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Faculté des Sciences
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New strategies toward the preparation and use of unstable nitroso species

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Kassin, Victor-Emmanuel ULiège
Promotor(s) : Monbaliu, Jean-Christophe ULiège
Date of defense : 27-Jun-2017 • Permalink : http://hdl.handle.net/2268.2/2493
Details
Title : New strategies toward the preparation and use of unstable nitroso species
Author : Kassin, Victor-Emmanuel ULiège
Date of defense  : 27-Jun-2017
Advisor(s) : Monbaliu, Jean-Christophe ULiège
Committee's member(s) : Damblon, Christian ULiège
Detrembleur, Christophe ULiège
Lemaire, Christian ULiège
Language : English
Number of pages : 83
Keywords : [en] Nitroso
[en] α-chloro-nitroso
[en] Hetero Diels-Alder
[en] Electrophilic amination
[en] Continuous-Flow processes
Discipline(s) : Physical, chemical, mathematical & earth Sciences > Chemistry
Research unit : Center for Integrated Technology and Organic Synthesis
Target public : Researchers
Professionals of domain
Student
Institution(s) : Université de Liège, Liège, Belgique
Degree: Master en sciences chimiques, à finalité approfondie
Faculty: Master thesis of the Faculté des Sciences

Abstract

[en] 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.


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Author

  • Kassin, Victor-Emmanuel ULiège Université de Liège > Master en sc. chimiques, à fin.

Promotor(s)

Committee's member(s)

  • Damblon, Christian ULiège Université de Liège - ULg > Département de chimie (sciences) > Chimie biologique structurale
    ORBi View his publications on ORBi
  • Detrembleur, Christophe ULiège Université de Liège - ULg > Département de chimie (sciences) > Centre d'études et de rech. sur les macromolécules (CERM)
    ORBi View his publications on ORBi
  • Lemaire, Christian ULiège Université de Liège - ULg > Centre de recherches du cyclotron
    ORBi View his publications on ORBi
  • Total number of views 58
  • Total number of downloads 12










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