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31.
L. S. Zakharov G. N. Molchanova T. M. Shcherbina P. V. Petrovskii M. I. Kabachnik 《Russian Chemical Bulletin》1998,47(9):1718-1724
A number of trialkylsilylmethyl diphenyl phosphates MeRR′SiCH2OP(O)(OPh)2 (1a-e: R=Et (a), Pr (b), CF3CH2CH2 (c, e), Me3SiCH2 (d); R′=Me (a-d), Et (e)) were synthesized and their thermal rearrangement, of the 1,2-shift type, was studied. The rearrangement consists of the
migration of an alkyl group from Si atom to the methylene carbon atom and gives the corresponding silyl esters. The rate of
the rearrangement was found to increase in the order1d<1b<1a<1 (R=R′=Me)<1c corresponding to the enhancement of the total inductive effect (−I) of the substituents at the Si atom. The relative migration ability of the substituents at the Si atom, determined by GC/MS
analysis of the disiloxane fraction resulting from hydrolysis of pyrolyzed phosphates1a-e, increases in the order R=Pr<Et<CF3CH2CH2<Me≪Me3SiCH2, which differs substantially from the order in which the rate of the rearrangement of phosphates1a-d changes. The electronegativity of the migrating group affects noticeably the relative ability to migrate.
For Part 4, see Ref. 1.
Deceased.
Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 9, pp. 1767–1772, September, 1998. 相似文献
32.
高分辨等离子体质谱法直接测定高纯镓中的痕量元素 总被引:9,自引:0,他引:9
建立高分辨电感耦合等离子体质谱法(HR-ICP-MS)测定高纯镓样品中Be、Mg、A l、S i、Ti、V、Cr、Mn、Fe、Co、N i、Cu、Zn、Ge、As、Mo、Ag、Cd、In、Sb、Ba、Pb、B i等痕量元素的方法。样品用HNO3 HC l经微波消解后,试液直接进样用HR-ICP-MS法同时测定上述元素,在高分辨质谱测量模式下避免了大量的质谱干扰,详细地研究了HC l和高纯镓所产生的基体效应,以Sc、Rh、Tl作为内标元素校正了基体效应,讨论和确定了实验的最佳测定条件。结果表明,23种痕量元素的检出限在0.001~0.21μg/L之间;回收率在89.8%~111.6%之间,相对标准偏差(RSD)小于3.3%。 相似文献
33.
Mohamed El Guendouzi Abderrahim Dinane Abdelfetah Mounir 《Journal of solution chemistry》2002,31(2):119-129
The mixed aqueous electrolyte system of ammonium and lithium chlorides has been studied by the hygrometric method at 25°C. The relative humidities of this system are measured at total molalities from 0.3 to 6 mol-kg– 1 for different ionic-strength fractions y of NH4Cl with y = 0.33, 0.50, and 0.67. The data obtained allow the deduction of new water activities and osmotic coefficients. The experimental results are compared with the predictions of the ECA (extended composed additivity) law proposed in our previous work. The Zdanovskii–Stokes–Robinson (ZSR), the Robinson–Stokes (RS), Reilly–Wood–Robinson (RWR), the Pitzer, and the Lietzke–Stoughton (LS II) models are also compared with our results. Predictions made using these models are, in general, consistent with our results. From these measurements, new Pitzer mixing ionic parameters are determined and used to predict the solute activity coefficients in the mixture for different ionic-strength fractions. 相似文献
34.
The reaction paths for the transformations of substituted acetylenes (X—CC—Y; X, Y = H, Me, Ph, CN) in reaction with phenylsulfenium cation were studied by quantum-chemical methods. It was shown that the reactions take place with the formation of acyclic and cyclic cationic intermediates. The factor that determines the structure and characteristics of these cations is the induction and polarizing action of the substituents in the acetylenes and to a lesser degree their electron-donor characteristics. The resonance effect of the phenyl substituent has a predominantly levelling action on the distribution of charges. 相似文献
35.
5,6-Bis(dimethylamino)acenaphthylene is readily involved in [4+2] cycloaddition reactions with symm-tetrazine derivatives to form new proton sponges with the diazafluoranthene skeleton. Under analogous condition, 1,8-bis(dimethylamino)-4-vinylnaphthalene gave 4-pyridazinyl derivatives. The relative reactivities of 5,6-bis(dimethylamino)acenaphthylene, 1,8-bis(dimethylamino)-4-vinylnaphthalene, 5-dimethylaminoacenaphthylene, and acenaphthylene in the reactions with 3,6-diphenyl-symm-tetrazine are in a ratio of 32 : 17 : 14 : 1. The site of protonation of 3,4-bis(dimethylamino)-7,10-diphenyl-8,9-diazafluoranthene is controlled by the basicity of the solvent. The reaction in acetonitrile afforded the cation stabilized by an intramolecular hydrogen bond, whereas the reaction in dimethyl sulfoxide gave rise to the resonance-stabilized cation. 6,7-Bis(dimethylamino)phenalen-1-one was protonated only at the carbonyl group. 相似文献
36.
Guerrero-Alvarez JA Moncayo-Bautista A Ariza-Castolo A 《Magnetic resonance in chemistry : MRC》2004,42(6):524-533
The relative configuration of 11 1,4-diazaspiro[4.5]decanes (1a-1j and 1m), 15 1,4-oxazaspiro[4.5]decanes (2a-2o) and 10 1,4-dioxaspiro[4.5]decanes (3a-3n) substituted at the 2-, 6-, 7- or 8-position by a methyl group or using the tert-butyl group as a model for the ananchomeric structure is reported. The relative stereochemistry was analyzed by 1H, 13C, 15N and 17O NMR and all isomers present were characterized spectroscopically. Compounds with a methyl group in the six-membered ring show a chair conformation preference with the methyl group in the equatorial position. Compounds with one or two nitrogens exhibit a tautomeric equilibrium between the imine-diazolidine forms, as demonstrated by IR and 13C NMR. 相似文献
37.
分别用MNDO和AM1两种半经验方法,对C59F2nHN (n = 1, 2) 的异构体进行几何构型全优化,结合频率分析及HF/6-31G单点能计算,确定了各异构体的基态结构及其相对稳定性。计算结果表明,C59HN的F加成物的立体选择性规律与C60的不同,最稳定异构体不是1-2加成物。C59F2HN的最稳定异构体是1-4加成的6, 18-或12, 15-异构体; C59F4HN的最稳定异构体是1-4,1-4加成的6, 18; 12, 15-异构体,其能量远小于其它各异构体的能量。N原子取代碳笼骨架C原子后,改变了碳笼F加成物的立体选择性规律。 相似文献
38.
《Journal of separation science》2003,26(8):701-708
A micellar electrokinetic chromatographic and a fast reversed‐phase liquid chromatographic method have been developed for determination of the purity of phenoxymethylpenicillin. The optimized running buffer composition was 40 mM phosphate–borate–125 mM SDS–3.5% (v/v) methanol. The HPLC method employed a monolithic silica C18 column and a mobile phase composed of phosphate buffer, pH 3.5, and ACN, the flow‐rate being 3.5 mL/min. Both methods were successfully validated. Linearity, intermediate precision, limits of quantitation, accuracy, and a good correlation of the HPLC and MEKC results were demonstrated. Both methods proved to be fast and reliable and sufficiently sensitive. A combination of the two methods can be very useful in impurity profiling. 相似文献
39.
Andrea Posilicano 《Potential Analysis》1996,5(3):241-271
We prove a convergence theorem for sequences of Diffusion Processes corresponding to Dirichlet Forms of the kind
.We obtain convergence in total variation norm of the corresponding probability measures on the path space C(+;d) under hypotheses which, for example, are satisfied in the case of H
loc
1
(
d
)-convergence of the 's, but we can allow more singular situations as regards the approximating sequences. We use then these results to give a criterion of convergence for generalized Schrödinger operators in which the potential function should not necessarily exists as a measurable function. We obtain convergence not only in strong resolvent sense, but we also obtain convergence in the uniform operator topology up to sets of arbitrarily small Lebesgue measure. Applications to the problem of the approximation of ordinary Schrödinger operators by generalized ones corresponding to zero-range interactions are given. 相似文献
40.
For the major, minor and trace element analysis of the inorganic compounds of a Ruhr-Saar coal different preparation techniques are investigated with X-ray fluorescence analysis, electron microprobe and classical wet chemical methods minimizing sample weight at standard preparation times and analytical accuracies. Considering accuracy as well as preparation efforts, determinations by electron microprobe on small sample amounts (<50 mg) proved to be superior to the other methods.Abbreviations AAS
atomic absorbtion spectrometry
- EMA
electron microprobe analysis
- IC
ion chromatography
- ISE
ion sensitive electrode
- PHOT
photometry
- WCA
wet chemical analysis
- XRF
X-ray fluorescence analysis
- LTA
low temperature plasma ashing
- HTA
high temperature ashing
- l.o.i.
loss on ignition 相似文献