- A comparison of the oxidation of lignin model compounds in conventional and ionic liquid solvents and application to the oxidation of lignin
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The oxidation of lignin model compounds was studied in conventional solvents in parallel with oxidations in ionic liquid solvents. Catalyst systems were investigated in ionic liquid solvents to determine how reaction rates and the selectivity for benzylic carbon oxidation were affected. Oxidation rates were often lower in ionic liquids than in conventional solvents-as indicated by lower conversion in a standard reaction time-likely due, at least in part, to the higher viscosity of ionic liquids. Selectivity of the TPPFeCl/t-BuOOH catalyst system for oxidation of the benzylic C-OH versus benzylic C-H was higher in the ionic liquids tested than in conventional solvents.
- Yao, Soledad G.,Meier, Mark S.,Pace, Robert B.,Crocker, Mark
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p. 104742 - 104753
(2016)
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Read Online
- Microwave synthesis of microstructured and nanostructured metal chalcogenides from elemental precursors in phosphonium ionic liquids
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We describe a general approach for the synthesis of micro-/nanostructured metal chalcogenides from elemental precursors. The excellent solubility of sulfur, selenium, and tellurium in phosphonium ionic liquids promotes fast reactions between chalcogens an
- Ding, Kunlun,Lu, Hong,Zhang, Yichi,Snedaker, Matthew L.,Liu, Deyu,Maci-Agull, Juan Antonio,Stucky, Galen D.
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- Comparative study of inclusion complexation of tetraalkylphosphonium and ammonium salts with cucurbit[7]uril
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Inclusion complexation of tetraalkylphosphonium salts (PSs) with cucurbit[7]uril (CB[7]) was studied spectrophotometrically using methylene blue as a chemical indicator. Differences in the inclusion behaviour caused by the central ions in PSs and tetraalkylammonium salts (ASs) are described herein. The inclusion complexation constant (K) of PS3 with a C3-alkyl chain is remarkably smaller than those of the other PSs, indicating that PS3 is most suitable for clathrate-hydrate formation in bulk solution. In the AS inclusions, AS4 with a C4-alkyl chain showed the small K value. Furthermore, the K values of PSs with CB[7] were measured under high pressure. The K values of CB[7] increased with increasing external pressure and decreasing solvent polarity. From the high-pressure results, the volume change (ΔVrepel) caused by water molecules released from the CB[7] cavity was evaluated. A volumetric study for the inclusion of PSs with CB[7] indicated that in PS6 and PS8 with long C6 and C8 chains, respectively, one alkyl chain was encapsulated in the CB[7] cavity. In the other PSs with short chains, two alkyl chains could be accommodated in the cavity. Based on the effects of temperature, substituents, and external pressure, differences in the inclusion mechanisms of PSs and ASs for CB[7] are discussed.
- Hagiwara, Seiya,Hanaya, Tadashi,Matsumoto, Yuki,Sueishi, Yoshimi
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- METHOD OF PRODUCING VINYL CHLORIDE
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A method of producing vinyl chloride is provided in the present invention. The method includes the following steps. First, 1,2-dichloroethane (EDC) is introduced into a reactor, and a residence time of the EDC in an ionic liquid catalyst is 5 seconds to 100 seconds, so as to perform a catalytic cleavage reaction. The ionic liquid catalyst is in a liquid phase. The ionic liquid catalyst includes tributylalkyl phosphonium halide, and the alkyl includes an alkyl group having 3 to 16 carbon atoms.
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Paragraph 0030
(2020/01/27)
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- Effects of charge balance and hydrophobicity of the surface of cytochrome: C on the distribution behaviour in an ionic liquid/buffer biphasic system
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Factors contributing to the different distribution behaviour of cytochrome c were investigated in a biphasic tetrabutylphosphonium 2,4,6-trimethylbenzenesulfonate and potassium phosphate buffer system, which shows a lower critical solution temperature. To change charge balance and hydrophobicity of cytochrome c, surface modification with a few modifier molecules was applied. Surface charge and hydrophobicity affected the distribution behavior of chemically modified cytochrome c in the tetrabutylphosphonium 2,4,6-trimethylbenzenesulfonate and potassium phosphate buffer biphasic system. The distribution ratio into tetrabutylphosphonium 2,4,6-trimethylbenzenesulfonate decreased with decreasing isoelectric point of cytochrome c. Furthermore, cytochrome c possessing a low isoelectric point showed different distribution ratio depending on surface hydrophobicity. Taken together, these findings indicate that isoelectric point and surface hydrophobicity of cytochrome c are important factors controlling the distribution behavior in temperature sensitive biphasic systems.
- Ikeda, Kazuma,Fujita, Kyoko,Ohno, Hiroyuki,Nakamura, Nobuhumi
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p. 7337 - 7341
(2019/08/15)
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- Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
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The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4?n (n=1–3) generates a disilane residue (MenSi2Cl6?n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.
- Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
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supporting information
p. 3809 - 3815
(2019/02/13)
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- Long sought synthesis of quaternary phosphonium salts from phosphine oxides: Inverse reactivity approach
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Quaternary phosphonium salts (QPS), a key class of organophosphorus compounds, have previously only been available by routes involving nucleophilic phosphorus. We report the realisation of the opposite approach to QPS utilising phosphine oxides as the electrophilic partner and Grignard reagents as nucleophiles. The process is enabled through the crucial intermediacy of the derived halophosphonium salts. The route does not suffer from the slow kinetics and limited availability of many parent phosphines and a broad range of QPS were prepared in excellent yields.
- Vetter, Anna C.,Nikitin, Kirill,Gilheany, Declan G.
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p. 5843 - 5846
(2018/06/13)
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- Promoted Ruthenium Catalyzed Conversion of Syngas to Alcohols
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This invention concerns a promoted catalyst system for making one or more alkanols from synthesis gas. The catalyst system contains a ruthenium compound and a halogen promoter dispersed in a low-melting tetraorganophosphonium salt. The halogen promoter is a compound capable of generating HX (where X═Cl, Br, or I) under reaction conditions. The invention also concerns a process for selectively preparing one or more alkanols from synthesis gas using the promoted catalyst system.
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Paragraph 0051
(2013/09/12)
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- Introduction of hydrophilic groups onto the ortho-position of benzoate anions induced phase separation of the corresponding ionic liquids with water
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Ionic liquids (ILs) composed of tetrabutylphosphonium cations and benzoate anion derivatives with hydrophilic hydroxyl or carboxyl groups introduced onto the ortho-position were found to be less hydrophilic and showed phase separation with water, whereas unmodified benzoate-type IL was freely miscible with water.
- Ando, Takashi,Kohno, Yuki,Nakamura, Nobuhumi,Ohno, Hiroyuki
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supporting information
p. 10248 - 10250
(2013/10/22)
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- Key factors to prepare polyelectrolytes showing temperature-sensitive lower critical solution temperature-type phase transitions in water
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Tetrabutylphosphonium styrenesulfonate and its homopolymer showed a lower critical solution temperature-type phase transition in water. As the hydrophobicity of these monomeric and polymeric salts affects phase behaviour, the phase transition temperature of the polyelectrolyte was changed by the introduction of monomers having different alkyl chain length on the phosphonium cations. Journal compilation CSIRO 2011.
- Kohno, Yuki,Ohno, Hiroyuki
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experimental part
p. 91 - 94
(2012/07/27)
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