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51.
Sixteen compounds containing the bicyclic moiety (3,8,10-trisubstituted 2,9-dioxo-5-thia-1,8-diazabicyclo[4.4.0]decane) were produced via solid-phase synthesis. Differing substitution at the 3- and 10-positions was used. These were analyzed using 2-D NMR techniques (ROESY) to determine the stereoselectivity of ring formation in the core heterocycle. Conformational analysis of the proposed transition state structure using Sybyl 6.8® was used to rationalize the stereochemical outcome of ring formation. 相似文献
52.
53.
Tomoyuki Yoshimura 《Tetrahedron letters》2004,45(50):9241-9244
Diastereoselective construction of the 19-epi-C18-C25 segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C22 and C23 as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place. 相似文献
54.
氯铝酸室温离子液体介质中正碳十二烯选择环化反应 总被引:3,自引:0,他引:3
在氯化1-丙基-3-甲基咪唑(PMImCl)、氯化1-丁基-3-甲\r\n基咪唑(BMImCl)、氯化1-丁基吡啶(BPCl)和溴化1-乙基吡啶(E\r\nPBr)季铵盐与AlCl3构成的室温离子液体介质中,首次发现正十二碳烯\r\n(简称十二烯)可以高选择性地发生环化反应生成环十二烷.依次在反\r\n应管中加入氯铝酸室温离子液体、乙醇和十二烯,其中AlCl3的量为0.\r\n01mol,AlCl3与季铵盐的摩尔比为2,乙醇为10ml,十二烯为2ml(9.\r\n3mmol).当反应体系中不添加乙醇时,十二烯转化率和环十二烷选择\r\n性仅分别为4.2%和73.1%.这是由于十二烯和氯铝酸离子液体形成\r\n两相体系而不易充分接触,故十二烯转化率和环十二烷选择性较低.当\r\n反应体系中加入乙醇时,十二烯和氯铝酸离子液体体系变为单相,使得\r\n十二烯和氯铝酸离子液体可以充分接触,十二烯转化率和环十二烷选择\r\n性可分别达到12.4%和82.9%.压力对提高十二烯转化率和环十二烷\r\n选择性有很大的影响.p(N2)=3.0~6.0MPa下反应12h,十二烯转\r\n化率和环十二烷选择性可分别达到27.2%和93.8%.反应结束后加热\r\n除去乙醇,产物自动与离子液体分层,便于分离,且离子液体介质可重\r\n复使用. 相似文献
55.
A. A. Avetissian G. G. Tokmajian L. V. Karapetian 《Chemistry of Heterocyclic Compounds》2005,41(7):841-844
The reaction of 3-acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyrone with the hydrazides of a series of carboxylic acids led to the
synthesis of 5-alkyl(cyanomethyl)carbonyl-3,5a,7,7-tetramethylpyrazolino-4,5-c]tetrahydro-2-pyrones, which are the products
from cyclization of the intermediately formed alkyl(cyanomethyl)hydrazones of 3-acetyl-4,6,6-trimethyl-5,6-dihydro-2-pyran.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 998–1001, July, 2005. 相似文献
56.
L. G. Shagun L. V. Klyba I. A. Dorofeev E. R. Zhanchipova I. A. Mikhailova M. G. Voronkov 《Chemistry of Heterocyclic Compounds》2007,43(2):166-168
2,5-Dimercapto-2,5-dimethyltetrahyrothiophene was synthesized by the reaction of 1-iodopropan-2-one with hydrogen sulfide
in an ether solution of hydrogen chloride at-70°C. Its structure was established by mass spectrometry, 1H and 13C NMR spectroscopy.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, 216–219, February, 2007. 相似文献
57.
The reaction of various α-silyl-α-keto esters with thiosemicarbazide at 50 °C in ethyl acetate was found to give α-silyl-substituted thiosemicarbazone-acetic acid esters in good yield. These may then be converted to their corresponding silyl-substituted 1,2,4-triazin-5-ones by cyclization under basic conditions. 相似文献
58.
Andrea Basso 《Tetrahedron letters》2004,45(3):587-590
Intramolecular Ugi reactions with bicyclic β-amino acids have been performed and the effects of the configuration and N-alkylation have been studied. We have proven that preferential ring contraction or nucleophilic attack by the solvent depend not only on the presence of N-alkylation but also on the relative disposition of the carboxyl group and the amine. Excellent results in terms of stereoselectivity have been obtained in the case of N-alkyl-3-exo-amino-7-oxabicyclo[2.2.1]-2-endo-carboxylic acids. 相似文献
59.
Sonia E. Blanco 《Tetrahedron letters》2007,48(14):2577-2581
By applying the B3LYP/6-31G(d) method with the SCIPCM model on seven 4X substituted 2-hydroxybenzaldehydes, some structural characteristics related with their conformational equilibria and intramolecular hydrogen bonds have been clarified. The compounds are almost completely under the planar conformation characterized by a strong intramolecular hydrogen bond, which decreases in those solvents that possess a higher hydrogen bond donating capability and polarity. The substituents exert a marked influence on the conformational equilibrium constants and the strength of the IHB. Moreover, the excellent Hammett-type equations obtained support the proposed conformational reactions to quantify the IHB in the o-hydroxybenzaldehydes studied. 相似文献
60.
Anton Meller Walter Maringgele Rainer Oesterle 《Monatshefte für Chemie / Chemical Monthly》1980,111(5):1087-1096
The reaction of galliumtrichloride and galliumtribomide resp. with 2,6-dimethyl- and 2,4,6-trimethyl-N-trimethylsilyl-trifluoroacetanilide leads to the trifluoracetanilidodihalogenogallanes1–3. The 2,6,9-trioxa-4,8-diaza-1,5-digalla-bicyclo-[3.3.1]-nonadiene derivatives1 a–3 a are formed probably as by products.N-Trimethylsilyltrifluoroacetamide reacts with galliumtrichloride to yield the trifluoroacetamido-dichlorogallane4.N-Trimethylsilyl-N,N,N-triorganyl-thioureas react with galliumtrichloride under elimination of chlorotrimethylsilane to give the thio-ureido-gallanes5 and6. IfN,N-diorganylureas andN,N-diorganyl-thio-ureas resp. are reacted with galliumtrichloride and methyl-gallium-dichloride resp., the thio-ureido- and ureido-gallanes7–9 are obtained by elimination of hydrogenchloride. The compounds are characterized by analysis and spectral data (NMR:1H,19F; MS; IR). The substances are monomeric in the gas phase, obviously due to internal coordination.
30. Mitt.:W. Maringgele undA. Meller, J. Organomet. Chem., im Druck. 相似文献