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1.
Addition of functionalized zinc-copper reagents to the title complexes proceeds in a highly diastereoselective fashion to afford dienol complexes. The relative configurations of adducts 3d were determined by single X-ray diffraction analysis. 相似文献
2.
To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007 相似文献
3.
Leonard M Khalilov Ludmila V Parfenova Askhat G Ibragimov Usein M Dzhemilev 《Journal of organometallic chemistry》2004,689(2):444-453
This paper is dedicated to a study of properties of the following novel optically active organoaluminium compounds (OACs): (1S,2S)-l,7,7-trimethyl-2-[(dialkylalumina)oxy]-bicyclo[2.2.1]heptanes and (1S)-N-(dialkylalumina)-6,7-dimethoxy-1-methyl-1,2,3,4- tetrahydroisoquinolines. The synthesis of the chiral OACs was carried out in the reaction of either natural camphor or salsolidine with both AlEt3 and i-Bu2AlH. The main goal of the research was to investigate the stereodifferentiating activity of the chiral OACs in the olefin carbo- and cycloalumination reactions, catalyzed by Cp2ZrCl2. 相似文献
4.
Maculalactones A, B and C from the marine cyanobacterium Kyrtuthrix maculans are amongst the only compounds based on the tribenzylbutyrolactone skeleton known in nature and (+) maculalactone A from the natural source possesses significant biological activity against various marine herbivores and marine settlers. We now report a concise synthesis of racemic maculalactone A in five steps from inexpensive starting materials. Maculalactones B and C were synthesized by a minor modification to this procedure, and the synthetic design also permitted an asymmetric synthesis of maculalactone A to be achieved in around 85% ee. The (+) and (−) enantiomers of maculalactone A were assigned, respectively, to the S and R configurations on the basis of the chiral selectivity expected for catecholborane reduction of an unsymmetrical ketone in the presence of Corey's oxazoborolidine catalyst. Surprisingly, it appeared that natural (+) maculalactone A was biosynthesized in K. maculans in a partially racemic form, comprising ca. 90-95% of the (S) enantiomer and 5-10% of its (R) enantiomer. Coincidentally therefore, the percentage enantiomeric excess of the product obtained from asymmetric synthesis almost exactly matched that found in nature. 相似文献
5.
The synthesis of enantiopure bis-THF is described, starting from d-mannitol. Bis-THF is used as chiral ligand for organolithium reagents in four different reactions. The enantioselectivity provided by this ligand is moderate, and the asymmetric induction is in line with the expected model. 相似文献
6.
Regioselective allylation reactions using crotyl Grignard reagent-CeCl3 systems are described. Regioselectivity depends on the lanthanide salts: α-product was predominantly produced with light rare earth elements such as La, Ce, Pr, Nd, whereas γ-product was formed when heavy rare earth elements were used. 相似文献
7.
Roxana S. Timofte 《Tetrahedron letters》2004,45(1):39-42
High surface area silica pellets are excellent supports for the preparation of silica supported reagents and solid-phase basal linkers through reaction with (RO)3Si(CH2)3FG (FG=NH2, NHMe, Cl, NHC(O)NH2, OC(O)CMe(CH2), NCO, NEt2). High loadings (0.66-2.15 mmol g−1) of grafted silane materials are realised at synthetically useful loadings per pellet (ca. 0.06 mmol). Preliminary trials show that trial linker chemistry and ligand synthesis can be carried out on these materials and that these reactions can be monitored by solid state 13C NMR studies on individual pellets. 相似文献
8.
A polymerized quaternary ammonium salt polydiallyldimethylammonium chloride, exhibiting high stability to heat and base, was prepared and applied as phase-transfer catalyst (PTC) in halogen-exchange (Halex) fluorination of chloronitrobenzenes to give excellent yields of corresponding fluoronitrobenzenes. Dimethyl sulfoxide was found to be the best solvent when microwave was applied as heating resource. 相似文献
9.
We wish to report synthesis of perfluorinated functionalized, branched ethers from their hydrocarbon analogues by direct fluorination. Yields up to 90%, with high purities, have been obtained at ambient temperature and pressure. This technique will likely develop into a new general method for producing perfluorinated, hyperbranched and dendritic polymers. 相似文献
10.
Ilga Mutule 《Tetrahedron letters》2004,45(20):3909-3912
Arylzinc reagents were readily prepared from aryl iodides using a Zn-Cu couple in a microwave environment. A sequential arylzinc formation-Negishi cross-coupling protocol suitable for parallel high-throughput synthesis has been developed. 相似文献