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11.
Earlier work by Lindenbaum and Boyd has demonstrated the important role of hydrophobic interactions involving the water solvent in determining the osmotic coefficients and properties of aqueous solutions of the tetraalkylammonium halides. Osmotic coefficients of solutions of tetramethyl-, tetraethyl-, tetrapropyl-, and tetrabutylammonium bromides in the more highly structured solvent D2O have now been determined by the gravimetric isopiestic method, using reference solutions of NaCl in D2O. The data were fitted to the Rush-Johnson and Pitzer equations. Satisfactory agreement with the results for aqueous solutions at comparable concentrations indicates that the solution chemistry of these quaternary ammonium bromides is not highly dependent on the degree of structure of the pure solvents. Supplementary data for mixtures of Me4NBr with Et4NBr, Pr4NBr, or Bu4NBr in both H2O and D2O are consistent with this conclusion.On leave 1980–82 from Banaras Hindu University, India 相似文献
12.
We previously reported the use of imidazole as starting compound for preparing a bicyclic imidazolium ionic liquid, [b-3C-im][NTf2], with an overall 29% isolated yield in four synthetic steps. This new room temperature ionic liquid was shown to be far more chemically stable than commonly used [bmim][PF6], [bdmim][PF6], and [bdmim][NTf2]. Because of this intriguing chemical stability, it prompted us to develop a more generalized and high yielding synthesis so that molecular diversity of bicyclic ionic liquids may be explored. In this work, we amended the previous synthetic route by employing 4-chlorobutyronitrile or 5-chlorovaleronitrile as starting materials and successfully developed a five-step synthesis of a series of novel bicyclic imidazolium-based ionic liquids in 40-53% overall isolated yields. We investigated intrinsic reactivity of all bicyclic ionic liquids prepared and found that, under strongly basic conditions, among all tested ionic liquids the 5,5-membered [R-3C-im][NTf2] ionic liquids were most stable to solvent deuterium isotope exchange while the previously reported [bdmim][NTf2] ionic liquid was 50% deuterium exchanged at its C-2 methyl in 30 min at ambient temperature. Under identical condition, the commonly used [bmim][NTf2] ionic liquid was deuterium exchanged instantaneously at its C-2 hydrogen. In the absence of bases, only [bmim][PF6] was deuterium exchanged (50% within 1 h) and all other ionic liquids gave no detectable exchanges even after 25 days at ambient temperature. Moreover, both [bmim][NTf2] and [bdmim][NTf2] ionic liquids were readily methylated at C-2 position with methyl iodide under basic condition at room temperature. Under the same condition, [R-3C-im][NTf2] and [R-4C-im][NTf2] ionic liquids were completely stable and chemically inert. We envisioned that [R-3C-im][NTf2] should be well suited as solvents for organic synthesis. 相似文献
13.
The solvothermal reaction (D2O) of 2,6-dideuterium-4-cyanopyridine with ZnCl2 in the presence of NaN3 offers a novel complex Zn(OD)(C6H2D2N4) (1) in which Zn has a distorted tetrahedron composed of two N atoms from one tetrazoyl group and pyridyl group and two O atoms from two deuteratohydroxy OD groups. Crystal data for 1: Pbcn, a=1.456 8(5) nm, b=0.659 2(2) nm, c=1.645 3(5) nm, α=90°, β=90°, γ=90°, V=1.580 0(9) nm3, Z=8, M=231.54, Dc=2.236 Mg·m-3, μ=3.070 mm-1, R1=0.043 4, wR2=0.120 6, S=1.029. CCDC: 660629. 相似文献
14.
Effects of Salt on the Orientational Order in Decylammonium Chloride/Ammonium Chloride/Water Systems
The effect of NH4Cl on the temperature dependence of deuterium oxide splitting (water order) and proton line width (surfactant order) in decylammonium chloride (DACl), D2O systems is reported. The molar ratio of DACl to D2O was held constant at .085 and the molar ratio of NH4Cl to D2O was varied from .012 to .029. We find for the above concentration ranges that in the nematic range the relative temperature dependence of the D2O splitting is little affected by changes on salt concentration. The slopes of the proton line widths as a function of temperature decrease with increasing salt concentration. The results are compared with earlier data on salt effects on order obtained with the disodium cromoglycate system. 相似文献
15.
High pressure/temperature annealing experiments are used to determine diffusivities of H+ and D+ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m2/s)?=?4?±?1?×?10?12 exp(?54?±?2 kJ?mol?1/RT). At low temperatures, H+ and D+ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H+ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H+ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H+, can only be calculated from H+ mobility data if the extent of defect coupling is constrained. 相似文献
16.
Thomas Özgün Dr. Klaus Bergander Dr. Lei Liu Dr. Constantin G. Daniliuc Prof. Dr. Stefan Grimme Dr. Gerald Kehr Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):11958-11961
The energy profile of a frustrated Lewis pair (FLP) dihydrogen splitting system was determined by a combined experimental kinetic and DFT study. A trimethylene‐bridged phosphane–borane FLP was converted into its endothermic H2‐cleavage product by sequential H+/H? addition. The system could be handled at low temperature, and the kinetics of the H2 elimination were determined to give a rate constant of kHH,exp(299 K)=(2.87±0.1)×10?4 s?1 in solution. The primary kinetic isotope effects were determined; for example, (kHH/kDD)exp=3.19. The system was accurately analyzed by DFT calculations. 相似文献
17.
Emeline Appert Dr. Agnès Martin-Mingot Dr. Omar Karam Dr. Fabien Zunino Dr. Bastien Michelet Dr. Fodil Bouazza Prof. Sébastien Thibaudeau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201583
The field of medicinal chemistry is currently witnessing a deuterium rush owing to the remarkable properties of this element as bioisoster of hydrogen atom. Aromatic hydrogen isotope exchange (HIE) is one of the most studied strategies nowadays as it promises to access deuterium-modified drugs directly from their non-labeled parents. While most of the recent studies focus on metal-catalyzed C−H activation strategy, the use of superacidic conditions has been largely overlooked. This study shows that the use of TfOD as reaction medium allows the late-stage polydeuteration of a broad library of pharmaceuticals bearing a wide array of functional groups, complementing existing procedures. 相似文献
18.
19.
As Reduced Activation Ferritic/Martensitic (RAFM) steel is considered the primary candidate for use as a structural material in fusion power reactors,many countries are developing different kinds of RAFM.China is developing new CLAM (China Low Activation Martensitic) steel.The study investigates microstructural changes in CLAM steel implanted with deuterium ions induced by 1250 keV electron irradiation from R.T.to 873 K,and observes both the growth and shrinkage of the defect clusters produced by deuterium ... 相似文献
20.
P. Mărginean I. Mercea V. Mercea A. Olariu 《Isotopes in environmental and health studies》2013,49(4):157-160
Es wird ein Heiβ-Kalt-System mit einfachem Durchfluβ der Fluide untersucht. Dabei wird gezeigt, daβ zwischen den Isotopenkonzentrationen des Gases und der Flüssigkeit lineare Beziehungen bestehen. Eine Möglichkeit zur experimentellen Bestimmung der realen Werte der Parameter der Kolonne wird angegeben. 相似文献