Ionic Liquids in Synthesis

Laali, Kenneth K.

doi:10.1055/s-2003-40869

Cited by 27 publications

(11 citation statements)

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“…[1][2][3][4][5][6][7][8][9] The main difference with respect to conventional organic solvents is their almost nonexistent vapor pressure as a result of the strong interactions between anions and cations. [1][2][3][4][5][6][7][8][9] The main difference with respect to conventional organic solvents is their almost nonexistent vapor pressure as a result of the strong interactions between anions and cations.…”

mentioning

confidence: 99%

“…Ionic liquids (ILs) are subject of high interest owing to their potential applications, for example, as electrolytes, in catalysis, and as green solvents, and experience a revival that began more than two decades ago. [1][2][3][4][5][6][7][8][9] The main difference with respect to conventional organic solvents is their almost nonexistent vapor pressure as a result of the strong interactions between anions and cations. The characterization of ILs and understanding the consequences of the strong interactions on the structural properties is a challenge, both experimentally [10] and theoretically.…”

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confidence: 99%

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Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

et al. 2016

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Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1-ethyl-3-methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered.

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confidence: 99%

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confidence: 99%

Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

et al. 2016

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“…And in TS2 an imaginary frequency (−505.79 cm −1 ) of a symmetric stretching vibration between C21 and F28 indicates formation of C21-F28 and breakage of C21-N4. (5) NBO theories indicate that the interaction between a LP orbital on N7 with the sigma antibond orbital of σ*(C8-N14), E (2) value (53.29 kJ mol −1 ), is much larger than that of other modes. (6) For IM, AIM explains ∇ 2 ρ(r)s of N7-C8 and N4-C21 bond are −0.5493 and −0.5612 a.u., respectively, which are defined as the covalent bond, while in TS1, ∇ 2 ρ(r) of N7-C8 has been changed to 0.1085 a.u., and the N7-C8 bond can be confirmed to have a covalent bond component, but the bond has begun to break.…”

Section: Aim Analysesmentioning

confidence: 99%

“…ILs can be made task-specific for a certain applications [1], including use as solvents in chemical synthesis and catalysis [2][3][4][5][6][7][8] and separation technology [9,10], as electrolytes in electrochemical devices [11][12][13], and as lubricants or as heat-transfer fluids [14]. In addition, the huge range of possible combinations between cation and anion adds to the design flexability of ILs [15].…”

Section: Introductionmentioning

confidence: 99%

Thermal reaction of the ionic liquid 1,2-dimethyl-(3-aminoethyl) imidazolium tetrafluoroborate: a kinetic and theoretical study

Zhou

Cao²,

Liu³

et al. 2016

J Mol Model

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Since the thermal stabilities of ionic liquids (ILs) are of significance for their application, an amine-functionalized IL 1,2-dimethyl-(3-aminoethyl) imidazolium tetrafluoroborate [aEMMIM][BF4] was chosen to study thermal decomposition mechanisms via the methods of FT-IR, (1)H NMR, TGA, TGA-MS and density functional theory (DFT) calculations. Theoretical and experimental results indicated that amine-functionalization reduces the thermal stability of [aEMMIM][BF4] compared to its non-functionalized counterpart. Moreover, we found that [aEMMIM][BF4] follows a unimolecular nucleophilic substitution (SN1) decomposition (98.8 %), whereas the bimolecular nucleophilic substitution (SN2) decomposition (1.2 %) is unfavorable. The SN1 and SN2 reactions were fully optimized at B3LYP/6-311++G(d,p) level, and the energies of reactant (R), intermediates (IM), transition state (TS) and product (P) were obtained and analyzed by reaction mechanism. The energy of the intermediate is higher than that of the reactants by 18.92 kJ mol(-1), and the energy of the TS is higher than that of the IM by 155.23 kJ mol(-1). This result indicates that the IM are also more stable than the P2 product, thus the reaction is endothermic. The chemical nature of the covalent and hydrogen bonds was analyzed by vibrational modes analysis (VMA), nature bond orbital (NBO) and the theory of atoms in molecules (AIM). Graphical Abstract Proposed thermal decomposition of [aEMMIM][BF4] via unimolecular ( SN1) and bimolecular( SN2) nucleophilic substitution mechanisms. The electrostatic potential surface (ESP) of the transition state illustrates that hydrogen bonds are generated when [BF4](-) is close to [aEMMIM](+), and SN1 decomposition is much favorable than SN2 decomposition.

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“…Many of them are nonflammable or non-volatile, it is considered to be the most promising functional material in green chemistry and clean technology, which is widely used in various fields [1][2][3]. As a common chemical material, poly (ethylene glycol) (PEG) also has good stability (thermal, chemical), no or null vapour pressure, high thermal and ionic conductivity, etc.…”

Section: Introductionmentioning

confidence: 99%

Determination of three physical properties of quinoline ionic liquids with hexafluorophosphate

Tang

Wang

Yao

et al. 2016

MATEC Web of Conferences

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6 ] 2 ) were determined. In addition, the solubilities of six ILs in six lower alcohols, water, acetonitrile and diethyl ether were measured at 288.15 K; and the hydroscopicity of above five ILs were measured at the temperature of 298.15 K and relative humidity of 79% for 24 h. Densities of five ionic liquids were determined between 283.15 and 333.15 K. Then the densities of five binary system (ILs/acetonitrile) were explored between 283.15 and 333.15 K, the type of the ionic liquid, the concentration of five ILs in CH 3 CN, and the effect of temperature on the binary systems, were correlated with the measured data.

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Ionic Liquids in Synthesis

Cited by 27 publications

References 0 publications

Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

Thermal reaction of the ionic liquid 1,2-dimethyl-(3-aminoethyl) imidazolium tetrafluoroborate: a kinetic and theoretical study

Determination of three physical properties of quinoline ionic liquids with hexafluorophosphate

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