ABSTRACT
Highly Brønsted-acidic boron trifluoride monohydrate, a widely used 'super acid-catalyst', is a colourless fuming liquid that releases BF3 at room temperature. Com-pared to the liquid com-ponents, i.e. boron trifluoride monohydrate and 1,4-dioxane, their 1:1 adduct, BF3H2O·C4H8O2, is a solid with pronounced thermal stability (m.p. 401-403â K). The crystal structure of the long-time-stable easy-to-handle and weighable com-pound is reported along with new preparative aspects and the results of 1H, 11B, 13C and 19F spectroscopic investigations, particularly documenting its high Brønsted acidity in aceto-nitrile solution. The remarkable stability of solid BF3H2O·C4H8O2 is attributed to the chain structure established by O-Hâ¯O hydrogen bonds of exceptional strength {O2â¯H1-O1 [Oâ¯O = 2.534â (3)â Å] and O1-H1â¯O3i [2.539â (3)â Å] in the concatenating unit >O2â¯H1-O1-H2â¯O3i<}, taking into account the mol-ecular (non-ionic) character of the structural moieties. Indirectly, this structural feature documents the outstanding acidification of the H2O mol-ecule bound to BF3 and reflects the super acid nature of BF3H2O. In detail, the C 2 2(7) zigzag chain system of hydrogen bonding in the title structure is characterized by the double hydrogen-bond donor and double (κO,κO') hydrogen-bond acceptor functionality of the aqua ligand and dioxane molecule, respectively, the almost equal strength of both hydrogen bonds, the approximatety linear arrangement of the dioxane O atoms and the two neighbouring water O atoms. Furthermore, the approximately planar arrangement of B, F and O atoms in sheets perpendicular to the c axis of the ortho-rhom-bic unit cell is a characteristic structural feature.
ABSTRACT
A solvent- and halogen-free synthesis of high purity triflate ionic liquids via direct alkylation of organic bases (amines, phosphines or heterocyclic compounds) with methyl and ethyl trifluoromethanesulfonate (methyl and ethyl triflate) has been developed. Cheap and non-toxic dimethyl and diethyl carbonate serve as source for the methyl and ethyl groups in the preparation of methyl and ethyl triflate by this invented process. The properties of ionic liquids containing the triflate anion are determined and discussed.
Subject(s)
Ionic Liquids/chemical synthesis , Mesylates/chemical synthesis , Alkylation , Amines/chemistry , Heterocyclic Compounds/chemistry , Ionic Liquids/analysis , Magnetic Resonance Spectroscopy , Mesylates/analysis , Molecular Structure , Phosphines/chemistry , Solvents/chemistry , TemperatureABSTRACT
Cellulose is an important renewable resource for the production of bioethanol and other valuable compounds. Several ionic liquids (ILs) have been described to dissolve water-insoluble cellulose and/or wood. Therefore, ILs would provide a suitable reaction medium for the enzymatic hydrolysis of cellulose if cellulases were active and stable in the presence of high IL concentrations. For the discovery of novel bacterial enzymes with elevated stability in ILs, metagenomic libraries from three different hydrolytic communities (i.e. an enrichment culture inoculated with an extract of the shipworm Teredo navalis, a biogas plant sample and elephant faeces) were constructed and screened. Altogether, 14 cellulolytic clones were identified and subsequently assayed in the presence of six different ILs. The most promising enzymes, CelA2, CelA3 (both derived from the biogas plant) and CelA84 (derived from elephant faeces), showed high activities (up to 6.4 U/mg) in the presence of 30% (v/v) ILs. As these enzymes were moderately thermophilic and halotolerant, they retained 40% to 80% relative activity after 34 days in 4 M NaCl, and they were benchmarked with two thermostable enzymes, CelA from Thermotoga maritima and Cel5K from a metagenome library derived from Avachinsky crater in Kamchatka. These enzymes also exhibited high activity (up to 11.1 U/mg) in aqueous IL solutions (30% (v/v)). Some of the enzymes furthermore exhibited remarkable stability in 60% (v/v) IL. After 4 days, CelA3 and Cel5K retained up to 79% and 100% of their activity, respectively. Altogether, the obtained data suggest that IL tolerance appears to correlate with thermophilicity and halotolerance.