Heterogeneous continuous flow synthetic system using cyclohexane-based multiphase electrolyte solutions

The discovery that supporting electrolytes can be effectively confined in typical organic solvents in a c-Hex-based multiphase electrolyte solution has led to the development of a novel heterogeneous continuous flow synthetic system. PTFE fiber functions as a separation filter that can efficiently isolate the c-Hex phase from multiphase electrolyte solutions. This system has demonstrated both electrochemical solvating and carbon-carbon bond forming reactions. Hydrophobic substrates can be introduced into the reactor as c-Hex solutions, which are then electrochemically transformed into the target hydrophobic products that pass through the PTFE fiber as c-Hex solutions.     

Rapid PCR in a continuous flow device

Continuous flow polymerase chain reaction (CFPCR) devices are compact reactors suitable for microfabrication and the rapid amplification of target DNAs. For a given reactor design, the amplification time can be reduced simply by increasing the flow velocity through the isothermal zones of the device; for flow velocities near the design value, the PCR cocktail reaches thermal equilibrium at each zone quickly, so that near ideal temperature profiles can be obtained. However, at high flow velocities there are penalties of an increased pressure drop and a reduced residence time in each temperature zone for the DNA/reagent mixture, that potentially affect amplification efficiency. This study was carried out to evaluate the thermal and biochemical effects of high flow velocities in a spiral, 20 cycle CFPCR device. Finite element analysis (FEA) was used to determine the steady-state temperature distribution along the micro-channel and the temperature of the DNA/reagent mixture in each temperature zone as a function of linear velocity. The critical transition was between the denaturation (95 degrees C) and renaturation (55 degrees C-68 degrees C) zones; above 6 mm s(-1) the fluid in a passively-cooled channel could not be reduced to the desired temperature and the duration of the temperature transition between zones increased with increased velocity. The amplification performance of the CFPCR as a function of linear velocity was assessed using 500 and 997 base pair (bp) fragments from lambda-DNA. Amplifications at velocities ranging from 1 mm s(-1) to 20 mm s(-1) were investigated. The 500 bp fragment could be observed in a total reaction time of 1.7 min (5.2 s cycle(-1)) and the 997 bp fragment could be detected in 3.2 min (9.7 s cycle(-1)). The longer amplification time required for detection of the 997 bp fragment was due to the device being operated at its enzyme kinetic limit (i.e., Taq polymerase deoxynucleotide incorporation rate).     

Residence time distribution from a continuous Couette flow device

This paper describes an experimental study of residence time distribution (RTD) by pulse response analysis in a continuous Couette flow device with rotating inner cylinder and stationary outer cylinder. The experiments were performed under conditions of (a) negligible and (b) significant influence of molecular diffusion and (c) Taylor vortex flow. Diethylene glycol and water were used as the test fluids with congo red dye and potassium permanganate solution as tracers respectively. A unique RTD described by an analytical expression was observed for experiments with low axial Reynolds number under the condition of negligible influence of molecular diffusion. For most experiments performed under conditions of significant influence of molecular diffusion and Taylor vortex flow regime over the ranges 0 < Ta < 118 and 0.4 < Re < 5.5, the RTD can be described by a dispersion model. The system behaves as a near-plug flow vessel at Ta ≈ 60. The critical Taylor number for this geometry as defined by the minimum dispersion number for a given flowrate is slightly higher than that without axial flow.     

Highly efficient continuous flow reactions using singlet oxygen as a "green" reagent

Described is a new method for the efficient in situ production of singlet oxygen in a simple continuous flow photochemical reactor. The extremely large interfacial area generated by running the biphasic mixture in a narrow channel at a high flow rate ensures high throughput as well as fast and efficient oxidation of various alkenes, 1,3-dienes, and thioethers on a preparative scale.     

A flow microreactor for laboratory high pressure vapor phase catalytic reactions

A high pressure laboratory flow microreactor was designed and built to study the kinetics of hydroprocessing reactions. New features of this system are: the high pressure saturator-condenser (up to 7·10⁶ Pa), the small size of the reactor (1 cm³), the automatic on-line analysis device. The operation of the unit is illustrated by conversion data for the hydrogenation of biphenyl.

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Microwave reactions under continuous flow conditions

Microwave chemistry has already impacted significantly on the everyday synthesis of organic molecules. The adoption and integration of this liberating technology has permitted a resurrection of many synthetic transformations that were previously considered too extreme in their conditions (temperatures, pressures, reaction times) to be synthetically useful. Furthermore, whole arrays of additional chemical transformations have been devised under microwave heating that allow access to more diverse chemical architectures via more expedient routes. Continuous flow processing of chemical intermediates taking advantage of the unique heating mechanism and characteristics of microwave irradiation will certainly be the next evolutionary step forward in this area. The synergistic combination afforded by the simultaneous application of these two core processing tools will enhance still further the synthetic capabilities of tomorrow's chemists. This short review aims to highlight the current developments and future potential offered by continuous flow microwave mediated synthesis.     

Benzene elimination from reformate gasoline by high pressure hydrogenation in a fixed-bed reactor

The reduction of benzene from benzene-rich real gasoline fractions has been studied in a high-pressure fixed-bed reactor using a Pt/TiO₂ catalyst. It was found that the yield of this process decreases with the toluene content in the feedstock, but it is independent of the kind of the saturated hydrocarbons. This revised version was published online in August 2006 with corrections to the Cover Date.     

Michael reactions carried out using a bench-top flow system

The Michael reaction between methyl 1-oxoindan-2-carboxylate and methyl vinyl ketone was achieved successfully by pumping solutions of the reactants in toluene through a fluid bed of Amberlyst A21 at 50 degrees C. The use of a fluid bed reactor is attractive as it allows gel-type beads, i.e. the type of bead used in most studies of polymer-supported (PS) organic reactions, to be used satisfactorily in a flow system. When polymer-supported cinchonidine was used in place of Amberlyst A21, the Michael product was obtained in high yield with an enantiomeric excess (ee) of 51%. This % ee is comparable to that achieved when the reaction was catalysed by cinchonidine itself.     

Instrumentation of high temperature and pressure reaction system with continuous flow and its hyphenation to a liquid chromatograph.

A continuous flow-type hydrothermal reaction system, in which both temperature and pressure were rapidly and dynamically controlled, was constructed. It is called a real time high temperature and pressure reaction system (RT-HighTP). The RT-HighTP was hyphenated with liquid chromatograph (RT-HighTP-LC) to achieve prompt analysis of the reaction products. The RT-HighTP system produced stable pressure under the supercritical and subcritical phases (%RSD < 3%). The RT-HighTP-LC was able to change the hydrothermal condition rapidly. The hydrothermal products under four conditions were analyzed within 70 min. Further, the hydrothermal products of lignin was easily taken out using the sample collecting loop and analyzed by an external instrument of GC/MS.     

Heck reactions using segmented flow conditions

Various Heck couplings have been carried out using segmented flow conditions to accelerate the reactions. Aryl iodides and aryl bromides as well as anilines in diazonium-type Heck reactions have been used successfully.     

Sub-second isoelectric focusing in free flow using a microfluidic device

Using a microfabricated chip with a bed volume of 0.2 microL we demonstrate the validity of the scaling laws for molecular mass transport of isoelectric focusing (IEF) in free flow. Nano- or microlitre sample volumes can be concentrated within 430 ms by a factor of up to 400. These very fast performances make the chip applicable to proteomic analysis and for continuous monitoring of biochemical processes.     

A simple device for determinations using Landolt reactions

Summary A device has been described which permits several Landolt reactions to be initiated simultaneously. All solutions remain at the same temperature, and mixing is rapid. This device improves the precision and the convenience of determinations using Landolt reactions.

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Zusammenfassung Eine Anordnung zur gleichzeitigen Ingangsetzung mehrerer Landolt-Reaktionen wurde beschrieben. Alle Lösungen werden bei gleicher Temperatur gehalten und rasch gemischt. Dadurch wird die Genauigkeit von Analysen mit Hilfe von Landolt-Reaktionen verbessert.

     

The use of high pressure DTA,heat flow and adiabatic calorimetry to study exothermic reactions

Cellulose, a commonly found carbohydrate, exhibits exothermic decomposition, when heated above 180C. These reactions have been detected and quantified by a range of thermal analysis and calorimetric techniques giving complementary information. The presented results are of interest for process safety.

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Zusammenfassung Cellulose, ein weit verbreitetes Kohlenhydrat, zeigt beim ErwÄrmen auf Temperaturen oberhalb 180C exotherme Zersetzung. Die damit verbundenen Reaktionen wurden mittels einer Reihe komplementÄrer thermoanalytischer und kalorimertrischer Methoden erfasst und quantifiziert. Die vorgestellten Resultate sind für die AbschÄtzung von Prozessrisiken bedeutungsvoll.

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The authors gratefully acknowledge many discussions with C. Foetisch (Linor, Orbe, CH), Prof. R. C. Reid (Lexington, Massachusetts, USA) and I. Horman (Nestlé Research Centre, Vers-chez-les-Blanc, CH).     

Tandem cross-metathesis/hydrogenation/cyclization reactions by using compatible catalysts

[reaction: see text] A one-pot tandem cross-metathesis/hydrogenation/cyclization procedure was achieved at room temperature, under 1 atm of hydrogen, in the presence of a ruthenium catalyst and PtO(2) showing the compatibility of the two catalysts. This tandem reaction allows the synthesis of substituted lactones and lactols from acrylic acid and acrolein, respectively, in the presence of unsaturated alcohols.     

Miniaturized continuous flow reaction vessels: influence on chemical reactions

This review offers an overview of the relatively young research area of continuous flow lab-on-a-chip for synthetic applications. A short introduction on the basic aspects of lab-on-a-chip is given in the first part. Subsequently, the effects of downscaling reaction vessels as well as the advantages of the continuous flow microfluidic approach over conventional chemical laboratory batch methodologies are illustrated by a number of examples of organic reactions carried out in microfluidic devices. The last part deals with a key issue of the lab-on-a-chip approach, viz. the integration of the microreactor with the analytical instrumentation to achieve high-throughput reaction monitoring.     

Rapid formation of amides via carbonylative coupling reactions using a microfluidic device

Carbonylative cross-coupling reactions of arylhalides to form secondary amides were rapidly carried out on a glass-fabricated microchip--the first time a microstructured device has been used to perform a gas-liquid carbonylation reaction.