S.D.) is 4.7% (n=5) at 5.0x10(-7) mol l(-1). This method was successfully applied to the determination of trace amounts of this disinfectant in water samples obtained from five different swimming pools. Satisfying recovery values were also obtained. 相似文献
20.
Abstract—The fluorescence spectra of salicylamide in cyclohexane, ethanol and at different pH in water were studied. The short and long wavelength fluorescences observed in the organic solvents originate from emissions of a weakly or non-intramolecularly hydrogen bonded conformer and from phototautomerization of a strongly intramolecularly hydrogen bonded conformer, respectively. Evidence for at least 2 conformers in the ground state exists in the excitation wavelength dependence of the ratio of short wavelength to long wavelength emission. In water, prototropic dissociation of the phenolic group of salicylamide in the lowest excited singlet state also shows an excitation wavelength dependence, indicating that the weakly or non-intramolecularly hydrogen bonded conformer in water is predominately responsible for photodissociation. 相似文献