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Investigating the photochemical reaction of an oxazolone derivative under continuous-flow conditions: from analytical monitoring to implementation in an advanced UVC-LED-driven microreactor

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Abstract

This study examined the photochemical transformation of an oxazolone derivative in a continuous microreactor irradiated by a UVC LED array (273 nm). The aim of this study was to transfer the reaction protocol originally developed under batch conditions to continuous flow and to further evaluate the scope of this application. A custom-built UVC-LED panel was combined with a microchip, and this microflow system allowed to work under perfectly controlled operating conditions. NMR and LC-MS were used to identify and quantify the main products obtained during the reaction. From this, an HPLC method was developed for imine separation, allowing for an easy and fast monitoring of the reaction progress. Subsequently, the influence of the operating conditions (residence time, photon flux density, temperature) on the selectivity and conversion was investigated to identify the most favorable conditions for a specific product. Temperature did not affect conversion but had an impact on the reaction’s selectivity. The developed UVC-LED-driven continuous-flow microreactor was found to be very efficient since a quantum photon balance ratio of 0.7 was enough to convert all the reactant, while at the same time achieving the maximal yield of the target product. Exhaustive irradiation did not change the molar ratio of each compound present in the reaction medium, thus excluding follow-up photoreactions of the products. This work opens promising perspectives for boosting flow photochemistry in the UV-C domain.

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Abbreviations

\(\overline{A}\) :

Averaged absorbance of the solution in the microchip (-)

Ai :

Area response of component i by HPLC (mAU.min)

Ci :

Concentration of specie i (mol.m-3)

d:

Depth of the channel (m)

ei :

HPLC Response factor of the product i (mAU.min.L.mol-1)

\({\varepsilon}_A^{\lambda }\) :

(Decadic) molar absorption coefficient of the compound A at the wavelength λ (m2.mol-1)

f λ :

Density function distribution of the LED panel (-)

Fwall :

Photon flux at the inner walls of the microchip (molphoton. s-1)

L:

Length of the channel (m)

l:

Width of the channel (m)

mi :

Mass of component i (kg)

Mi :

Molar mass of component i (kg.mol-1)

QA :

Molar flux of the reactant A at the inlet of the reactor (mol.s-1)

qr :

Photon flux density received at the outer top surface of the microchip and measured by the radiometer (molphoton.m2.s-1)

R:

Quantum Photon balance ratio (-)

S0 :

Irradiated surface area of the microchannel (m2)

Ti :

Transmittance of the microchip’s material i (-)

V:

Volume of the microchannel (m3)

yi :

Molar ratio of the compound i (-)

θ:

Temperature (°C)

τ:

Residence time (s)

τR :

Retention time (min)

φ:

Quantum yield (mol.molphoton-1)

DAD:

Diode Array Detection

ESI:

Electrospray Source Ionization

FEP:

Fluorinated Ethylene Propylene

HPLC:

High-Performance Liquid Chromatography

LC-MS:

Liquid Chromatography – Mass Spectroscopy

LED:

Light Emitting Diode

UHPLC:

Ultra High-Performance Liquid Chromatography

PDMS:

Polydimethylsiloxane

PTFE:

Polytetrafluoroethylene

STY:

Space Time Yield

PSTY:

Space Time Yield per unit of emitted radiant Power

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Acknowledgments

This work was funded by the French National Research Agency (ANR) through the project IMPHOCHEM ANR-18-CE07-0026. The authors thank Dr. Norbert Hoffman and Dr. Mohammed Latrache for the supply of samples of compounds A, B and C and for useful discussions. The authors also thank Dr. Isaac Rodríguez-Ruiz and Prof. Sébastien Teychené for their advice on choosing the best microchip type and their help in the microchip fabrication.

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Authors and Affiliations

  1. Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France

    Gaëlle Lebrun, Marie Schmitt, Jean-François Blanco & Karine Loubière

  2. Faculty of Chemistry and Biology, Hochschule Fresenius - University of Applied Sciences, 65510, Idstein, Germany

    Michael Oelgemöller

  3. Université de Toulouse, UPS, Service Commun de RMN, 118 route de Narbonne, F31062, Toulouse, France

    Marc Vedrenne

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  1. Gaëlle Lebrun
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Correspondence to Karine Loubière.

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Highlights

• Successful transfer from batch to continuous flow for an oxazolone photochemical transformation.

• Imine separation and identification by combining HPLC, NMR and MS analyses.

• Microchips irradiated by UVC-LEDs allow for an efficient control of selectivity and yield.

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Lebrun, G., Schmitt, M., Oelgemöller, M. et al. Investigating the photochemical reaction of an oxazolone derivative under continuous-flow conditions: from analytical monitoring to implementation in an advanced UVC-LED-driven microreactor. J Flow Chem 13, 413–425 (2023). https://doi.org/10.1007/s41981-023-00284-y

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