Synthesis of 4-trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyl with various anions for investigation of ionic liquids

A new synthetic way is described to prepare 4-trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyl bearing tetrafluoroborate, hexafluorophosphate or bis(trifluoromethylsulfonylimide) by an anion metathesis of 4-trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyl iodide using the corresponding silver salts. 4-Trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyl iodide is obtained by the methylation of 4-amino-2,2,6,6-tetramethylpiperidine-1-yloxyl with methyliodide. The new spin probe 4-trimethylammonio-2,2,6,6-tetramethylpiperidine-1-yloxyl bistrifluoromethylsulfonylimide and the spin probes containing tetrafluoroborate or hexafluorophosphate may be useful for an effective investigation of ionic liquids with similar anions.     

2,2,6,6-Tetramethylpiperidine-1-yloxyl bound to the imidazolium ion by an acetamido group for investigation of ionic liquids

New spin probes bearing the 2,2,6,6-tetramethylpiperidine-1-yloxyl covalently bound to the imidazolium ion via a methylene spacer and an amide group are synthesized. If the anion is bis(trifluoromethylsulfonylimide) instead of iodide, the new spin probe has a similar structure as that of an ionic liquid. Nevertheless, the new spin probes are useful tools to investigate ionic liquids.     

Synthesis of a new ionic spin probe for investigation of polar and non-polar solvents

A synthesis is described for the new ionic spin probe potassium-(18-crown-6)-4-sulfonatooxy-2,2,6,6-tetramethyl-piperidine-1-yloxyl. This new spin probe shows an improved solubility in both polar and non-polar solvents in comparison with the potassium-4-sulfonatooxy-2,2,6,6-tetramethylpiperidine-1-yloxyl. Furthermore, the solubility of potassium-(18-crown-6)-4-sulfonatooxy-2,2,6,6-tetramethyl-piperidine-1-yloxyl is also improved in ionic liquids relative to the potassium salt comprising no crown ether moiety. The spin probe potassium-(18-crown-6)-4-sulfonatooxy-2,2,6,6-tetramethyl-piperidine-1-yloxyl is highly suitable for investigation of both less polar and highly polar environments.     

Synthesis and structure of redox derivatives of 4-(2-Amino-2-oxoethyl)-2,2,6,6-tetramethylpiperidine-1-yloxyl

According to X-ray diffraction (XRD) analysis and ¹H NMR spectra 2-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl)acetamide, 4-(2-amino-2-oxoethyl)-2,2,6,6-tetramethylpiperidin-1-yloxyl, and 4-(2-amino-2-oxoethyl)-2,2,6,6-tetramethyl-1-oxopiperidinium perchlorate in the crystalline state and in solution possess the chair conformation, equatorial orientation of CH₂C(O)NH₂ group, and differ by the geometry of the N¹ atom of the heterocycle. At growing oxidation state of the piperidine nitrogen atom the pyramidal location of substituents at N¹ in the hydroxyl derivative changes to weakly pyramidal in the piperidinoxyl and turned into planar in the oxoammonium cation. Simultaneously the N¹-O¹ bond shortens transforming from an ordinary (1.451 Å) through a sesquialteral (1.289 Å) into a double (1.189 Å) bond. The insignificant changes in the structure of compounds in the transition piperidinoxyl-oxopiperidinium cation correspond to the low energy of the transition process and result in the ease of the redox-reactions involving this pair.     

Synthesis and preliminary use of novel acrylic ester-derived task-specific ionic liquids

Novel electrophilic alkenes bearing an ionic liquid-type appendage have been prepared and used in Diels-Alder cycloadditions, 1,4-additions, Heck couplings and Stetter reactions; this new type of support allows easy monitoring of the reactions by NMR and MS as well as simple and efficient work-up and isolation procedures.     

Palladium-catalyzed hydroesterification of styrene derivatives in the presence of ionic liquids

The palladium-catalyzed hydroesterification of olefins occurs efficiently in a range of ionic liquid media. Selectivities ranging from 5-7:1 for the linear ester were obtained with styrene in a range of IL solvents. The use of ILs allowed the catalyst to be easily separated from the organic product by either extraction or distillation. The (Ph₃P)₂PdCl₂ precatalyst could be recovered unchanged from the ionic liquid phase. The IL/catalyst phase could be recycled five times with an average yield of 68%.     

ESR spin probes in ionic liquids.

The spin probes 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), and 2,2,6,6-tetramethyl-4-trimethylammoniumpiperidine-1-oxylIodide (CAT-1) are examined in a number of ionic liquids based on substituted imidazolium cations and tetrafluoroborate and hexafluorophosphate anions, respectively. The reorientation correlation times tau(R) of the spin probes in these systems have been determined by complete spectra simulation and, for rapid reortientation, by analysis of the intensities of the hyperfine lines of the electron spin resonance (ESR) spectra. A comparison of the results with those from the model system glycerol/water and selected organic solvents is made. Additions of diamagnetic and paramagnetic ions allow the conclusion that salt effects and spin exchange are present, and that both are superimposed by motional effects. Specific interactions in the ionic liquids, as well as between the spin-probe molecules and the constituents of the ionic liquids are reflected in the spectra of the spin probes, depending on their molecular structure.     

Design and synthesis of fused-ring chiral ionic liquids from amino acid derivatives

Six novel imidazolium salts, which contain a chiral moiety as well as a fused-ring system, have been designed, synthesized, and fully characterized. The synthesis of these ionic liquids is concise and practical due to the commercial availability of the starting materials. These imidazolium compounds were readily prepared from 1-methyl-2-imidazoliumcarboxaldehyde and chiral amino alcohols. Salts that contain the PF₆ anion were solids, but salts with the NTf₂ anion were liquids at room temperature. We envision that these new chiral imidazolium compounds can serve as effective reaction media as well as chiral catalysts for asymmetric reactions, which are presently being investigated in our lab.     

Confined rapid thermolysis/FTIR/ToF studies of imidazolium-based ionic liquids

Rapid scan FTIR spectroscopy and time-of-flight (ToF) mass spectrometry were utilized to study thermal decomposition of three imidazolium-based ionic liquids, with 1-ethyl-3-methyl-imidazolium (emim) as the cation, and NO₃⁻, Cl⁻, and Br⁻ as the anions. The thermal decomposition involved heating rates of 2000 K/s and temperatures to 435 °C in an ambient inert gas at 1 atm. Using sub-milligram quantities of each compound, examinations of the evolution of gas-phase species revealed that the most probable sites for proton transfer and subsequent secondary reactions were primarily the methyl group and secondarily the ethyl group. The ring appeared to remain intact, as there was no evidence of the formation of HCN, imines or related products. The most reactive compound is [emim]NO₃, since the nitrate group served as a strong oxidizer and reacted strongly with the methyl/ethyl groups at the elevated temperatures to produce common final products from combustion.     

Microwave-promoted synthesis of polyhydroxydeoxybenzoins in ionic liquids

A microwave-promoted synthesis of polyhydroxydeoxybenzoins and -phenylpropanones has been developed, using bis{(trifluoromethyl)sulfonyl}amine (HNTf₂) or BF₃·OEt₂ in an ionic liquid solvent.     

Dissolution and regeneration of polybenzimidazoles using ionic liquids

We report here the initial results that polybenzimidazole can be dissolved in and regenerated from, 1-butyl-3-methylimidazolium chloride and other hydrophilic ionic liquids, which may enable the application of ionic liquids as alternatives to environmentally undesirable solvents currently used for dissolution of this polymer.     

Review of ionic liquids with fluorine-containing anions

Interest in ionic liquids has grown markedly in recent years. The syntheses, characterization and properties of quaternary alkyl-substituted ammonium, imidazolium, triazolium and pyridinium salts with a variety of fluorine-containing anions have been studied in detail; however, ionic liquids with other cations and anions continue to be discovered. This review is limited to the literature from 2000 to 2005 dealing with ionic liquids with fluorine-containing anions.     

Synthesis and properties of 3,5-dibromo-4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl radical

Bromination of 1-hydroxy-4-oxo-2,2,6,6-tetramethylpiperidine gives 3,5-dibromo-1-hydroxy-4-oxo-2,2,6,6-tetramethylpiperidine hydrobromide. Oxidation of the latter generates 3,5-dibromo-4-oxo-2,2,6,6-tetramethylpiperdine-1-oxyl radical, which represents a convenient acylating spin trap.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 73–74, January, 1992.     

Synthesis, characterization, and catalytic activity of ionic liquids based on biosources

New room-temperature ionic liquids were synthesized from natural and easily available feedstocks (choline hydroxide and amino acids) following an economical and green route in which the only by-product was water. They were successfully applied as catalysts for the Knoevenagel test reaction between benzaldehyde and different active methylene compounds, at room temperature and under solvent-free conditions, to produce α,β-unsaturated carbonyl compounds, exhibiting good conversions and high selectivities. The catalytic role of cholinium and aminoacetate ions in the Knoevenagel condensation is discussed.     

Alanine-supported protic ionic liquids as efficient catalysts for aldol condensation reactions

A series of novel protic ionic liquids were immobilized on alanine, a cheap readily available amino acid. These short aliphatic chain ionic liquids have a low cost of preparation, a low toxicity, and need simple synthesis/purification processes. Their catalytic activity was tested for citral–acetone and benzaldehyde–acetone condensations, two reactions with an interest for pharmacological as well as flavor and fragrance industry. Good results were obtained in terms of conversion and selectivity; moreover, the catalysts can be recycled and reused for several consecutive cycles without significant loss of activity.     

A novel ionic liquids grafted polysiloxane for capillary gas chromatography

A new ionic liquids grafted polysiloxane used as stationary phase for capillary gas chromatography(CGC) is described.The stationary phase of 1-vinyl-3-hexylimidazolium hexafluorophosphate anchored to polysiloxane(PMHS-[VHIm][PF_6]) was synthesized, characterized and coated onto capillary columns by static coating.The results show that the present stationary phase exhibits a very good chromatographic resolution and selectivity for Grob test mixture and alcohols with baseline resolution and symmetry peaks....     

Novel Lewis-base ionic liquids replacing typical anions

We have synthesized two kinds of new Lewis-base ionic liquids (ILs); one is based on the relatively strong Lewis basic acetate anion, and the other is a salt composed of a mono-alkylated diamine such that the Lewis base site is incorporated in the cation. 1-Octyl-4-aza-1-azonia-bicyclo[2.2.2]octane bis(trifluoromethanesulfonyl)amide, [C₈dabco]TFSA, and N-butyl-N-methylpyrrolidinium acetate, [p_1,4]OAc, melted into fluid liquids at 26 and 81 °C, respectively. The thermal decomposition of [p_1,4]OAc started at around 150 °C, whereas the thermal stability of [C₈dabco]TFSA was almost equal to that of typical TFSA-based ILs in spite of the Lewis base site. This suggests that if the Lewis base site is incorporated into the cation the IL can maintain higher thermal stability. In addition, as a further result of the presence of the basic nitrogen, [C₈dabco]TFSA can dissolve hydrated Cu(NO₃)₂ whereas the other TFSA-based ILs cannot.     

New chiral imidazolium ionic liquids: 3D-network of hydrogen bonding

New hydrophobic chiral ionic liquids bearing an imidazolium core have been stereospecifically prepared from the chiral pool; their enantiomeric purity and 3D-network of hydrogen bonding were analysed by NMR and X-ray diffraction, respectively.     

Alkylation of ambident indole anion in ionic liquids

Alkylation of indole salts in different ionic liquids is reported. Ionic liquids increase the alkylation reaction rate of ambident indole anion and reduce the effects of counter ions and/or additives, the alkylation reaction rates being independent of the presence of small amounts of protic solvents or water.