Lake Como 2|4 October 2011 - CHIMICA Oggi/Chemistry Today
Lake Como 2|4 October 2011 - CHIMICA Oggi/Chemistry Today Lake Como 2|4 October 2011 - CHIMICA Oggi/Chemistry Today
Scalable in situ diazomethane generation in continuous-fl ow reactors Emiliano Rossi a , Pierre Woehl b , Michele Maggini a a Dipartimento di Scienze Chimiche dell’Università degli Studi di Padova, Via Marzolo 1, 35131, Padova, Italy b Corning European Technology Center, 7-bis Avenue de Valvins, 77210, Avon, France Diazomethane is a highly reactive and selective reagent for the synthesis of pharmaceuticals and fine chemicals (1). However, its acute toxicity and explosive characteristics strongly discourage a large-scale use in synthesis. In this communication we report an optimized continuous generation of diazomethane through the base-induced decomposition of the precursor N-methyl-N-nitrosourea which is safer to store than other diazomethane precursors. Process scale-up was quickly and efficiently achieved on a modular continuous-flow platform that allowed the production and use of diazomethane up to 19 mol d -1 at a total flow rate of 53 ml min -1 , while maintaining the amount of diazomethane itself in the reactor limited to 6.5 mmol. POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER 1 Microstructured glass reactors and LED illumination: photochemistry as good as it can get Simone Silvestrini, Christian Corrado De Filippo, Tommaso Carofi glio, Michele Maggini Dipartimento di Scienze Chimiche, Università di Padova, via Marzolo 1, 35131 Padova (PD) Italy Light emitting diodes (LEDs) are interesting cold light sources with very high power conversion (80-90%) and narrow emission bands. They find application in consumer electronic devices and lighting. LED light has only found limited use in photochemistry because of the difficulty to obtain low-cost diodes that emit in the deep UV region. However, since new materials for LED applications is rapidly filling this gap, LED-driven photochemistry has the potential to become an important tool to access selective and efficient chemical syntheses. In this presentation we show how organic photochemists and material scientists can benefit from LEDs through the use of microstructured glass reactors. To this end, we present two examples that best encompass the most interesting features of LED illumination: (i) low power consumption, resulting in economical and environmental friendly processes and (ii) narrow emission bands, resulting in highly selective reaction paths. (i) Low-power commercial white LED arrays can be used for the quantitative conversion of reagents in photocycloadditions thanks to their high efficiency and the optimal geometry of glass microreactors. The reduced thickness of the microfluidic channel, ensures a uniform illumination of the reaction mixture, reduced reaction times and high space time yields. POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER 2 This process productivity could, at least in principle, fulfill the needs of small pharma or fine chemical companies. Best reaction parameters were first developed on a smallvolume flow reactor (0.9-1.35 ml) for minimal reagents consumption. Then a 10-folds production improvement was achieved by increasing the flow reactor dimensions (15-25 ml) with a very limited optimization effort. (1) G. Maas, Angew. Chem. Int. Ed., 48, 2009, 8186. (ii) Illumination of small (3 nm) silver nanoparticles (AgNPs) results in a growth along preferential directions, depending on the wavelength of the radiation. This effect can be used to produce AgNPs with specific shapes and plasmonic properties that depend on the excitation wavelength used. In this case, microfluidic reactors allow to quickly produce AgNPs that can be functionalized with thiols or used immediately for surface enhanced raman spectroscopy (SERS) analysis. 23 Lake Como 2|4 October 2011
Process intensifi cation under high-temperature/pressure conditions using microwave technology Doris Dallinger a , Hans-Jörg Lehmann b , Jonathan D. Moseley c , Alexander Stadler d , C. Oliver Kappe a a Christian Doppler Lab. for Microwave Chemistry and Inst. of Chemistry, Karl-Franzens-Univ. of Graz, Heinrichstrasse 28, A-8010 Graz, Austria b Preparation Laboratories, Global Discovery Chemistry, Novartis Institute for BioMedical Research, Basel, Switzerland c AstraZeneca, Process Research and Development, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, UK d Anton Paar GmbH, Anton-Paar Strasse 20, A-8054 Graz, Austria The direct scalability of microwave-assisted organic synthesis (MAOS) in a new bench-top microwave reactor (Masterwave, Anton Paar) is investigated. Several different organic reactions have been scaled-up typically from 1 mmol up to the 2.5 mol scale. The transformations include the Biginelli multicomponent reaction, transition metal-catalyzed carbon-carbon crosscoupling protocols (Heck and Suzuki reactions), a Diels-Alder cycloaddition, the Newman-Kwart reaction, the synthesis of 2-methylbenzimidazole and 3-acetylcoumarin, the Knoevenagel and a S Ar reaction. A N range of different solvents (high and low microwave absorbing), and varying reaction times and temperatures have been explored. In all cases, it was possible to achieve similar isolated product yields on going from a small scale (2 mL processing volume) via medium scale (20 mL) to large scale (max 750 mL volume) without changing the previously optimized reaction conditions (direct scalability). Up to 300 g in a single run could be accomplished, allowing a daily output in the kg range. The multimode microwave instrument used in the present study currently allows batch processing in a 1 L PTFE vessel with maximum operating limits of 250 °C and 30 bar of pressure and potentially could be adopted to continuous fl ow processing. POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER 3 Highly selective pressure driven etching of femtosecond laser irradiated silica Walter Navarrini a , Francesco Venturini a , Maurizio Sansotera a , Roberto Osellame b , Giulio Cerullo b a Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica ”Giulio Natta”, Via Luigi Mancinelli, 7, 20133 Milan, Italy b Istituto di Fotonica e Nanotecnologie - CNR, Dipartimento di Fisica - Politecnico di Milano, Piazza Leonardo da Vinci, 32, 20133 Milan, Italy Micro-machining a device onto glass using standard photo-lithographic techniques is troublesome since glass is isotropically etched. This absence of a preferential etching direction doesn’t allow the production of complex micro-devices. However, when compared to silicon, glass is characterized by good transparency, good corrosion resistance and it is also much cheaper. Therefore glass may be an excellent candidate to be used as a bulk material for micro-fluidic devices if it could be possible to find an efficient way to control the aspect ratio of the etched trenches. To overcome the glass isotropic etching limitations and locally modify the glass structure by making it more reactive against etching agents, a femtosecond laser irradiation methodology has been developed. With this technique it is theoretically possible to produce three dimensional micro-channels, chambers and complex structures inside transparent solid materials. Femtosecond laser irradiation followed by chemical etching (FLICE) with Hydrogen Fluoride (HF) is an emerging technique for the fabrication of directly buried, threedimensional micro-fluidic channels in silica. The procedure described in literature consists in irradiating a silica slab followed by a chemical etching step using an HF solution. With aqueous HF the etching process is self-terminating due to diffusion resistances, leading to a maximum micro-channel depth of about 1.5 mm while the use of low-pressure gaseous HF can quickly produce 3 mm long channels with an aspect ratio (Depth / Diameter) higher than 25. Unfortunately the high aspect ratio is not constant but depends on the depth of the channel. When the micro-channel is short the aspect ratio increases rapidly until it reaches its maximum value at lengths of around 1400um. Thereafter the aspect ratio starts to decrease slowly. In this poster we present a variation of the etching methodology that is based on the dynamic displacement of the etchant. This method resulted in a slight increase of the aspect ratio compared to the standard low-pressure gaseous HF method. By adopting the appropriate experimental conditions, we’ve obtained an aspect ratio (Depth/Diameter) value of 29, and an etching speed of 4 μm/min. POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER 4444444444444444444444 24 Lake Como 2|4 October 2011
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Process intensifi cation under high-temperature/pressure conditions using microwave<br />
technology<br />
Doris Dallinger a , Hans-Jörg Lehmann b , Jonathan D. Moseley c , Alexander Stadler d , C. Oliver Kappe a<br />
a<br />
Christian Doppler Lab. for Microwave <strong>Chemistry</strong> and Inst. of <strong>Chemistry</strong>, Karl-Franzens-Univ. of Graz, Heinrichstrasse 28, A-8010 Graz, Austria<br />
b<br />
Preparation Laboratories, Global Discovery <strong>Chemistry</strong>, Novartis Institute for BioMedical Research, Basel, Switzerland<br />
c<br />
AstraZeneca, Process Research and Development, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, UK<br />
d<br />
Anton Paar GmbH, Anton-Paar Strasse 20, A-8054 Graz, Austria<br />
The direct scalability of microwave-assisted organic synthesis (MAOS) in a new<br />
bench-top microwave reactor (Masterwave, Anton Paar) is investigated.<br />
Several different organic reactions have been scaled-up typically from<br />
1 mmol up to the 2.5 mol scale. The transformations include the Biginelli<br />
multicomponent reaction, transition metal-catalyzed carbon-carbon crosscoupling<br />
protocols (Heck and Suzuki reactions), a Diels-Alder cycloaddition,<br />
the Newman-Kwart reaction, the<br />
synthesis of 2-methylbenzimidazole<br />
and 3-acetylcoumarin, the<br />
Knoevenagel and a S Ar reaction. A<br />
N<br />
range of different solvents (high and<br />
low microwave absorbing), and varying reaction times and temperatures have been explored. In<br />
all cases, it was possible to achieve similar isolated product yields on going from a small scale (2 mL<br />
processing volume) via medium scale (20 mL) to large scale (max 750 mL volume) without changing<br />
the previously optimized reaction conditions (direct scalability). Up to 300 g in a single run could be<br />
accomplished, allowing a daily output in the kg range. The multimode microwave instrument used in<br />
the present study currently allows batch processing in a 1 L PTFE vessel with maximum operating limits<br />
of 250 °C and 30 bar of pressure and potentially could be adopted to continuous fl ow processing.<br />
POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER<br />
3<br />
Highly selective pressure driven etching of femtosecond laser irradiated silica<br />
Walter Navarrini a , Francesco Venturini a , Maurizio Sansotera a , Roberto Osellame b , Giulio Cerullo b<br />
a Politecnico di Milano, Dipartimento di Chimica, Materiali e Ingegneria Chimica ”Giulio Natta”, Via Luigi Mancinelli, 7, 20133 Milan, Italy<br />
b Istituto di Fotonica e Nanotecnologie - CNR, Dipartimento di Fisica - Politecnico di Milano, Piazza Leonardo da Vinci, 32, 20133 Milan, Italy<br />
Micro-machining a device onto glass using standard photo-lithographic techniques is troublesome since glass is isotropically<br />
etched. This absence of a preferential etching direction doesn’t allow the production of complex micro-devices. However,<br />
when compared to silicon, glass is characterized by good transparency, good corrosion resistance and it is also much<br />
cheaper. Therefore glass may be an excellent candidate to be used as a bulk material for micro-fluidic devices if it could be<br />
possible to find an efficient way to control the aspect ratio of the etched trenches. To overcome the glass isotropic etching<br />
limitations and locally modify the glass structure by making it more reactive against etching agents, a femtosecond laser<br />
irradiation methodology has been developed. With this technique it is theoretically possible to produce three dimensional<br />
micro-channels, chambers and complex structures inside transparent solid materials. Femtosecond laser irradiation followed<br />
by chemical etching (FLICE) with Hydrogen Fluoride (HF) is an emerging technique for the fabrication of directly buried, threedimensional<br />
micro-fluidic channels in silica. The procedure described in literature consists<br />
in irradiating a silica slab followed by a chemical etching step using an HF solution. With<br />
aqueous HF the etching process is self-terminating due to diffusion resistances, leading to<br />
a maximum micro-channel depth of about 1.5 mm while the use of low-pressure gaseous<br />
HF can quickly produce 3 mm long channels with an aspect ratio (Depth / Diameter)<br />
higher than 25. Unfortunately the high aspect ratio is not constant but depends on the<br />
depth of the channel. When the micro-channel is short the aspect ratio increases rapidly<br />
until it reaches its maximum value at lengths of around 1400um. Thereafter the aspect ratio<br />
starts to decrease slowly. In this poster we present a variation of the etching methodology<br />
that is based on the dynamic displacement of the etchant. This method resulted in a slight<br />
increase of the aspect ratio compared to the standard low-pressure gaseous HF method.<br />
By adopting the appropriate experimental conditions, we’ve obtained an aspect ratio<br />
(Depth/Diameter) value of 29, and an etching speed of 4 μm/min.<br />
POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER POSTER<br />
4444444444444444444444<br />
24<br />
<strong>Lake</strong> <strong>Como</strong><br />
<strong>2|4</strong> <strong>October</strong> <strong>2011</strong>
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