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21.
22.
Gareth J. Rowlands Author Vitae 《Tetrahedron》2010,66(9):1593-501
23.
24.
Benan K?lba?Author VitaeMetin BalciAuthor Vitae 《Tetrahedron》2011,67(13):2355-2389
25.
Kazem D. Safa Farnaz Behmagham Khatereh Ghorbanpour 《Journal of organometallic chemistry》2011,696(9):1840-1844
The magnesium bromide-diethyl etherate-catalyzed ring-opening of (3-(naphthalen-2-yl)-2,2-bis(trimethylsilyl)oxiran 2 with thiophenols affords (1-trimethylsilylvinyl)sulfides 3 and the (1-bromovinyl)silane 4. Nucleophilic attack occurs regioselectively at the position α- to silicon. The compound 2 has been converted into the (1-trimethylsilylvinyl)amide 5 with an excess of acetonitrile and into the (1-trimethylsilylvinyl)acetate 6 with acetic acid/acetic anhydride. These reactions proceed with catalytic amounts of boron trifluoride-diethylether. Treatment of 2 with acetic acid alone gives naphthaldehyde. The epoxide 2 reacts also with MgBr2·OEt2, MeLi/CuI, HX (XBr or Cl) and LiAlH4 with nucleophilic attack at the bis(trimethylsilyl)-substituted carbon. 相似文献
26.
Through SiP bond cleavage, the reaction of P7(SiMe3)3 with one equivalent of KOtBu or LiOtBu afforded different isomers of the heptaphosphanide anion [P7(SiMe3)2]−. With LiOtBu, concomitant inversion at an equatorial (silylated) phosphorus atom occurred and the Cs symmetric isomer characterized by a mirror plane formed. With KOtBu, inversion did not occur and the resulting asymmetric anion with C1 symmetry formed. With NaOtBu, a mixture of both isomers was obtained. The symmetries and structures of the anions were elucidated with 31P{1H} and 29Si{1H} NMR spectroscopy, and relative stabilities were calculated employing the B3LYP/6-31+G* method.The reaction of KP7(SiMe3)2 or LiP7(SiMe3)2 with 1,2-dichlorotetramethyldisilane led to (SiMe3)2P7SiMe2SiMe2P7(SiMe3)2, a molecule composed of two P7-cages connected by a disilane bridge. It can also be obtained through silyl exchange using P7(SiMe3)3 and ClMe2SiSiMe2Cl. The compound was characterized with 31P and 29Si-NMR spectroscopy and elemental analysis. Treatment of P7(SiMe3)3 with HypCl (Hyp = hypersilyl = Si(SiMe3)3) in DME led to the quantitative formation of Hyp2P7SiMe3. Single crystal X-ray diffraction as well as 31P and 29Si-NMR spectroscopy proves the presence of a heteroleptically substituted heptaphosphane cage.Quantum chemical HF and B3LYP/6-31G* calculations of equilibrium structures for the two possible isomers of P7(SiMe3)3 (sym and asym) reveal that asym is destabilized by about 30-40 kJ mol−1, which explains why its formation could not be observed. The phosphorus inversion barrier for the sym → asym transition is calculated as 60-70 kJ mol−1. 相似文献
27.
A rapid gas chromatography-tandem mass spectrometry (GC-MS/MS) analytical method was developed for the simultaneous analysis of 7 estrogenic hormones (17α-estradiol, 17β-estradiol, estrone, mestranol, 17α-ethynylestradiol, levonorgestrel, estriol) and 5 androgenic hormones (testosterone, androsterone, etiocholanolone, dihydrotestosterone, androstenedione) in aqueous matrices. This method is unique in its inclusion of all 12 of these estrogens and androgens and is of particular value due to its very short chromatographic run time of 15 min. The use of isotope dilution for all analytes ensures the accurate quantification, accounting for analytical variabilities that may be introduced during sample processing and instrumental analysis. Direct isotopically labelled analogues were used for 8 of the 12 hormones and satisfactory isotope standards were identified for the remaining 4 hormones. Method detection levels (MDLs) were determined to describe analyte concentrations sufficient to provide a signal with 99% certainty of detection. The established MDLs for most analytes were 1-5 ngL(-1) in a variety of aqueous matrices. However, slightly higher MDLs were observed for etiocholanolone, androstenedione, testosterone, levonorgestrel and dihydrotestosterone in some aqueous matrices. Sample matrices were observed to have only a minor impact on MDLs and the method validation confirmed satisfactory method stability over intra-day and inter-day analyses of surface water and tertiary treated effluent samples. 相似文献
28.
The regioselectivity of alkylation of lithium (trimethylsilyl)tetramethylcyclopentadienide C5Me4SiMe3
−Li+ was studied by 1H and 13C NMR spectroscopy using its reactions with MeI, MeOTs, ClCH2CH2Br, and ClCH2CH2I in different solvents as representative examples. Sterically non-hindered MeI and MeOTs presumably attack the C atom bonded to the silyl group giving 1,2,3,4,5-pentamethylcyclopentadienylsilane. For bulkier alkyl halides, such as ClCH2CH2Br and ClCH2CH2I, the regioselectivity of alkylation changes to form preferentially gem-dialkyl-substituted cyclopentadienes. The reaction of C5Me4SiMe3
−Li+ with formaldehyde affords 1,2,3,4-tetramethylfulvene in a high yield, providing an alternative synthetic approach to a number of ω-functionalized peralkylated cyclopentadienes. The quantum-chemical calculations of the C5Me4SiMe3
− anion by the RHF and DFT (RMPW1PW91) methods in the valence-split 6-311+G(d,p) basis set are in good agreement with the experimental data.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2089–2093, October, 2004. 相似文献
29.
ShuJieHOU ChuanChunZOU PingShengLEI DeQuanYU 《中国化学快报》2005,16(5):593-596
Using thioglycosides as donors, trimethylsilyl trifluoromethanesulfonate (TMSOTf) and N-iodosuccinimide(NIS) as promoter, a modified procedure for the glycosylation of spirostanol was developed. A series of saponins were synthesized in mild condition with excellent yields. 相似文献
30.
Hélène Pellissier Author Vitae 《Tetrahedron》2007,63(16):3235-3285