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91.
Jean Martin Schmid Masaaki Uchida Peter Rüedi Conrad Hans Eugster 《Helvetica chimica acta》1982,65(7):2164-2180
Partial Syntheses and Reactions of Abietanoid Derivatives (Lanugones) from Plectranthus lanuginosus and of Related Compounds Interconversions by partial syntheses of several lanugones establish their absolute configuration at C(15). Unexpected reactions exemplify the unique reactivity of these abietanoic diterpenes, - Lanugone O ( 4 ) was prepared in several steps from (15S)-coleon C ( 8a ; Scheme 2) thus establishing its (15S)-configuration. One of the intermediates, the 12-O-acetyl-6-oxoroyleanone 12 , through acetyl-migration sets up an equilibrium with the vinylogous quinone 13 (Scheme 3). - The chirality at C(15) in the dihydrofuran moiety of lanugone Q ( 16 ) was proven by acid-catalyzed conversion of lanugone O ( 4 ) to 16 . - Instead of the usual nucleophilic attack shown by quinomethanes, lanugone L (1 ) is electrophilically substituted at C(7) by acetic anhydride/pyridine (Scheme 1). - In a homosigmatropic [1,5]-H-shift, lanugone G ( 17 ) in solution is converted to the corresponding allyl substituted royleanone 18 (Scheme 4). - Methanolysis of lanugone J ( 19 ) leads to the expected royleanone 20 having the 2-methoxypropyl side chain ( Scheme 5 ). Similar reactions were found in acetolytic reactions. However, treatment-of spirocoleons with SOCl2/DMF produces mainly 12-deoxyroyleanones with allyl- and 2-chloropropyl groups, i. e. 19 → 26 and 27 ; 28 → 29 . The possible natural occurrence of these compounds is emphasized. 相似文献
92.
Zusammenfassung Die Ionisationskonstanten des Aniliniumions, der drei Chlor- und der drei Nitroaniliniumionen in Methanol bei 2°C, 15°C und 25°C werden mit Hilfe eines spektralphotometrischen Verfahrens bestimmt. Da die Amine im ultravioletten oder im sichtbaren Bereich starke Absorptionsbanden aufweisen, während die Ionenformen fast nicht absorbieren, ist es möglich, durch Messung der Extinktion von Lösungen, in, denen Anilin (substituiertes Anilin) mit Aniliniumion (substituiertem Aniliniumion) im Gleichgewicht steht, die Ionensationskonstante zu ermitteln.Es zeigt sich, daß die Basizität der untersuchten Amine in Methanol größer als in Wasser ist und daß die Einführung eines Chloratoms oder einer Nitrogruppe in den aromatischen Ring eine Abnahme der Basizität verursacht. Dieser Effekt ist bei den Nitroanilinen stärker als bei den Chloranilinen, und bei den o-Verbindungen stärker als bei den m- und p-Verbindungen ausgeprägt.Die Temperaturabhängigkeit der Ionisationskonstanten und damit auch die Ionisationsenthalpien der Aniliniumionen sind in Methanol ebenfalls größer als in Wasser.Mit 2 AbbildungenAus der Diplomarbeit vonW. Melhardt, Technische Hochschule Wien, 1962. 相似文献
93.
K. Nagaiah D. Sreenu R. Srinivasa Rao G. Vashishta J.S. Yadav 《Tetrahedron letters》2006,47(26):4409-4413
trans-Fused pyrano- and furanotetrahydroquinoline derivatives have been synthesized via a one-pot three-component aza-Diels-Alder reaction of aryl imines formed in situ from aromatic amines and arylaldehydes with cyclic enol ethers,such as 3,4-dihydro-2H-pyran and 2,3-dihydrofuran,in the presence of 1 mol % of phosphomolybdic acid under solvent-free conditions at room temperature in good to excellent yields. 相似文献
94.
G. Goll H. v. Löhneysen U. Kreibig G. Schmid 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,20(1):329-331
Specific-heat measurements on the cluster compound Au55(P(C6H5)3)12Cl6 at temperatures 0.06 K ≤T≤3 K and in magnetic fields 0≤B≤6 T are reported. While above 0.6 K the specific heatC is dominated by the inter-cluster vibrational contribution observed previously, an anomalous increase ofC towards lowT is observed below 0.3 K, withC ~T ?2. This contribution develops into a Schottky-like anomaly forB≥0.4 T, indicating that it might be attributed to local moments which are also observed in ESR measurements. From the height of the anomaly one can infer that approximately one tenth of the Au55 clusters carry a magnetic moment. For 0.6 K≤T≤1 K andB=0 our data indicate the absence of a linear electronic specific-heat contribution expected for bulk Au. This possibly constitutes the first direct observation of the quantum-size effect on electronic energy levels in the specific heat. 相似文献
95.
Rudolf Schmid Joseph Foricher Marco Cereghetti Peter Schnholzer 《Helvetica chimica acta》1991,74(2):370-389
The new axially dissymmetric diphosphines (R)- and (S)-(6,6′-dimethoxybiphenyl-2,2′-diyl)bis(diphenyl phosphine) ((R)- and (S)- 5a ; ‘MeO-BIPHEP’) and the analogues (R)- and (S)- 5b and 5c have been synthesized in enantiomerically pure form. These ligands have become readily available by a synthetic scheme which employs, as key steps, an ortho-lithiation/iodination reaction of the (m-methoxyphenyl)diprienylphosphine oxides 8 and a subsequent Ullmann reaction of the resulting iodides 9 to provide the racemic bis(phosphine oxides) 10 . The bis(phosphine oxides) 10 subsequently are resolved with (?)-(2R,3R)- and (+)-(2S,3S)-O-2,3-dibenzoyltartaric acid and reduced to diphosphines 5 . The Ullmann reaction constitutes a new and efficient route to 2,2′-bis(phosphinoyl)-substituted biphenyl systems. Absolute configurations were established for (R)- 5a by X-ray analysis of the derived Pd complex (R,R)- 17a , and for 5b and 5c by means of 1H-NMR comparisons of the derived Pd complexes 16 or 17 , respectively, and by means of CD comparisons. The MeO-BIPHEP diphosphine 5a proved to be as efficient as the previously described BIPHEMP diphosphine ((6,6′-dimethylbiphenyl-2,2′-diyl)bis(diphenylphosphine)) in enantioselective isomerizations and hydrogenations. 相似文献
96.
On the Photochemistry of 1, 2-Benzisoxazoles in Strongly Acidic Solution The 1, 2-benzisoxazoles 1a, 1b and 1d when dissolved in 96% sulfuric acid and irradiated through a quartz filter with a mercury high-presure lamp yield, after work-up, mixtures of 2, 5- and 2, 3-dihydroxy-acylbenzenes ( 2 and 3 , respectively; cf. Schemes 1 and 3 and Table 1). Irradiation of 3, 5-dimethyl-1, 2-benzisoxazole ( 1c ) in 96% sulfuric acid leads to the formation of 2, 3-dihydroxy-5-methyl-acetophenone ( 3c ) in only 6% yield (cf. Table 1). It is assumed that the 1, 2-benzisoxazolium ions react in the excited singlet state by heterolytic cleavage of the N, O-bond to yield the corresponding aryl oxenium ions 7 in the singlet ground state (see Scheme 5). Reaction of 7 with HSO 4 ? ions, present in 96% sulfuric acid, yields, after hydrolysis, the dihydroxy compounds 2 and 3 . Photolysis of 3-methyl-1, 2-benzisoxazole ( 1b ) in diluted sulfuric acid (0,5 to 9 M ) in methanol or water leads only to the formation of 2-amino-phenol ( 6 ; see Scheme 3), presumable via photo-isomerization of 1b to 2-methylbenzoxazole ( 5b ) which then is hydrolyzed to give 6 . 相似文献
97.
The irradiation of the 3-phenyl-2H-azirines 1a–c in the presence of diethyl benzoylphosphonate ( 8 ) in cyclonexane solution, using a mercury high pressure lamp (pyrex filter), yields the diethyl (4, 5-diphenyl-3-oxazolin-5-yl)-phosphonates 9a–c (Scheme 3). In the case of 1b a mixture of two diastereomeric 3-oxazolines, resulting from a regiospecific but non-stereospecific cycloaddition of the benzonitrile-benzylide dipole 2b to the carbonyl group of the phosphonate 8 , was isolated. Benzonitrile-isopropylide ( 2a ), generated from 2,2-dimethyl-3-phenyl-2H-azirine ( 1a ), undergoes a cycloaddition reaction to the ester-carbonyl group of diethyl ethoxycarbonylphosphonate ( 15 ) with the same regiospecificity to give the 3-oxazoline derivative 16 (Scheme 5). The azirines 1a–c , on irradiation in benzene in the presence of diethyl vinylphosphonate ( 17 ) give non-regiospecifically the Δ1-pyrrolines 13a–c and 14a–c (Scheme 6). 相似文献
98.
From the feeding of young plants of Strychnos nux-vomica with [14C]-1-and [14C]-2-acetate it could be deduced that the C-atoms 22 and 23 were derived from acetate. [14C]-2-mevalonate, [14C]-2-geraniol and [14C]-2-geranyl pyrophosphate were also incorporated into strychnine. The distribution of radioactivity in the «mevalonate-strychnine» was in agreement with the monoterpenoid hypothesis. Feeding experiments especially with [14C]-tryptophane showed that the main production centre of the alkaloid lay in the roots and that only a small part of it was carried to the leaves. Tritium labelled WIELAND GUMLICH aldehyde as well as N(a)-[14C]-1-acetyl WIELAND GUMLICH aldehyde were not converted into strychnine by S. nux-vomica. 相似文献
99.
On Phosphazo Compounds from Nitriles. IV. The Reaction of Tri, Di, and Monochloroacetonitrile with [Cl3P?N? PCl3]Cl. Improved Preparation of [Cl3P?N? PCl3]Cl Trichloroacetonitrile reacts with P2NCl7 to give Cl3C? CCl2? N?PCl2? N?PCl3 I , dichloroacetonitrile to give Cl2C?CCl? N?PCl2? N?PCl3 II , and chloroacetonitrile to give the ring compound III . Preparation, n.m.r. and mass spectra of the new compounds are described. The mechanism of formation is discussed. An improved procedure for the preparation of P2NCl7 is given. 相似文献
100.
Zusammenfassung Die Struktur der isotypen Phasen V3Si2, Nb3Si2, Ta3Si2 und Cr3Si2 wurden nach dem Vorschlag vonAronsson (RaumgruppeD
2d
11) gerechnet. Die röntgenographische Analyse dieser Phasen spricht mehr für eine Zusammensetzung von M5Si3.Im System Nb–Si und Ta–Si wurde eine isotype Phase gefunden, die als Hoch- bzw. Tieftemperaturmodifikation der M3Si2-Phasen angesprochen werden kann. Sie läßt sich tetragonal indizieren.Die durch Kohlenstoff stabilisierten M5Si3-Phasen mitD 88-Typ bilden bei V5Si3–Nb5Si3 eine lückenlose Mischreihe, während bei dem Paar V5Si3–Zr5Si3 möglicherweise eine geringe Mischungslücke besteht.VSi2 und NbSi2 sind ebenfalls im festen Zustande lückenlos mischbar; das System VSi2–MoSi2 zeigt eine sehr starke Löslichkeit auf der VSi2-Seite. MoSi2 nimmt dagegen nur wenig VSi2 auf.Mit 2 Abbildungen.Herrn Professor Dr.Emil Abel aus Anlaß seines 80. Geburtstages in aufrichtiger Verehrung gewidmet. 相似文献