共查询到20条相似文献,搜索用时 15 毫秒
1.
Chatani N Inoue H Kotsuma T Murai S 《Journal of the American Chemical Society》2002,124(35):10294-10295
The skeletal reorganization of enynes is achieved by the presence of GaCl3 as the catalyst. This reaction demonstrates the first example of the skeletal reorganization of enynes catalyzed by typical metal complexes. The process is simple and provides a diverse range of enynes in good to high yields. The reaction of enynes bearing a monosubstituent at the terminal olefinic carbon proceeds in a stereospecific manner with respect to the geometry of the olefin moiety. Enynes, bearing two substituents at the olefinic terminal carbon, undergo an efficient skeletal reorganization, these substrates having been known to be unsuitable substrates for the skeletal reorganization of enynes. 相似文献
2.
[reaction: see text] The skeletal reorganization of enynes is achieved by the presence of InCl(3) as the catalyst. The reaction of enynes having a terminal acetylenic moiety proceeds in a stereospecific manner to give 1-vinylcycloalkenes. The reaction of enynes containing an alkyl group on the acetylenic terminal carbon resulted in a new type of skeletal reorganization to give 1-allylcycloalkenes, formation of which involves a double cleavage of the C-C double bond and the triple bond. 相似文献
3.
The excited-state triple proton relay of 7-hydroxyquinoline (7HQ) along a hydrogen-bonded methanol chain in room temperature ionic liquids (RTILs) has been investigated using picosecond time-resolved fluorescence spectroscopy. The rate constant of the proton relay in a methanol-added RTIL is found to be slower by an order of magnitude than that in bulk methanol and to have unity in its kinetic isotope effect. These suggest that the excited-state tautomerization dynamics of 7HQ in methanol-added RTILs is mainly controlled by the solvent reorganization dynamics to form a cyclically hydrogen-bonded complex of 7HQ·(CH(3)OH)(2) upon absorption of a photon due to high viscosity values of RTILs. Because the cyclic complex of 7HQ·(CH(3)OH)(2) at the ground state is unstable in RTILs, the collision-induced slow formation of the cyclic complex should take place upon excitation prior to undergoing subsequent intrinsic proton transfer rapidly. 相似文献
4.
Ionic liquids (ILs) have attracted intensive attention in academia and industry due to their unique properties and potential applications. Nowadays, much interest is focused on finding out what is the main force that determines the properties of ionic liquids. Intuitively like NaCl, in high-temperature molten salt (HTMS) the electrostatic Coulomb force is regarded as the dominant factor that determines the behaviors of ILs. However, a large amount of evidence indicates that such a molten-salt-based simplified explanation is not consistent with the corresponding experimental results. Besides the Coulomb force, the hydrogen bond is another important noncovalent interaction in the IL and is closely related to some important properties and applications, as suggested in some new research results. Therefore in this review, we present results concerning the hydrogen bond in ILs, from the perspective of experiment and calculation, to shed light on its effects and roles. The deep insights into structure, in particular the hydrogen bonds, can provide us with a rational design for the new ILs to fulfill the demands in some complicated chemical processes. 相似文献
5.
Cooperativity in ionic liquids is investigated by means of static quantum chemical calculations. Larger clusters of the dimethylimidazolium cation paired with a chloride anion are calculated within density functional theory combined with gradient corrected functionals. Tests of the monomer unit show that density functional theory performs reasonably well. Linear chain and ring aggregates have been considered and geometries are found to be comparable with liquid phase structures. Cooperative effects occur when the total energy of the oligomer differs from a simple sum of monomer energies. Cooperative effects have been found in the structural motifs examined. A systematic study of linear chains of increasing length (up to nine monomer units) has shown that cooperativity plays a more important role than expected and is stronger than in water. The Cl...H distance of the chloride to the most acidic proton increases with an increasing number of monomer units. The average bond distance approaches 218.9 pm asymptotically. The dipole moment grows almost linearly and the dipole moment per monomer unit reaches the asymptotic value of 16.3 D. The charge on the chloride atoms decreases with an increasing chain length. In order to detect local hydrogen bonding in the clusters a new parametrization of the shared-electron number method is introduced. We find decreasing hydrogen bond energies with an increasing cluster size for both the first hydrogen bond to the most acidic proton and the average hydrogen bond. 相似文献
6.
Gayet F Marty JD Brûlet A Lauth-de Viguerie N 《Langmuir : the ACS journal of surfaces and colloids》2011,27(16):9706-9710
The formation of vesicles from 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) in several room-temperature ionic liquids, namely, 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF(4)), 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF(6)), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf(2)), and N-benzylpyridinium bis(trifluoromethylsulfonyl)imide (BnPyNTf(2)), as well as in a water/BmimBF(4) mixture, was investigated. In pure ionic liquids, observations by staining transmission electron microscopy demonstrated clearly the formation of spherical structures with diameters of 200-400 nm. The morphological characteristics of these vesicles in ionic liquids, in particular, the membrane thicknesses, were first investigated by small-angle neutron scattering measurements. The mean bilayer thickness was found to be ~63 ± 1 ? in a deuterated ionic liquid (BnPyNTf(2)-d). This value was similar to that observed in water. The effect of ILs on the modification of the phase physical properties of multilamellar vesicles (MLVs) was then investigated by differential scanning calorimetry. In pure IL as in water, DPPC exhibited an endothermic pretransition followed by the main transition. These transition temperatures and the associated enthalpies in ILs were higher than those in water because of a reduction of the electrostatic repulsion between zwitterionic head groups. To better understand the effect of ionic liquid on the formation of multilamellar vesicles, mixtures of BmimBF(4) and water, which are miscible in all proportions, were analyzed (BmimBF(4)/water ratio from 0% to 100%). SANS and DSC experiments demonstrated that the bilayer structure and stability were strongly modified by the IL content. Moreover, matching SANS experiments showed that BmimBF(4) molecules prefer to be located inside the DPPC membrane rather than in water. 相似文献
7.
Microwave-assisted separation has been applied to recover ionic liquid (IL) from its aqueous solution as an efficient method with respect to time and energy compared to the conventional vacuum distillation. Hydrophilic ILs such as 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF(4)]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([Bmim][TfO]) and 1-ethyl-3-methylimidazolium methylsulfate ([Emim][MS]) could be recovered in 6 min from the mixture of ILs and water (1:1, w/w) under microwave irradiation at constant power of 10 W while it took at least 240 min to obtain ILs containing same water content (less than 0.5 wt%) by conventional vacuum oven at 363.15 K with 90 kPa of vacuum pressure. Energy consumptions per gram of evaporated water from the homogeneous mixture of hydrophilic ILs and water (1:1, w/w) by microwave-assisted separation were at least 52 times more efficient than those in conventional vacuum oven. It demonstrated that microwave-assisted separation could be used for complete recovery of ILs in sense of time and energy as well as relevant purity. 相似文献
8.
Ionic liquids are salts that are liquid at or near room temperature. Their wide liquid range, good thermal stability, and very low vapor pressure make them attractive for numerous applications. The general approach to creating ionic liquids is to employ a large, unreactive, low symmetry cation with and an anion that largely controls the physical and chemical properties. The most common cations used in ionic liquids are N-alkylpyridinium and N,N′-dialkylimidazolium. Another very effective cation for the creation of ionic liquids is tetraalkylphosphonium, [PR1R2R3R4]+. The alkyl groups, Rn, generally are large and not all the same. The halide salts of several phosphonium cations are available as starting materials for metathesis reactions used to prepare ionic liquids. The large phosphonium cations can combine with relatively large anions to make viscous but free flowing liquids with formula mass greater than 1000 g mol−1. Some other more massive salts are waxes and glasses. The synthesis and the physical, chemical, and optical properties of phosphonium-ionic liquids having anions with a wide range of masses were measured and are reported here. 相似文献
9.
Siriwardana AI Crossley IR Torriero AA Burgar IM Dunlop NF Bond AM Deacon GB Macfarlane DR 《The Journal of organic chemistry》2008,73(12):4676-4679
The alkylation reaction of 2-mercapto-1-methylimidazole 1a with iodoethane and chlorobutane produced S-alkylmethimazole halides 2a and 2b which were subjected to anion metathesis with two different metal salts (MA) to afford methimazole-based room-temperature ionic liquids 3a, 3b, and 3c in 82%, 85%, and 87% yields, respectively. S-Alkylation giving 2a and 2b suggests that methimazole reacts through the thione tautomer. 相似文献
10.
The continuous dehydration of D-glucose into 5-hydroxymethylfurfural(HMF) was carried out under mild conditions,using SO3H-functionalized acidic ionic liquids as catalysts and H2O-4-methyl-2-pentanone(MIBK) biphasic system as solvent.High glucose conversion of 97.4% with HMF yield of 75.1%was obtained at 120 8C for 360 min,also,small amounts of levulinic acid(LA) and formic acid were generated.Generally,the dosage of catalyst and the initial content of glucose influenced the reaction significantly; the HMF selectivity decreased with the excessive elevation of temperature and prolonging of time; and water content in the system had a negative effect on the reaction.The ionic liquid catalyst could be recycled and exhibited constant activity for five successful runs.This paper provided a new strategy for HMF production from glucose. 相似文献
11.
12.
Hai Yan Wang Da Xiong Han The Key Laboratory of Global Change Marine-Atmopheric Chemistry Third Institute of Oceanography of State Oceanic Administration Xiamen China Department of Pharmacy Medical College of Xiamen University Xiamen China 《中国化学快报》2007,18(6):764-767
In this work, a new method of a series of ion liquids (ILs) 1-alkyl-3-methylimidazolium chloride [Cnmim]Cl (n = 2, 4, 6, 8) intercalation into layered zirconium phosphates was investigated. It was found that theα-ZrP-2BA (i.e. pre-intercalated BA was arranged in a bilayer mode in the galleries ofα-ZrP) was a suitable host for intercalation ILs: ILs was inserted through exchanging pre-intercalated BA. And the intercalation orientation was investigated by use of X-ray diffraction (XRD) experiments and molecular modeling calculation. 相似文献
13.
Endres F 《Physical chemistry chemical physics : PCCP》2012,14(15):5008-5009
14.
Armstrong JP Hurst C Jones RG Licence P Lovelock KR Satterley CJ Villar-Garcia IJ 《Physical chemistry chemical physics : PCCP》2007,9(8):982-990
Eight common imidazolium based ionic liquids have been successfully evaporated in ultra-high vacuum, their vapours analysed by line of sight mass spectrometry and their heats (enthalpy) of vapourisation determined. They were found to evaporate as ion pairs, with heats of vapourisation which depend primarily on the coulombic interactions within the liquid phase and the gas phase ion pair. An electrostatic model is presented relating the heats of vapourisation to the molar volumes of the ionic liquids. 相似文献
15.
Ionic liquids have recently gained popularity in the scientific community owing to their special properties and characteristics. One of the reasons why ionic liquids have been termed “green solvents” is due to their negligible vapour pressure. Their use in electrochemical, biological and metal extraction applications is discussed. Wide research has been carried out for their use in batteries, solar panels, fuel cells, drug deliveries and biomass pretreatments. This work aims to consolidate the various findings from previous works in these areas. DOI 10.1002/tcr.201100036 相似文献
16.
Reactivity of ionic liquids 总被引:2,自引:0,他引:2
Shahana Chowdhury Author Vitae Author Vitae Janet L. Scott Author Vitae 《Tetrahedron》2007,63(11):2363-2389
Ionic liquids are becoming widely used in synthetic organic chemistry and yet relatively little attention has been paid to the intrinsic reactivity of these low temperature molten salts. Clues to the non-innocent nature of many ionic liquids are contained in the reports of altered reactivity of dissolved substrates, unexpected catalytic activity and unforeseen by-product formation. In this review, we focus on the reactivity of ionic liquids, as opposed to reactivity in ionic liquids (although discussion of the latter is often included where it aids understanding of the former). 相似文献
17.
Electrowetting of ionic liquids 总被引:1,自引:0,他引:1
Millefiorini S Tkaczyk AH Sedev R Efthimiadis J Ralston J 《Journal of the American Chemical Society》2006,128(9):3098-3101
We have successfully demonstrated that imidazolium- and pyrrolidinium-based commercial room-temperature ionic liquids can electrowet (with a dc voltage) a smooth fluoropolymer (Teflon AF1600) surface. Qualitatively, the process is analogous to the electrowetting of aqueous electrolyte solutions: the contact angle versus voltage curve has a parabolic shape which saturates at larger voltages (positive or negative). On the other hand we observed several peculiarities: (i) the efficiency is significantly lower (by about an order of magnitude); (ii) the influence of the bulky cation is larger and the importance of the smaller anion is lesser, especially with respect to electrowetting saturation; (iii) there is an asymmetry in the saturation contact angles found for positive and negative voltages. The asymmetry may be correlated with the cation-anion asymmetry of the ionic liquids. The low efficiency may be caused by the presence of water and other impurities in these commercial materials. 相似文献
18.
A number of trifluoroacetates, mesylates, and triflates have been studied in ionic liquids. Several lines of evidence indicate that all of these substrates react via ionization to give carbocationic intermediates. For example, cumyl trifluoroacetates give mainly the elimination products, but the Hammett rho+ value of -3.74 is consistent with a carbocationic process. The analogous exo-2-phenyl-endo-3-deutero-endo-bicyclo[2.2.1]hept-2-yl trifluoroacetate gives an elimination where loss of the exo-hydrogen occurs from a cationic intermediate. 1-Adamantyl mesylate and 2-adamantyl triflate react to give simple substitution products derived from capture of 1- and 2-adamantyl carbocations by the residual water in the ionic liquid. The triflate derivative of pivaloin, trans-2-phenylcyclopropylcarbinyl mesylate, 2,2-dimethoxycyclobutyl triflate, the mesylate derivative of diethyl (phenylhydroxymethyl)-thiophosphonate, and Z-1-phenyl-5-trimethylsilyl-3-penten-1-yl trifluoroacetate all give products derived carbocation rearrangements (kDelta processes). anti-7-Norbornenyl mesylate gives products with complete retention of configuration, indicative of involvement of the delocalized 7-norbornenyl cation. 1,6-Methano[10]annulen-11-yl triflate reacts in [BMIM][NTf2] to give 1,6-methano[10]annulen-11-ol, along with naphthalene, an oxidized product derived from loss of trifluoromethanesulfinate ion. Analogous loss of CF3SO2- can be seen in reaction of PhCH(CF3)OTf. Ionic liquids are therefore viable solvents for formation of carbocationic intermediates via kC and kDelta processes. 相似文献
19.
Erik J. Stalcup Ralf Seemann Stephan Herminghaus Bruce M. Law 《Journal of colloid and interface science》2009,338(2):523-528
The spreading of ionic liquids on molecularly smooth solid surfaces has been little studied in the past. We show that the spreading behaviors of the two ionic liquids, [EMIM] ethyl sulfate and ECOENG™ 500, are well described by the combined molecular kinetic and hydrodynamic model of de Ruijter, de Coninck, and Oshanin [M.J. de Ruijter, J. de Coninck, G. Oshanin, Langmuir 15 (1999) 2209] with reasonable values for the molecular friction coefficient ζ, molecular displacement λ, and frequency K0 associated with contact line motion, as well as reasonable values for the microscopic cutoff a associated with hydrodynamic dissipation. 相似文献
20.
This tutorial review covers the use of ionic liquids as (co)solvents for the olefin metathesis reaction. Olefin metathesis is a simple and effective synthetic tool used to create many compounds which otherwise would require complex multistep syntheses. It is expected that the application of ionic liquids (IL) as well as the development of IL-enabled catalysts and separation techniques will create a green aspect to this important methodology. 相似文献