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61.
The diastereoselectivity of the mercuration of acyclic alkenes can be reversed by changing the substituent in the allylic position; with alcohols the erythro isomers and with esters or hemiacetals the threo isomers and are formed predominantly (Table I). 相似文献
62.
On Ternary Chalcogenides. XXIV. The Structure of TlGaSe2 TlGaSe2 is monoclinic with a = 10.772(3), b = 10.771(5), c = 15.636(8) Å, ß = 100.6(3)°, Z = 16, space group Cc. The refinement yielded an R value of 0.082 for 1366 unique observed reflections (MoKα). The compound crystallizes with a layer structure with two anion layers perpendicular to c* in the unit cell. The structural motive of the layers are large corner-linked Ga4Se10- tetraeder consisting of four corner-linked GaSe4 tetrahedra. Two adjacent layers are turned relative to each other by 90°. They are kept together by Tl1+ ions, which are situated on straight lines parallel to the edges of the Ga4Se10 groups. They are surrounded by six selenium atoms forming trigonal-prismatic TlSe6 polyhedra. 42 screw-axes within the layers are the reason for a strongly pronounced pseudo tetragonal symmetry. Different possibilities of stacking cause a onedimensional disorder along the c* direction. The relations between the TlGaSe2 type and the TlSe type and also the high-pressure modifications of some compounds with the TlGaSe2 structure are discussed. 相似文献
63.
Jolanta Olkowska‐Oetzel Dieter Fenske Petra Scheer Andreas Eichhfer 《无机化学与普通化学杂志》2003,629(3):415-420
Syntheses and Thermal Properties of Cluster Molecules, formed from Groups 11‐13‐16 Elements In the presence of PPh3, CuX (X = Cl, CH3COO) or AgOC(O)C6H5 and GaCl3 react in THF with S(SiMe3)2 or Se(SiMe3)2 to yield [Cu6Ga8Cl4S13(PPh3)6] ( 1 ), [Cu6Ga8Cl4Se13(PPh3)6] ( 2 ), [Ag6Ga8Cl4S13(PPh3)6] ( 4 ) and [Ag6Ga8Cl4Se13(PPh3)6] ( 5 ). The use of PnPr2Ph instead of PPh3 and subsequent layering with n‐hexane leads to the formation of the cluster [Cu6Ga8Cl4Se13(PnPr2Ph)12] ( 3a , 3b ). Reaction of CuCl, GaCl3 and PnPr3 with Se(SiMe3)2 in THF results in the crystallisation of the ionic cluster (HPnPr3)2[Cu2Ga4Cl4Se6(PnPr3)4] ( 6 ). The structures of 1 — 6 were determined by X‐ray single crystal structure analysis. Thermogravimetric measurements of the cluster molecules and powder diffraction patterns of the remaining powders reveal the potential use of them as single source precursor compounds for the synthesis of the related ternary solid state materials. 相似文献
64.
On the Reaction of Germanium with Germanium Tetrachloride and on the Existence of the Oxidechlorides GeOCl2 and GeOCl6 at the Equilibrium The above equilibrium was measured in a Gauge-manometer and the enthalpy of formation and the entropy for GeCl2,g were derived from these results. From total pressure measurements and transport experiments of GeO2 with GeCl4 follows, that the oxidechlorides Ge2OCl6 and GeOCl2 are not present in measurable concentrations, that means the enthalpy of formation of GeOCl2 must be higher than ?327 kJ · mol?1. 相似文献
65.
Enantioselective Synthesis of Allyl-, Propargyl-, and 4-En-2-ynyl-amines via 1,2-Addition of Organocerium Reagents to Chiral Aldehyde Imines (E)- and (Z)-Allyl-, propargyl-, and 4-en-2-ynyl-amines 5 and 14 , useful bifunctional building blocks and of pharmaceutical interest, are synthesized in high enantiomeric purity (e.e. ≥ 97%). Key step is the diastereoselective 1,2-addition (d.e. 86 to ≥ 98%) of organocerium reagents to chiral α,β-unsaturated aldehyde imines 3 or 8 to produce adduct amines 4 and 9 (Schemes 1 and 4, resp.). The propargylamine 9 is a substrate for Pd-catalyzed coupling with alkenyl halides to produce the enynylamine 11a and the thienyl-substituted alkynylamine 11b . The chiral auxiliary (S,S)- 2 is removed from 4 and 11 in 3 steps affording the title compounds 5 and 14 . Diastereoisomer enrichment of the hydrochloride of 6 by crystallization is possible. 相似文献
66.
Synthesis, IR Spectrum, and Crystal Structure of N,N'-Bis(trimethylsilyl)benzamidinium Tetrachloroferrate(III) The title compound [C6H5? C(NHSiMe3)2][FeCl4] is obtained by the reaction of FeCl3 with N,N,N'-tris(trimethylsilyl)benzamidine in the presence of tetrahydrofurane, forming yellow, moisture sensitive crystals. The compound is characterized by its IR spectrum as well as by an X-ray structure determination. Space group P21/n, Z = 8, 5974 independent observed reflexions, R = 0.066. The lattice dimensions are at ?70°C: a = 2110.7, b = 1109.5, c = 2120.4 pm; β = 111.17º. The compound forms ion pairs, in which the H atoms of the amidinium cation are coordinated with one chlorine ligand of the FeCl4? ion in a chelating manner. 相似文献
67.
The phenolic oxidation of 2',4-dihydroxy-4'-methoxy-β-methylchalcone using alkaline potassium ferricyanide gives an aurone rather than an isoflavone. This result is discussed in the context of current theories regarding the biosynthesis of flavonoid and isoflavonoid compounds. 相似文献
68.
Max Schmidt und Dieter Franz 《Fresenius' Journal of Analytical Chemistry》1965,215(5):395-400
Zusammenfassung Es wird ein Verfahren zur Bestimmung von Stibin beschrieben, das sich sowohl zur Analyse von SbH3 in organischen Lösungsmitteln als auch zur Bestimmung von flüssigem oder festem SbH3 eignet. Hierbei wird das Stibin mit überschüssigem Brom zu SbV oxydiert, danach mit SO2 zu SbIII reduziert und dieses oxydimetrisch mit Jod oder Bromat titriert.
Herrn Professor Dr. C. Mahr zum 65. Geburtstag gewidmet. 相似文献
Summary A method is proposed for the determination of stibine, applicable to its solutions in organic solvents and also to the solvent-free liquid or solid substance. The procedure involves oxidation of SbH3 with an excess of bromine to SbV, reduction to SbIII with SO2, and oxidimetric titration of the trivalent antimony with iodine or bromate.
Herrn Professor Dr. C. Mahr zum 65. Geburtstag gewidmet. 相似文献
69.
The cover picture shows a model of the "progenitor-TADDOLs" in front of a panorama of the Fünffingersstocks and the Wenden Glacier in the Titlisgebiet (Switzerland). The model is flanked by a stylized view of the general mechanistic model for the preferred stereochemical pathway of the Ti-TADDOLate-catalyzed reaction of chelating substrates (left) and a blackboard (right) showing formulae of compounds that can be prepared with high enantioselectivity by nucleophilic addition in the presence of titanium TADDOLates. From TADDOL, introduced in 1982, a genuine auxiliary system for the "introduction of chirality" (not only by reaction) has been developed, which, in the final sprint against the competition has a good chance of securing a place on the winning podium. The photograph of the mountain landscape was taken by Dr. J. Frackenpohl, the cover picture was generated by one of the authors (A.H.) of the comprehensive review of TADDOLs in this issue (p. 92 ff.) with the help of the program Povray. Supporting information for this article is available on the WWW under http://www.angewandte.com or from the author. 相似文献
70.
The efficient esterification of various sulfonic acids and sulfonates using polymer-bound triazenes based on the triazene T2 linker is described. Esterification of enantiopure alpha-substituted sodium sulfonates was performed in the presence of an alkylating resin without racemization. Racemization is a serious drawback in the esterification route via sulfonyl chlorides because of intermediate sulfene formation. To demonstrate the versatility of this protocol, phosphoric and phosphinic acids have been converted into the corresponding esters as well. All products were obtained in good yield and excellent purities without any further purification steps. 相似文献