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. 2022 Aug 1;7(32):27980-27990.
doi: 10.1021/acsomega.2c01803. eCollection 2022 Aug 16.

First Evidence of the Double-Bond Formation by Deoxydehydration of Glycerol and 1,2-Propanediol in Ionic Liquids

Andrea Mascitti  1 , Giuseppe Scioli  1 , Lucia Tonucci  2 , Valentino Canale  3 , Raimondo Germani  4 , Pietro Di Profio  3 , Nicola d'Alessandro  1
Affiliations

First Evidence of the Double-Bond Formation by Deoxydehydration of Glycerol and 1,2-Propanediol in Ionic Liquids

Andrea Mascitti et al. ACS Omega. .

Abstract

Deoxydehydration (DODH) reaction of glycerol (GL) and 1,2-propanediol (1,2-PD), in ionic liquids (ILs), catalyzed by methyltrioxorhenium (MTO) and Re2O7, was studied in detail. To better understand the ability of ILs to improve the catalytic performance of the rhenium catalyst, several experiments, employing eight different cations and two different anions, were carried out. Among the anions, bis(trifluoromethylsulfonyl)imide (TFSI) appears to be more appropriate than PF6 -, for its relatively lower volatility of the resulting IL. Regarding the choice of the most appropriate cation, the presence of a single aromatic ring seems to be a necessary requirement for a satisfying and convenient reactivity. With the aim to extend the recyclability of the catalyst, experiments involving the readdition of polyol to the terminal reaction mixture were carried out. Worthy of interest is the fact that the presence of the IL prevents the inertization process of the catalyst, allowing us to obtain the alkene also after a readdition of fresh polyol.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Chart 1
Chart 1. ILs used in this study; only cations have been reported here, while as the counterion, they contain the bis(trifluoromethane)sulfonimide anion (TFSI), and only for MBIm, also the hexafluorophosphate derivative (MBIm-PF6) has been considered.
Figure 1
Figure 1
Schematic representation of the DODH reactions. The apparatus is sealed, just allowing a gas flux of about 1 bubble per second (air or H2), which helps to remove continuously the alkene and transfer it inside the appropriate ice cold trap. Temperature of the oil bath is 140 °C.
Figure 2
Figure 2
Series of Raman spectra of MTO treated at 140 °C with 2-propanol: from the top, 0 min (dark blue), 15 min (green), 45 min (red), and 120 min (light blue).
Figure 3
Figure 3
Series of Raman spectra of Re2O7 treated at 140 °C with 2-propanol: from the top, 0 min (dark blue), 15 min (green), 45 min (red), and 120 min (light blue) (we omitted the part of spectra from 2000 to 3000 cm–1 since no signals appeared).
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