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Dissertation
New strategies toward the preparation and use of unstable nitroso species
Authors: --- --- --- ---
Year: 2017 Publisher: Liège Université de Liège (ULiège)

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Abstract

Nitroso species and their wide variety are known for decades and are involved in numerous applications such as hetero Diels-Alder reactions or electrophilic aminations on α-ketones. However, they intrinsic poor stability, toxicity and their relative hazardous profile tuned down their potential use at an industrial-scale. In a conventional batch reactor, these reactions are relatively long (20-45 min) and the conversions associated are uncomplete.
In this work, safe and efficient continuous-flow procedures for the preparation of α-chloro-nitroso species from aqueous sodium hypochlorite and oximes were developed. The conditions were first developed in a microfluidic setup, and next transposed to an industrial mesofluidic flow reactor. The lab-scale continuous-flow setup developed in this project affords complete conversion within minutes for different kinds of starting oximes (aliphatic and alicyclic, including chiral substrates). The process is very safe, and in-line IR analysis complements the control over the process conditions. The setup is amenable to the generation of libraries of α-chloro-nitroso and sustains productivities of up to 6 mL min-1, delivering ready-to-use α-chloro-nitroso species. 
The scope of the method was next assessed with a concrete application of α-chloro-nitroso species toward the synthesis of pharmacological active norephedrine. The optimized strategy toward norephedrine from propiophenone involved four steps with an overall isolated yield of 53%. Besides, several α-chloro-nitroso classes (aliphatic, alicyclic and chiral) were tested. In the last part of this work, we assessed the full development of a continuous-flow process toward norephedrine from a propiophenone derivative. Encouraging preliminary data was obtained.

Flow and transport processes with complex obstructions : applications to cities, vegetative canopies, and industry
Authors: --- ---
ISBN: 1280803665 9786610803668 1402053851 1402053835 1402053843 Year: 2007 Volume: 236 Publisher: Dordrecht : Springer,

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Abstract

The NATO Advanced Study Institute “Flow and Transport Processes in Complex - structed Geometries: from cities and vegetative canopies to engineering problems” was held in Kyiv, Ukraine in the period of May 4 - 15, 2004. This book based on the papers presented there provides an overview of this new area in ?uid mechanics and its app- cations that have developed over the past three decades. The subject, whose origins lie both in theory and in practice, is now rapidly developing in many directions. The focus of applied ?uid mechanics research has steadily been shifting from - gineering to environmental applications. In both ?elds there has been great interest in the study of ?ows around obstacles; initially single isolated obstacles, and then groups, together with the e?ects of nearby resistive surfaces, such as the walls of a pipe, the ground or a free surface in hydraulics. Simpli?ed theoretical analysis began with studies of axisymmetric and cylind- cal free-mounted bodies. However other methods had to be used for quantifying the complete ?ow ?elds past arbitrary blu? bodies, either by using experiments or, when powerful computers became available, by direct calculation and solution of the full equations of ?uid dynamics. In most practical cases the Reynolds numbers are too large to compute all the small scale eddy motions which therefore have to be described statistically.

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