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1.
P. K. Sazonov G. A. Artamkina I. P. Beletskaya 《Russian Journal of Organic Chemistry》2006,42(3):438-447
The nucleophilic aromatic and vinyl substitution using diaza-18-crown-6 as nucleophile afforded a number of its N,N’-diaryl-[aryl = 2,4-(NO2)2C6H3, 4-C5F4N, 4-CF3C6F4] and N,N’-dialkenyl-substituted derivatives [alkenyl = PhC(O)CH=CH, MeOCOCH=CH, (EtO2C)2C=C(Ph), etc.]. Arylation of diaza-18-crown-6 with nonactivated aryl bromides, such as 4-Me2NC6H4Br, 4-MeOC6H4Br, C6H5Br, and 4-CF3C6H4Br, was effected under catalysis by palladium complexes. N,N’-Diaryldiaza-18-crowns-6 having electron-acceptor substituents in the aromatic rings turned out to be incapable of forming complexes with metal cations, while their analogs containing electron-donor para-methoxy and para-dimethylamino groups gave complexes with barium perchlorate. 相似文献
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Sazonov P. K. Artamkina G. A. Beletskaya I. P. 《Russian Journal of Organic Chemistry》2001,37(4):480-495
Reactions were studied between 1-chloro-2-(trifluoromethyl)-hexafluorocyclopent-1-ene with anions [CpFe(CO)2]-, [Re(CO)5]-, [Mn(CO)5]-, [CpMo(CO)3]-, and [CpW(CO)3]-. The effect of proton donors on the composition of reaction products was established. The reactions with [Re(CO)5]- and [Mn(CO)5]- were shown to proceed quantitatively along nucleophilic route (SN2Vin) resulting in -vinyl complexes of rhenium and manganese. The [CpMo(CO)3]- and [CpW(CO)3]- anions turned out to be 104 times less nucleophilic than [Mn(CO)5]-. In this case the main course of the reaction is the metal-halogen exchange with concurrent nucleophilic substitution. In reaction of [CpMo(CO)3]- and [CpW(CO)3]- with 1-chloro-2- (trifluoromethyl)-hexafluorocyclopent-1-ene the -vinyl complexes arise along an unusual autocatalytic mechanism: the reaction of carbonyl occurs not with the initial substrate but with pentafluoromethylcyclopent-1-ene that forms from the substrate under the action of a fluoride ion. In an extremely fast reaction of the same substrate with [CpFe(CO)2]K the main process is carbonylate oxidation along unestablished mechanism. The reaction between carbonylates and 1-chloro-2-(perfluoro-tert-butyl)hexafluorocyclopent-1-ene proceeds exclusively as metal-halogen exchange that with [Re(CO)5]- furnishes anionic acyl complex cis[C9F1
5C(O)Re(CO)4Cl]-. The reaction of Z and E isomers of -chloro-,-difluorostyrenes with [CpFe(CO)2]- in the presence of proton donors confirmed the previously assumed (SN2Vin) mechanism of nucleophilic substitution and also the intermediate formation of alkenyl carbanions in the parallel redox process. 相似文献
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L. Kh. Minacheva P. K. Sazonov V. S. Sergienko G. A. Artamkina I. P. Beletskaya A. Yu. Tsivadze 《Russian Journal of Inorganic Chemistry》2006,51(7):1071-1081
It has been shown that N,N’-diaryldiaza-18-crown-6 ethers with p-dimethylamino-and p-methoxy groups in the benzene ring (aryl is 4-Mc2NC6H4) (I) and 4-MeOC6H4 (II) form complexes with potassium and barium salts. The influence of these salts on the UV and 1H NMR spectra of crown ethers I and II has been studied. The stability constants (logβ) of the complexes increase in the series II · Ba(ClO4)2 (2.0), I · Ba(ClO4)2 (2.3), II · KBr (2.8), I · KBr (3.0). N,N’-bis(4-dimethylphenylamine)diaza-18-crown-6 (L, I) and its complex with barium perchlorate Ba(ClO4)2 · L (III) are characterized by X-ray crystallography. The crystals of I are monoclinic: a = 13.778(2) Å, b = 5.9731(9) Å, c = 17.542(3) Å, β = 106.65(1)°, V = 1383.1(4) Å3, Z = 2, space group P21/n, R = 0.0374 for 990 reflections with I > 2σ(I). The crystals of III are monoclinic: a = 17.275(4) Å, b = 8.017(2) Å, c = 26.935(4) Å, β = 100.47(2)°, V = 3669(1) Å3, Z = 4, space group C2/c, R = 0.0320 for 1897 reflections with I > 2σ(I). The molecules of I and III are centrosymmetric. In III, the Ba atom is in the center of substituted diaza-18-crown-6 (DA18C6). The Ba atom is coordinated by all six donor atoms of diaza-18-crown-6 (av. Ba-O, 2.779(3) Å; Ba-N, 3.004(4) Å) and four oxygen atoms of two asymmetrically bound perchlorate groups (Ba-O, 2.832(4) and 3.031(4) Å) arranged below and above the plane of substituted diaza-18-crown-6. The conformations of the macrocycle in free and coordinated L are different. 相似文献
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T. V. Magdesieva I. I. Kukhareva D. P. Krut'ko G. A. Artamkina K. P. Butin I. P. Beletskaya 《Russian Chemical Bulletin》1994,43(5):881-883
Interaction of the 5-cyclopentadienyldicarbonyliron(II) anion with pentafluorobenzoyl chloride affords C6F5COFe(CO)2Cp, CpFe(CO)2C6F4COFe(CO)2Cp, and CpFe(CO)2C6F4C6F4Fe(CO)2Cp. The reaction products are characterized by1H,13C and19F NMR spectra.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 935–937, May, 1994. 相似文献
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Artamkina G. A. Petrov A. R. Serushkina O. V. Dutov M. D. Shevelev S. A. Beletskaya I. P. 《Russian Journal of Organic Chemistry》2003,39(6):846-859
Arylation catalyzed by palladium complexes of substituted anilines obtained by modification of 2,4,6-trinitrotoluene makes possible preparation of various diaryl- and arylheterylamines in high yields. 相似文献