509 research outputs found
Ionic Liquids Made with Dimethylcarbonate: Solvents as well as Boosted Basic Catalysts for the Michael Reaction
Abstract: This article describes 1) a methodology for the green synthesis of a class of methylammonium and methylphosphonium ionic liquids (ILs), 2) how to tune their acid–base properties by anion exchange, 3) complete neat-phase NMR spectroscopic characterisation of these materials and 4) their application as active organocatalysts for base-promoted carbon– carbon bond-forming reactions. Methylation of tertiary amines or phosphines with dimethyl carbonate leads to the formation of the halogen-free methyl-onium methyl carbonate salts, and these can be easily anion-exchanged to yield a range of derivatives with different melting points, solubility, acid–base properties, stability and viscosity. Treatment with water, in particular, yields bicarbonate-exchanged liquid onium salts. These proved strongly basic, enough to efficiently catalyse the Michael reaction; experiments suggest that in these systems the bicarbonate basicity is boosted by two orders of magnitude with respect to inorganic bicarbonate salts. These basic ionic liquids used in catalytic amounts are better even than traditional strong organic bases. The present work also introduces neat NMR spectroscopy of the ionic liquids as a probe for solute– solvent interactions as well as a tool for characterisation. Our studies show that high catalytic efficacy of functional ionic liquids can be achieved by integrating their green synthesis, along with a fine-tuning of their structure. Demonstrating that ionic liquid solvents can be made by a truly green procedure, and that their properties and reactivity can be tailored to the point of bridging the gap between their use as solvents and as catalysts. Keywords: dimethyl carbonate · green chemistry · ionic liquids · Michael addition · NMR spectroscop
Continuous Flow Photooxidative Degradation of Azo Dyes with Biomass-Derived Carbon Dots
The presence of persistent organic pollutants in industrial
wastewaters is becoming a problem of major concern. In the
present study we explored the degradation of azo dyes, wellknown common hazardous contaminants, by a green and
efficient procedure using continuous flow photooxidative
degradation. In particular, carbon dots synthesized from fishery
waste (bass-CDs) were used as a cheap and readily available
photocatalyst in combination with oxygen and UV light. Methyl
orange, acid red 18, amaranth, sunset yellow and chromotrope
were chosen as model substrates and their degradation was
studied both in batch and in continuous flow conditions. All the
azo dyes were fully degraded with both techniques highlighting
the suitability of bass-CDs for the decontamination of wastewater. The main advantages are of using a “disposable” photocatalyst, in aqueous solvent and in continuous flow. In
particular, continuous flow operation allowed faster decompositions: circa 2 min versus 1–3 hours needed in batc
CO2-assisted hydrolytic hydrogenation of cellulose and cellulose-based waste into sorbitol over commercial Ru/C
A single-step protocol was developed for the hydrolytic hydrogenation of microcrystalline cellulose into sorbitol over commercial carbon-supported Ru, in the presence of gaseous CO2 as an acid source and molecular hydrogen as a reductant. Under these conditions, cellulose was first hydrolysed to glucose by reversibly formed carbonic acid in water and then instantaneously hydrogenated on Ru/C. By tuning the reaction parameters, such as temperature, time and the relative pressure of CO2 and hydrogen gas, cellulose was fully converted at 220 & DEG;C in 18 h under 30 and 40 bar of H-2 and CO2, respectively, with a sorbitol yield of 81%. Blank experiments revealed that without a catalyst and hydrogen, the reaction exhibited <5% conversion and glucose was the only detected product when the reaction was performed under CO2 pressure. XRD measurements on CO2-treated cellulose surprisingly revealed no noticeable changes in the crystallinity index (<10% with respect to microcrystalline cellulose), suggesting that hydrolytic hydrogenation took place on crystalline, not amorphous, cellulose. Furthermore, not only several cellulosic feedstocks, including filter paper, cotton wool, and cotton fiber, but also typical cellulose-based wastes such as a cardboard pizza box were also tested and under the optimized conditions sorbitol was obtained with yields ranging from 56% up to 72% in all cases. No less significant was the Ru/C catalyst stability, which could be recycled at least six times without any noticeable activity loss
Concatenated batch and continuous flow procedures for the upgrading of glycerol-derived aminodiols via N-acetylation and acetalization reactions
An unprecedented two-step sequence was designed by combining batch and continuous flow (CF) protocols for the upgrading of two aminodiol regioisomers derived from glycerol, i.e., 3-amino-1,2-propanediol and 2-amino-1,3-propanediol (serinol). Under batch conditions, at 80-90 \ub0C, both substrates were quantitatively converted into the corresponding amides through a catalystfree N-acetylation reaction mediated by an innocuous enol ester as isopropenyl acetate (iPAc). Thereafter, at 30-100 \ub0C and 1-10 atm, the amide derivatives underwent a selective CF-acetalisation in the presence of acetone and a solid acid catalyst, to afford the double-functionalized (amideacetal) products
Concatenated batch and continuous flow procedures for the upgrading of glycerol-derived aminodiols via N-acetylation and acetalization reactions
An unprecedented two-step sequence was designed by combining batch and continuous flow (CF) protocols for the upgrading of two aminodiol regioisomers derived from glycerol, i.e., 3-amino-1,2-propanediol and 2-amino-1,3-propanediol (serinol). Under batch conditions, at 80-90 °C, both substrates were quantitatively converted into the corresponding amides through a catalystfree N-acetylation reaction mediated by an innocuous enol ester as isopropenyl acetate (iPAc). Thereafter, at 30-100 °C and 1-10 atm, the amide derivatives underwent a selective CF-acetalisation in the presence of acetone and a solid acid catalyst, to afford the double-functionalized (amideacetal) products
The Conversion of Platform Chemicals from Biomass: Multiphase Hydrogenation/Dehydrogenation of Levulinic Acid to to -valerolactone (GVL)
A flexible Pinner preparation of orthoesters: the model case of trimethylorthobenzoate
In the absence of additional solvents{,} a novel procedure was implemented for the synthesis of trimethylorthoesters through the Pinner reaction. At 5 [degree]C{,} the reaction of both aliphatic and aromatic nitriles (RCN; R = Et{,} Bu{,} Ph) with a moderate excess of MeOH and gaseous HCl gave the corresponding imidate hydrochlorides [RC([double bond{,} length as m-dash]NH)OR[prime or minute][middle dot]HCl] in excellent yields (>90%). At 25-65 [degree]C{,} the methanolysis of alkyl imidate salts provided trimethylortho-propionate and valerate{,} while only traces of trimethylorthobenzoate (TMOB) were observed. However{,} the aromatic hydrochloride could be readily converted into the hydrogenphosphate salt [PhC([double bond{,} length as m-dash]NH)OR[prime or minute][middle dot]H3PO4] which{,} in turn{,} underwent a selective (>80%) reaction with MeOH to produce TMOB in a 62% isolated yield. This allowed for an unprecedented Pinner-type synthesis of TMOB starting from benzonitrile{,} rather than from the highly toxic trichloromethylbenzene. Overall{,} remarkable improvements in safety and process intensification were achieved
Bridging the gap of storage ring light sources and linac-driven free-electron lasers
High-gain free-electron lasers (FELs) are driven by short, high-charge density electron beams as only produced at dedicated single pass or recirculating linear accelerators. We describe new conceptual, technical, and modeling solutions to produce subpicosecond, up to 100 \u3bcJ energy extreme ultra-violet and soft x-ray FEL pulses at high- and tunable repetition rates, from diffraction-limited storage ring light source. In contrast to previously proposed schemes, we show that lasing can be simultaneous to the standard multibunch radiation emission from short insertion devices, and that it can be obtained with limited impact on the storage ring infrastructure. By virtue of the high-average power but moderate pulse energy, the storage ring-driven high-gain FEL would open the door to unprecedented accuracy in time-resolved spectroscopic analysis of matter in the linear response regime, in addition to inelastic scattering experiments
Non Catalytic Continuous-Flow Transesterification of Dialkyl Carbonates with Glycerol Acetals
Upgrade of glycerol derivatives: the selective catalytic etherification of glycerol formal and solketal with dialkyl carbonates
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