Radical 1,4-aryl transfer in arylcarboxamides leading to phthalimides, biaryls and enantiomerically enriched beta-arylethylamines

5-exo Cyclisation of vinyl-, aryl- and alkyl-radicals onto the aryl group of arylcarboxamides is followed by beta-scission of the resulting spirocyclohexadienyl radicals with ejection of a carbamoyl radical. The fate of this radical depends on the substrate but, in the cases studied, either 5-endo cyclisation or direct reduction follows to give phthalimides, biaryls or beta-arylethylamines.

Ligand differentiated complementary Rh-catalyst systems for the enantioselective desymmetrization of meso-cyclic anhydrides

Two distinct systems for the rhodium-catalyzed enantioselective desymmetrization of meso-cyclic anhydrides have been developed. Each system has been optimized and are compatible with the use of in situ prepared organozinc reagents. Rhodium/PHOX species efficiently catalyze the addition of alkyl nucleophiles to glutaric anhydrides, while a rhodium/phosphoramidite system is effective in the enantioselective arylation of succinic and glutaric anhydrides.

Pyrrolidinium Ionic Liquid Crystals

N-Alkyl-N-methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium-containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)-imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2-thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl] counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group CnH2n+1 was varied from eight to twenty carbon atoms (n =8. 10-20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal. columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the Molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X-ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self-assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium-containing mesogens, luminescence can be induced by dissolving them in an ionic: liquid matrix. The europium-containing compound shows intense red photoluminescence with high colour Purity.

Thermotropic Ruthenium(II)-Containing Metallomesogens Based on Substituted 1,10-Phenanthroline Ligands

Imidazo[4,5-f]-1,10-phenanthroline and pyrazino[2,3-f]-1,10-phenanthroline substituted with long alkyl chains are versatile ligands for the design of metallomesogens because of the ease of ligand substitution. Whereas the ligands and the corresponding rhenium(I) complexes were not liquid-crystalline, mesomorphism was observed for the corresponding ionic ruthenium(II) complexes with chloride, hexafluorophosphate, and bistriflimide counterions. The mesophases were identified as smectic A phases by high-temperature small-angle X-ray scattering (SAXS) using synchrotron radiation. The transition temperatures depend on the anion, the highest temperatures being observed for the chloride salts and the lowest for the bistriflimide salts. The ruthenium(II) complexes are examples of luminescent ionic liquid crystals.

Coordination environment of [UO2Br4](2-) in ionic liquids and crystal structure of [Bmim](2)[UO2Br4]

The complex formed by the reaction of the uranyl ion, UO22+, with bromide ions in the ionic liquids 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmiml[Tf2N]) and methyl-tributylammonium bis(trifluoromethylsulfonyl)imide ([MeBu3N][Tf2N]) has been investigated by UV-Vis and U L-III-edge EXAFS spectroscopy and compared to the crystal structure of [Bmim](2)[UO2Br4]. The solid state reveals a classical tetragonal bipyramid geometry for [UO2Br4](2-) with hydrogen bonds between the Bmim(+) and the coordinated bromides. The UV-Vis spectroscopy reveals the quantitative formation of [UO2Br4](2-) when a stoichiometric amount of bromide ions is added to UO2(CF3SO3)(2) in both Tf2N-based ionic liquids. The absorption spectrum also suggests a D-4h symmetry for [UO2Br4](2-) in ionic liquids, as previously observed for the [UO2Cl4](2-) congener. EXAFS analysis supports this conclusion and demonstrates that the [UO2Br4](2-) coordination polyhedron is maintained in the ionic liquids without any coordinating solvent or water molecules. The mean U-O and U-Br distances in the solutions, determined by EXAFS, are, respectively, 1.766(2) and 2.821(2)angstrom in [Bmim][Tf2N], and, respectively, 1.768(2) and 2.827(2) angstrom, in [MeBu3N][Tf2N]. Similar results are obtained in both ionic liquids indicating no significant influence of the ionic liquid cation either on the complexation reaction or on the structure of the uranyl species. (C) 2009 Elsevier Ltd. All rights reserved.

Pyrrolidinium Ionic Liquid Crystals with Pendant Mesogenic Groups

New ionic liquid crystals (including ionic metallomesogens) based oil the pyrrolidinium core are presented. N-Methylpyrrolidine was quaternized with different mesogenic groups connected to a flexible, omega-bromosubstituted alkyl spacer. The length of the flexible alkyl spacer between the cationic head group and the rigid mesogenic group was varied. The substituted pyrrolidinium cations were combined with bromide, bis(trifluoromethylsulfonyl)imide, tetrakis (2-thenoyltrifluoroacetonato)europate(III), and tetrabromouranyl anions. The influence of the type of mesogenic unit, the lengths of the flexible spacer and terminal alkyl chain, the size of the mesogenic group, and the type of anion oil the thermotropic mesomorphic behavior was investigated. Furthermore, the phase behavior was thoroughly compared with the previously reported mesomorphism of N-alkyl-N-methylpyrrolidinium salts. Low-ordered smectic A phases of the de Vries type, smectic C phases, higher-ordered smectic F/I phases, as well its crystal smectic phases (E and G, J, H, or K) were observed and investigated by polarizing optical microscopy, differential scanning calorimetry, and powder X-ray diffraction.

Phase transition and decomposition temperatures, heat capacities and viscosities of pyridinium ionic liquids

Ionic liquids are organic salts with low melting points. Many of these compounds are liquid at room temperature in their pure state. Since they have negligible vapor pressure and would not contribute to air pollution, they are being intensively investigated for a variety of applications, including as solvents for reactions and separations, as non-volatile electrolytes, and as heat transfer fluids. We present melting temperatures, glass transition temperatures, decomposition temperatures, heat capacities, and viscosities for a large series of pyridinium-based ionic liquids. For comparison, we include data for several imidazolium and quaternary ammonium salts. Many of the compounds do not crystallize, but form glasses at temperatures between 188 K and 223 K. The thermal stability is largely determined by the coordinating ability of the anion, with ionic liquids made with the least coordinating anions, like bis(trifluoromethylsulfonyl)imide, having the best thermal stability. In particular, dimethylaminopyridinium bis(trifluoromethylsulfonyl)imide salts have some of the best thermal stabilities of any ionic liquid compounds investigated to date. Heat capacities increase approximately linearly with increasing molar mass, which corresponds with increasing numbers of translational, vibrational, and rotational modes. Viscosities generally increase with increasing number and length of alkyl substituents on the cation, with the pyridinium salts typically being slightly more viscous than the equivalent imidazolium compounds. (c) 2005 Elsevier Ltd. All rights reserved.

Strategies toward the design of energetic ionic liquids: nitro- and nitrile-substituted N,N '-dialkylimidazolium salts

Twelve novel 1,3-dialkylimidazolium salts containing strongly electron-withdrawing nitro-and cyano-functionalities directly appended to the cationic heterocyclic rings have been synthesized; the influences of the substituents on both formation and thermal properties of the resultant ionic liquids have been determined by DSC, TGA, and single crystal X-ray diffraction, showing that an electron-withdrawing nitro-substituent can be successfully appended and has a similar influence on the melting behaviour as that of corresponding methyl group substitution. Synthesis of di-, or trinitro-substituted 1,3-dialkylimidazolium cations was unsuccessful due to the resistance of dinitro-substituted imidazoles to undergo either N-alkylation or protonation, while 1-alkyl- 4,5-dicyanoimidazoles were successfully alkylated to obtain 1,3-dialkyl-4,5-dicyanoimidazolium salts. Five crystal structures ( one of each cation type) show that, in the solid state, the NO2-group has little significant effect, beyond the steric contribution, on the crystal packing.

Prediction of the formation and stabilities of energetic salts and ionic liquids based on ab initio electronic structure calculations

A computational approach to predict the thermodynamics for forming a variety of imidazolium-based salts and ionic liquids from typical starting materials is described. The gas-phase proton and methyl cation acidities of several protonating and methylating agents, as well as the proton and methyl cation affinities of many important methyl-, nitro-, and cyano- substituted imidazoles, have been calculated reliably by using the computationally feasible DFT (B3LYP) and MP2 (extrapolated to the complete basis set limit) methods. These accurately calculated proton and methyl cation affinities of neutrals and anions are used in conjunction with an empirical approach based on molecular volumes to estimate the lattice enthalpies and entropies of ionic liquids, organic solids, and organic liquids. These quantities were used to construct a thermodynamic cycle for salt formation to reliably predict the ability to synthesize a variety of salts including ones with potentially high energetic densities. An adjustment of the gas phase thermodynamic cycle to account for solid- and liquid-phase chemistries provides the best overall assessment of salt formation and stability. This has been applied to imidazoles (the cation to be formed) with alkyl, nitro, and cyano substituents. The proton and methyl cation donors studied were as follows: HCl, HBr, HI, (HO)(2)SO2, HSO3CF3 (TfOH), and HSO3(C6H4)CH3 (TsOH); CH3Cl, CH3Br, CH3I, (CH3O)(2)SO2, CH3SO3CF3 (TfOCH3) and CH3SO3(C6H4)CH3 (TsOCH3). As substitution of the cation with electron-withdrawing groups increases, the triflate reagents appear to be the best overall choice as protonating and methylating agents. Even stronger alkylating agents should be considered to enhance the chances of synthetic success. When using the enthalpies of reaction for the gas-phase reactants (eq 6) to form a salt, a cutoff value of - 13 kcal mol(-1) or lower (more negative) should be used as the minimum value for predicting whether a salt can be synthesized.

On the solubilization of water with ethanol in hydrophobic hexafluorophosphate ionic liquids

The solubility of water in the hydrophobic 1-alkyl-3-methylimidazolium hexafluorophosphate (alkyl = butyl, hexyl, and octyl) ionic liquids, can be significantly increased in the presence of ethanol as a co-solute. 1-Hexyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium hexafluorophosphate are completely miscible with ethanol, and immiscible with water, whereas 1-butyl-3-methylimidazolium hexafluorophosphate is totally miscible with aqueous ethanol only between 0.5-0.9 mole fraction ethanol at 25degreesC. At higher and lower mole fraction of ethanol, the aqueous and IL components are only partially miscible and a biphasic system is obtained upon mixing equal volumes of the IL and aqueous ethanol. The observation of a large range of total miscibility between water and the IL in the three-component system has important implications for purifications and separations from IL.

Efficient, halide free synthesis of new, low cost ionic liquids: 1,3-dialkylimidazolium salts containing methyl- and ethyl-sulfate anions

New low-cost ionic liquids containing methyl- and ethyl-sulfate anions can be easily and efficiently prepared under ambient conditions by the reaction of 1-alkylimidazoles with dimethyl sulfate and diethyl sulfate. The preparation and characterization of a series of 1,3-dialkylimidazolium alkyl sulfate and 1,2,3-trialkylimidazolium alkyl sulfate salts are reported. 1,3-Dialkylimidazolium salts containing at least one non-methyl N-alkyl substituent are liquids at, or below room, temperature. Three salts were crystalline at room temperature, the single crystal X-ray structure of 1,3-dimethylimidazolium methyl sulfate was determined and shows the formation of discrete ribbons comprising of two anion-cation hydrogen-bonded chains linked via intra-chain hydrogen-bonding, but little, or no inter-ribbon hydrogen-bonding. The salts are stable, water soluble, inherently 'chloride-free', display an electrochemical window of greater than 4 V, and can be used as alternatives to the corresponding halide salts in metathesis reactions to prepare other ionic liquids including 1-butyl-3-methylimidazolium hexafluorophosphate.

Increased cerebral output of free radicals during hypoxia: implications for acute mountain sickness?

Bailey DM, Taudorf S, Berg RMG, Lundby C, McEneny J, Young IS, Evans KA, James PE, Shore A, Hullin DA, McCord JM, Pedersen BK, Moller K. Increased cerebral output of free radicals during hypoxia: implications for acute mountain sickness? Am J Physiol Regul Integr Comp Physiol 297: R1283-R1292, 2009. First published September 2, 2009; doi: 10.1152/ajpregu.00366.2009.-This study examined whether hypoxia causes free radical-mediated disruption of the blood-brain barrier (BBB) and impaired cerebral oxidative metabolism and whether this has any bearing on neurological symptoms ascribed to acute mountain sickness (AMS). Ten men provided internal jugular vein and radial artery blood samples during normoxia and 9-h passive exposure to hypoxia (12.9% O-2). Cerebral blood flow was determined by the Kety-Schmidt technique with net exchange calculated by the Fick principle. AMS and headache were determined with clinically validated questionnaires. Electron paramagnetic resonance spectroscopy and ozone-based chemiluminescence were employed for direct detection of spin-trapped free radicals and nitric oxide metabolites. Neuron-specific enolase (NSE), S100 beta, and 3-nitrotyrosine (3-NT) were determined by ELISA. Hypoxia increased the arterio-jugular venous concentration difference (a-v(D)) and net cerebral output of lipid-derived alkoxyl-alkyl free radicals and lipid hydroperoxides (P

Near-infrared photoluminescence of lanthanide complexes containing the hemicyanine chromophore

The near-infrared luminescence properties of three (E)-N-hexadecyl-N',N'-dimethylamino-stilbazolium tetrakis(1-phenyl-3-methyl-4-benzoyl-5-pyrazolonato) lanthanide(III) complexes are described. These three complexes, containing trivalent neodymium, erbium and ytterbium, respectively, show near-infrared luminescence in acetonitrile solution upon UV irradiation. Luminescence decay times have been measured. The complexes consist of a positively charged hemicyanine chromophore with a long alkyl chain and a tetrakis(pyrazolonato) lanthanide(III) anion. Because of the absence of an alpha-hydrogen atom in the pyrazolonato ligands, and because of the saturation of the coordination sphere by four bidentate ligands, the luminescence properties are enhanced when compared to, e.g. quinolinate complexes. (C) 2007 Elsevier Ltd. All rights reserved.

Fully fluorinated imidodiphosphinate shells for visible- and NIR-Emitting lanthanides: Hitherto unexpected effects of sensitizer fluorination on lanthanide emission properties

In this paper we demonstrate that the effect of aromatic C-F substitution in ligands does not always abide by conventional wisdom for ligand design to enhance sensitisation for visible lanthanide emission, in contrast with NIR emission for which the same effect coupled with shell formation leads to unprecedented long luminescence lifetimes. We have chosen an imidodiphosphinate ligand, N-{P,P-di-(pentafluorophinoyl)}-P,P-dipentafluoro-phenylphosphinimidic acid (HF(20)tpip), to form ideal fluorinated shells about all visible- and NIR-emitting lanthanides. The shell, formed by three ligands, comprises twelve fully fluorinated aryl sensitiser groups, yet no-high energy X-H vibrations that quench lanthanide emission. The synthesis, full characterisation including X-ray and NMR analysis as well as the photophysical properties of the emissive complexes [Ln(F(20)tpip)(3)], in which Ln=Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, Y, Gd, are reported. The photophysical results contrast previous studies, in which fluorination of alkyl chains tends to lead to more emissive lanthanide complexes for both visible and NIR emission. Analysis of the fluorescence properties of the HF(20)tpip and [Gd(F(20)tpip)(3)] reveals that there is a low-lying state at around 715 nm that is responsible for partially quenching of the signal of the visible emitting lanthanides and we attribute it to a pi-sigma* state. However, all visible emitting lanthanides have long lifetimes and unexpectedly the [Dy(F(20)tpip)(3)] complex shows a lifetime of 0.3 ms, indicating that the elimination of high-energy vibrations from the ligand framework is particularly favourable for Dy. The NIR emitting lanthanides show strong emission signals in powder and solution with unprecedented lifetimes. The luminescence lifetimes of [Nd(F(20)tpip)(3)], [Er(F(20)tpip)(3)] and [Yb(F(20)tpip)(3)] in deuteurated acetonitrile are 44, 741 and 1111 mu s. The highest value observed for the [Yb(F(20)tpip)(3)] complex is more than half the value of the Yb ion radiative lifetime.

Alkali-metal salts of aromatic carboxylic acids: Liquid crystals without flexible chains

The alkali-metal salts of meta-substituted benzoic acids exhibit a smectic A mesophase at high temperatures. These compounds are examples of liquid crystals without terminal alkyl chains. The influence of the metal ion and of the type of substituents on the transition temperatures is discussed. Compounds with the substituent in the ortho- and para-positions are non-mesomorphic. The crystal structures of the compounds Rb(C7H4ClO2)(C7H4ClO2H), Na(C7H4IO2)(H2O), K(C7H4ClO2)(C7H4ClO2H) and Rb(C7H4BrO2)(C7H4BrO2H) have been determined by X-ray crystallography. These compounds possess a layerlike structure in the solid state. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)