全文获取类型
收费全文 | 2863篇 |
免费 | 282篇 |
国内免费 | 290篇 |
专业分类
化学 | 2959篇 |
晶体学 | 35篇 |
力学 | 8篇 |
综合类 | 16篇 |
数学 | 139篇 |
物理学 | 278篇 |
出版年
2024年 | 4篇 |
2023年 | 29篇 |
2022年 | 67篇 |
2021年 | 66篇 |
2020年 | 95篇 |
2019年 | 82篇 |
2018年 | 78篇 |
2017年 | 83篇 |
2016年 | 111篇 |
2015年 | 88篇 |
2014年 | 129篇 |
2013年 | 254篇 |
2012年 | 134篇 |
2011年 | 177篇 |
2010年 | 156篇 |
2009年 | 167篇 |
2008年 | 175篇 |
2007年 | 171篇 |
2006年 | 178篇 |
2005年 | 160篇 |
2004年 | 179篇 |
2003年 | 177篇 |
2002年 | 145篇 |
2001年 | 59篇 |
2000年 | 70篇 |
1999年 | 44篇 |
1998年 | 40篇 |
1997年 | 44篇 |
1996年 | 49篇 |
1995年 | 39篇 |
1994年 | 36篇 |
1993年 | 26篇 |
1992年 | 26篇 |
1991年 | 10篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 13篇 |
1987年 | 8篇 |
1986年 | 8篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1982年 | 8篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有3435条查询结果,搜索用时 93 毫秒
51.
Cédric Kalinski Michael Umkehrer Nadine Jäger Wolfgang Hiller 《Tetrahedron letters》2006,47(12):2041-2044
A combinatorial synthetic route yielding fused tetrazolo[1,5-a]quinoxalines is described. The use of 2-fluorophenylisocyanide in the Ugi-tetrazole reaction (tetrazole-U-4CR) followed by a nucleophilic aromatic substitution (SNAr) affords the tricylic tetrazolo[1,5-a]quinoxaline moiety in good yields and with high diversity. 相似文献
52.
报道了用H_2Fe(CO)_4制备trans-Fe(CO)_3(PR_3)_2的新的羰基取代反应。在 过量质子存在下,H_2Fe(CO)_4中的羰基被活化,中心铁原子对膦的亲核进攻更为 敏感。在这种条件下H_2Fe(CO)_4与膦反应时,首先失去氢生成Fe(CO)_4(PR_3), Fe(CO)_4-(PR_3)再与第二个膦反应可高产率的得到trans-Fe(CO)_3(PR_3)_2。用 PPh_3与Fe(CO)_4(PPh_3)在过量质子存在下反应生成trans-Fe(CO)_3(PR_3)_2,证 实了上述过程。 相似文献
53.
G.V.M. Sharma J. Janardhan Reddy P. Sree Lakshmi Palakodety Radha Krishna 《Tetrahedron letters》2004,45(41):7729-7732
A practical and efficient electrophilic substitution reaction of indoles with a variety of aldehydes was carried out using catalytic trichloro-1,3,5-triazine (10 mol %) in acetonitrile to furnish the corresponding bis(indolyl)methanes in excellent yields. Similarly, sugar derived aldehydes gave hitherto unknown bis(indolyl)glycoconjugates in very good yields. 相似文献
54.
55.
S. V. Koroteev D. S. Ermekov Z. V. Todres A. D. Malievskii 《Russian Chemical Bulletin》1992,41(1):60-64
Reaction of cis-,-dinitrostilbene (substrate) with morpholine (reagent) in n-hexane leads to cis--nitro--morpholinostilbene (end product). The process is of first order with respect to the substrate and second order with respect to the reagent. Possible reaction mechanisms are analyzed, and it is established that the following are most probable on the basis of kinetic patterns and stereochemistry: development of a charge transfer complex having a hydrogen bond between the substrate nitro group and reagent amino group; reaction of the complex with a second reagent molecule and formation of a carbanion (this stage determines the overall reaction rate); and detachment of a nitrite ion from the nitrocarbanion and its protonation to form the end product.N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. A. N. Nesmeyanov Institute of Heteroorganic Compound, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 78–83, January, 1992. 相似文献
56.
3,4-Dihydro-5(1H)-pyrromethenones are easier attacked at themeso-position by electrophiles than 5(1H)-pyrromethenones. This is demonstrated both by aMannich-type-substitution or deuterium-exchange-experiments and by the addition of O-, S-, and N-Nucleophiles to the exocyclic double bond of the model-dihydropyrromethenone (Z)-1 under very mild reaction conditions. Applying these results to the chemistry of 2,3-dihydro-bilatrienes-abc, their chemical characteristics—especially their tautomeric behavior and their dominant C-5-selectivity towards electrophiles—become better understandable. 相似文献
57.
Laurel A. Goj 《Journal of organometallic chemistry》2003,687(2):498-507
Cycloisomerization of 4,4-bis(acetoxymethyl)-1,6-heptadiene (5) catalyzed by [(phen)Pd(Me)CNCH3]+ [BAr4]− [Ar=3,5-C6H3(CF3)2] (2) to form predominantly 3,3-bis(acetoxymethyl)-1,5-dimethylcyclopentene (6) was ∼400 times faster than was the cycloisomerization of dimethyl diallylmalonate (1) under identical conditions. Mechanistic studies performed in conjunction with density functional theory calculations attribute the large rate acceleration of the cycloisomerization of 5 relative to the cycloisomerization of 1 to the formation of a stable oxo chelate complex as an intermediate in the cycloisomerization of 1, but not in the cycloisomerization of 5. 相似文献
58.
Shigeru Matsuo Tomoyoshi Murakami Ryuichi Takasawa 《Journal of polymer science. Part A, Polymer chemistry》1993,31(13):3439-3446
Crystalline poly(arylene ether nitrile) could be prepared by the polycondensation of 2,6-dihalobenzonitrile with resorcinol at 200°C in N-methylpyrrolidone in the presence of sodium carbonate. A reaction temperature of at least 200°C was necessary to attain high molecular weight polymer. Spectral data indicated that the polymer had the structure of a poly(meta-phenylene ether) with pendent nitrile groups on every other phenylene unit. Despite this structure, the crystallinity and the crystallization rate of the polymer were greater than those of the corresponding polymer with a para-linked structure. The glass transition temperature and the melting temperature of the polymer were almost the same as those of poly(etheretherketone) (PEEKTM). A series of other new poly(arylene ether nitriles) were also examined. The polymers derived from 4,4′-biphenol, dihydroxytetra-phenylmethane, dihydroxydiphenylsulfone, and 1,5-isoquinolinediol had high glass transition temperatures. The poly(arylene ether nitriles) exhibited excellent tensile strength compared with the corresponding ketone- or sulfone-containing polymers. Comparing the three different kinds of polymers containing the same bisphenol units, the order of glass transition temperature was found to be sulfone- > nitrile- > ketone-containing polymers, while the order of tensile strength was nitrile- > ketone- > sulfone-containing polymers. The excellent mechanical properties are attributable to dipole-dipole interactions of nitrile groups. © 1993 John Wiley & Sons, Inc. 相似文献
59.
Marc Wende 《Journal of fluorine chemistry》2003,124(1):45-54
Most compounds designed for immobilization in fluorous media feature linear pony tails of the formula (CH2)m(CF2)n−1CF3 [(CH2)mRfn]. This paper presents a first-generation approach to compounds with branched or “split” pony tails of the formula (CH2)lCH[(CH2)mRfn]2. Allyl tri(n-butyl)tin is reacted twice with perfluorooctyl iodide (Rf8I; first, photochemical, 78-81%; second, thermal with radical initiator, 71%; 13-18 g scales) to give the secondary alkyl iodide ICH(CH2Rf8)2 (3). A subsequent Ni(Cl)2(PPh3)2-catalyzed reaction with allyl tri(n-butyl)tin yields the branched alkene H2CCHCH2CH(CH2Rf8)2 (74%). A palladium-catalyzed Heck coupling with OP(p-C6H4Br)3 gives the fluorous phosphine oxide OP(p-C6H4CHCHCH2CH(CH2Rf8)2)3 (84%), and Pd/C-catalyzed hydrogenation affords OP(p-C6H4(CH2)3CH(CH2Rf8)2)3 (>99%). Reduction with SiHCl3 gives P(p-C6H4(CH2)3CH(CH2Rf8)2)3, which is protected as the air-stable borane adduct H3B·P(p-C6H4(CH2)3CH(CH2Rf8)2)3 (9, 64%). The CF3C6F11/toluene partition coefficient of 9 is much higher than that of the analog with p-(CH2)3Rf8 groups (96.6:3.4 versus 37.3:62.7). The iodide 3 is unreactive towards PAr3 at 175-250 °C. However, a CuBr-catalyzed reaction with C6H5MgBr gives C6H5CH(CH2Rf8)2, which also exhibits a high partition coefficient (97.9:2.1). 相似文献
60.