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11.
Compounds of general formulatrans-ArNi(PR3)2OAr' (R = Et, cyclohexyl; Ar = 2-MeC6H4, 2-FC6H4; Ar' = 4-FC6H4, 4-NO2C6H4) were synthesized by the reaction of Ar'OK with cationic nickel complexes generated by treatment of ArNi(PR3)2Cl with TlBF4. Syntheses of 4-fluorophenoxide complexes, ArNi(PR3)2OC6H4F-4, additionally give some quantities oftrans-[ArNi(PR3)2OC6H4F-4][HOC6H4F-4] adducts. Exchange reactions MeC6H4Ni(PEt3)2OC6H4F-4 + XC6H4OH 2-MeC6H4Ni(PEt3)2OC6H4X + 4-FC6H4OH were studied in THF. The equilibrium is shifted to the right as the acidity of ArOH increases. A linear relationship between lgK
eq and pK
a of XC6H4OH in DMSO was found. A conclusion concerning the strong polarization of the Ni-O bond was made on the basis of an analysis of the chemical shifts of fluorine atoms in 2-MeC6H4Ni(PEt3)2OC6H4F-4.Translated fromIvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2271, November, 1995. 相似文献
12.
Different stationary phases were prepared by mixing a series of inorganic salts with dimethylsiloxane polymer (SE-30) and then tested by capillary gas chromatography. It was demonstrated that the polarity (as evaluated by measurement of Rohrschneider constants) of the mixed stationary phases, which is inferior or equal to that of a medium-polar OV-25 phases, reached even lower values than SE-30 alone. The influence of NaF, NaCl, NaBr, AgNO3, and other inorganic salts on the polarity of capillaries is reflected by a better resolution and shorter retention time of cis/trans isomers of fatty acid methyl esters (FAMES) as well as positional isomers of triglycerides. 相似文献
13.
Micelles of different amphiphiles adopt different shapes and internal packing arrangements in water, depending on their chemical
structures and the conditions of the medium. Two microenvironmental features, namely the polarity and the microviscosity that
the aggregate offers to a solubilized molecule, have been monitored using extrinsic fluorescence probes. While the differences
between micelles of spherical and rod-like shapes are not always distinct, stacked micelles and peptide micelles offer distinctly
lower polarity and higher microviscosity to solubilizates than the others. 相似文献
14.
15.
B. A. Arbuzov Z. G. Isaeva M. G. Belyaeva V. V. Ratner O. N. Kataeva I. A. Litvinov V. A. Naumov 《Russian Chemical Bulletin》1992,41(1):117-119
Oxidation of 2-carene by lead tetraacetate in acetic acid afforded p-menth-1(10),2-dien-7-ol, 2-acetyl-6,6-dimethylbicyclo[3.1.0]hexane, p-menth-2-ene-1,7-diol, p-menth-1-ene-3,7-diol, and 2-(m-tolyl)propanol-2.Deceased.A. M. Butlerov Scientific Research Chemical Institute, V. I. Ul'yanov-Lenin Kazan' State University, 420008 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 147–150, January, 1992. 相似文献
16.
单体极性对甲基丙烯酸甲酯/丙烯酸丁酯/甲基丙烯酸钠无皂乳液共聚合的影响 总被引:1,自引:0,他引:1
研究了少量甲基丙烯酸钠(NaMA)存在下单体极性对甲基丙烯酸甲酯(MMA)/丙烯酸丁酯(BA)无皂乳液共聚合的影响.单体极性降低,使粒径减小、聚合速率提高、乳液表面张力和粘度降低、粒子表面电荷密度增大、聚合物分子量提高.MMA/NaMA无皂乳液聚合物只呈现一个玻璃化温度Tg,BA/NaMA无皂乳液聚合物呈现两个Tg,MMA/BA比为2∶1~1∶2的MMA/BA/NaMA无皂乳液聚合物呈现四个Tg,这是由于粒子外面相对富含OSO-3和COO-基聚合物的亚层溶解了较多的水,使BA向粒子中心扩散,MMA向外扩散,造成组成差异和相分离而引起的. 相似文献
17.
Y. Marcus 《Journal of solution chemistry》1991,20(9):929-944
Taft and Kamlet's -scale of solvent hydrogen bond donation ability is reexamined with regard to its correlations with three widely used polarity scales: Dimroth and Reichardt's E
T
(30), Kosower's Z and Mayer's A
N
, as well as with the m values of the solvents when present as monomeric solutes. The correlation with E
T
serves to extend the solvent -scale according to the expression:
相似文献
18.
The new 3-hydroxychromone derivative 2-(6-diethylaminobenzo[b]furan-2-yl)-3-hydroxychromone (FA) displays a dramatic solvent-dependent transformation of fluorescence spectra in the range of low-polarity solvents. The two well-separated emission bands change their relative intensities so that the short-wavelength band being of a very low intensity in hexane becomes dominant in the more polar ethyl acetate and trichloromethane. We suggest the participation in this effect of excited-state intramolecular proton transfer, which is characteristic for other 3-hydroxychromone and 3-hydroxyflavone derivatives, in the range of solvents of much higher polarities. Because of these unique properties, a number of spectroscopic parameters (positions of absorption and two fluorescence maxima, the ratio of their intensities and the fluorescence quantum yield) can be measured in this solvent range with multiparametric analysis of the data. In terms of solvent polarity, the shifts in both emission bands and their intensity ratio demonstrate a good correlation with empirical polarity scales ETN, Py and SPP, while the absorption spectra reveal some deviations for the tested oxygen-containing solvent molecules. A good cross-correlation is observed between fluorescence spectral shifts and the ratio of band intensities. The latter provides the means for a dramatic amplification of solvent response. Thus, a new approach for ultrasensitive scaling and probing the solvent polarity in the low-polararity range can be suggested. It involves very simple ratiometric measurements at two emission bands and can be posed for a variety of applications. We present examples of these applications for distinguishing of polarities between methylated benzene derivatives, for quantitative assay of polar impurities in low-polar solvents and for detection of the changes of solvent polarity as a function of temperature. 相似文献
19.
The solvatochromic behavior of a penta‐tert‐butyl prydinium N‐phenolate betaine dye was studied using UV‐visible spectrophotometry in several binary mixture solvents. The solvent polarity parameter, ET (1) (kcal. mol?1) was calculated from the position of the longest‐wavelength intramolecular charge transfer absorption band of this penta‐tert‐butyl betaine dye. For binary solvent mixtures, all plots of ET (1) versus the mole fraction of a more polar component are nonlinear owing to preferential solvation of the probe by one component of the binary solvent mixture. In the computation of ET (1) it was assumed that the two solvents mixed interact to form a common structure with an ET (1) value not always intermediate between those of the two solvents mixed. The results obtained are explained by the strong synergism observed for some of the binary mixtures with strong hydrogen bond donors (HBD) solvents such as alcohols. 相似文献
20.
Empirical solvent parameters of silica surfaces are determined by means of solvatochromic dyes, e.g., Cu(tmen) (acac)+ ClO
4
–
/B(C6H5)
4
–
, Fe(phen)2(CN)2, and Michlers Ketone dissolved in 1,2-dichloroethane or cyclohexane. The values obtained by UV/VIS-measurements are compared with both the polarity scales of Kamlet and Taft and with Gutmann's donor and acceptor numbers. Kamlet and Taft's -parameter (the hydrogen-bond donation capacity of a solvent) is determined independently by means of salicylideneaniline. The * of silica is determined using 5-N,N-dimethylamino-5-nitro-2,2-bithiophene and the complex of tetracyanoethylene with Michlers Ketone, respectively. Further on the reliabilities of the obtained Kamlet-Taft parameters , , and * are checked by comparism with experimental and calculated values of theE
T(30)-parameter of silica by means of multi-parameter regression analysis. The surface properties of silica are influenced mainly by HBD-properties (75%) and dipolarity/polarizability * (20%), but hardly by the HBA-properties (<5%). UV/VIS-measurements were carried out in a special equipment with glass fiber optics, A drawing of the apparatus is given. 相似文献
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