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111.
Gupta HK Stradiotto M Hughes DW McGlinchey MJ 《The Journal of organic chemistry》2000,65(12):3652-3658
Tetracyclone, 2a, reacts with C(6)F(5)Li to yield 2-pentafluorophenyl-2,3,4,5-tetraphenylcyclopent-3-en-1-one, 7, and 5-hydroxy-5-pentafluorophenyl-1,2,3,4-tetraphenylcyclopentadiene, 8, as the result of 1,6 and 1,2 additions, respectively. In contrast, treatment of 3-ferrocenyl-2,4,5-triphenylcyclopentadienone, 2b, with lithiopentafluorobenzene leads to 4-ferrocenyl-4-pentafluorophenyl-2, 3,5-triphenylcyclopent-2-en-1-one, 9, and 5-hydroxy-5-pentafluorophenyl-2-ferrocenyl-1,3, 4-triphenylcyclopentadiene, 10, the products of 1,4 and 1,2 addition, respectively. The structures of 7-9 have been established by X-ray crystallography, and the barriers to rotation (19-21 kcal mol(-)(1)) of the pentafluorophenyl groups in 8-10 have been studied by variable-temperature (19)F NMR. Nucleophilic attack at the ferrocenyl-bearing carbon in 2b is rationalized in terms of a zwitterionic structure in which the positive charge of the "cyclopentadienyl cation" is delocalized onto the iron atom in the organometallic substituent. 相似文献
112.
Summary Thorium and zirconium can be quantitatively precipitated by quinaldinic acid atph 2.7 and 3, respectively. As the precipitates are of nonstoichiometric composition they are to be ignited to oxides. By this reagent thorium can be quantitatively separated from arsenic (As3+), mercury (Hg2+), rare earths, manganese, magnesium and alkaline earths and zirconium from all the aforesaid ions excepting rare earths which contaminate to a slight extent. 相似文献
113.
A method was developed for direct determination of minor and trace amounts of Cr, Mn, Cu, Ni, Co, Li, Pb, Cd, Bi, Sb, Be and Ag in silicate rock, lake and stream sediments using a microwave oven dissolution method and a multi-element graphite furnace atomic absorption spectrometer equipped with a Zeeman-effect background correction device. The measurement technique was also suitable for direct determination of trace and ultra-trace amounts of these elements in drinking and seawater samples. A rock or sediment sample was brought into solution in a Teflon vessel by heating in a microwave oven with a mixture of hydrofluoric acid and aqua regia, followed by a further heating with a mixture of boric acid and ethylenediaminetetraacetic acid. The specified elements were directly determined in a group of four elements in one firing and eight elements in two firings from this solution or from a diluted solution using the optimum operating parameters developed in this work. The method, tested with 23 international reference rocks and sediments and seven international quality control and reference water samples, showed good to excellent agreement with the recommended values. 相似文献
114.
Summary Fifteen palladium(II) square-planar complexes containing monodentate and/or bidentate anti- and syn-furan-2-aldoxime (FDH) have been isolated and characterized by elemental analysis, molecular weight determination, conductance studies, magnetic moments and i.r. spectral studies. The monodentate ligand coordinates through the nitrogen atom while the bidentate ligand coordinates through the furan oxygen atom and the nitrogen atom. The C-O-C stretching frequency of the furan ring may be taken as the criterion for the denticity of this ligand and is observed at 1240 and 1270 cm– in anti- and syn-furan-2-aldoxime respectively. A shift to lower frequency occurs (in the complex) if the ligand is bidentate, however this frequency is unaffected if the ligand is monodentate. 相似文献
115.
An indirect UV photometric detection technique is described in which a low concentration of a UV-absorbing compound (UVAC) is added to the mobile phase in reversed phase liquid chromatography, thereby making it possible for non UV-absorbing compounds such as the lower alcohols to be detected by the UV detector. This happens because the injected analyte may extract a portion of the UV absorbing compound from the mobile and/or stationary phase and the complex is co-eluted as a positive peak at the retention time of the analyte. Alternatively, the injected analyte may appear as a negative peak if the UV-absorbing compound is transferred to the mobile and stationary phases. In any case, the injected compound appears either as a positive or negative peak depending on the relative polarities and concentrations of all the compounds in the system. In addition, the resulting excess or deficiency of detection agent in the stationary phase is eluted separately as a positive or negative peak, indicating that the system has returned to equilibrium. In the work described herein, the chromatographic conditions and variables of the indirect photometric technique were studied to develop a quantitative HPLC method for UV-transparent compounds. It was found that under optimal conditions it is possible to determine some analytes quantitatively at concentrations as low as 0.05%. 相似文献
116.
A simple and sensitive method for the determination of isoproturon, a widely used herbicide is described here which is based on alkaline hydrolysis of isoproturon to its corresponding primary amine followed by diazotization and coupling with p-aminoacetophenone in alkaline medium. The absorption maxima of the coloured compound formed is measured at 525 nm. Beer's law is obeyed over the concentration range of 0.5-5.0 mug in a final solution volume of 25 ml (0.02-0.2 ppm). The molar absorptivity and Sandell's sensitivity were found to be 8.6x10(5) l mol(-1) cm(-1) and 0.0002 mug cm(-2), respectively. The method has been satisfactorily applied to the determination of isoproturon in environmental and biological samples. 相似文献
117.
Localized modes due to H?Na+H? complex impurity in KCl crystal have been computed by a Green function method and compared with experimental data. 相似文献
118.
Tara Chandra Gupta Abani K. Bhattacharya 《Fresenius' Journal of Analytical Chemistry》1960,172(6):428-430
Summary The only method recommended for the direct estimation of ferric iron in presence of HCl is to reduce the ferric iron to ferrous iron and then to titrate against KMnO4 solution by adding Reinhardt-Zimmermann reagent (MnSO4 + H2SO4 + H3PO4). The solubility of the phosphato complexes of ferric chloride and phosphoric acid is much reduced by adding a nonaqueous solvent, ethyl alcohol or acetone. This property has been availed of to find out a method of estimating ferric iron directly against standard solution of phosphoric acid in aqueous-nonaqueous medium using K4Fe(CN)6 or cupferron as external indicators. A slight discrepancy at the end point, however, exists in the direct titration but it can be removed by applying a correction factor determined from the estimated results. 相似文献
119.
Zinc powder was found to be a highly efficient catalyst for the synthesis of aromatic ethers using microwave heating in the presence of N,N-dimethylformamide as well as under stirring in an oil-bath using tetrahydrofuran as solvent without any inorganic base. This method can be used for selective mono-, di- or tri-O-alkylations. 相似文献
120.
Computations of the Diels-Alder (DA) reactions of azaphosphole representative namely, thiazolo[3,2-d][1,4,2]diazaphosphole with 1,3-butadiene and isoprene at the density functional theory level reveal concerted mechanisms via asynchronous transition states. The activation energies (B3LYP/6-311++G**// B3LYP/6-311G**), 16-19 kcal mol−1, are much smaller than the value (32.57 kcal mol−1) calculated for the DA reaction of the non-phosphorus analogue, imidazo[2,1-b]thiazole with 1,3-butadiene. An electron-withdrawing group at the 3-position of the dienophile enhances both stereo- and regioselectivities, which agree nicely with the experimental values. Inclusion of solvent effect (PCM model) reveals that the stereo- and regioselectivities are not affected appreciably. The relative stabilities of the transition structures corresponding to the endo/exo stereoisomers and meta (P/Me, 1:3)/para (P/Me, 1:4) regioisomers have been rationalized on the basis of the secondary molecular orbital interactions. 相似文献