In this work, we firstly report on the use of highly active and selective Aquivion superacid resins as heterogeneous catalysts for the acylation of 1,2-methylenedioxybenzene (MDB) with propionic anhydride (AP). The reaction was investigated and optimized using solvent-free conditions to selectively produce 3,4-methylenedioxypropiophenone (MDP1P), a key intermediate for the manufacture of active ingredients used in insecticide formulations with a volume of production of roughly 3000 t/y. Interestingly, Aquivion-based catalysts allows to work in mild reaction conditions (i. e. 80 °C), obtaining MDP1P yields as high as 44 % after only 1 h of reaction (selectivity 83 %). A detailed study of the AP reactivity demonstrated its tendency to promote oligomerization reactions that, as confirmed by ex-situ and in-situ FT-ATR analyses, caused the deactivation of the catalyst forming surficial carbonaceous residues. In this context, a fast oxidation of the resin surface organic residues using a diluted HNO3 (or H2O2) solution was proven to be an efficient method to regenerate the catalyst, which can be reused for several reaction cycles. The results obtained in preliminary scale-up tests were basically unaffected by the reaction volume (up to 800 mL), paving the way for possible future applications of the process.
Superacid Resin-Based Heterogeneous Catalysts for the Selective Acylation of 1,2-Methylenedioxybenzene / Schiaroli N.; Allegri A.; Eberle M.; Billi S.; Guerrini A.; Albonetti S.; Vaccari A.; Tabanelli T.; Lucarelli C.. - In: CHEMSUSCHEM. - ISSN 1864-564X. - ELETTRONICO. - 16:21(2023), pp. e202300903.1-e202300903.11. [10.1002/cssc.202300903]
Superacid Resin-Based Heterogeneous Catalysts for the Selective Acylation of 1,2-Methylenedioxybenzene
Schiaroli N.
;Allegri A.;Eberle M.;Albonetti S.;Vaccari A.;Tabanelli T.
;Lucarelli C.
2023
Abstract
In this work, we firstly report on the use of highly active and selective Aquivion superacid resins as heterogeneous catalysts for the acylation of 1,2-methylenedioxybenzene (MDB) with propionic anhydride (AP). The reaction was investigated and optimized using solvent-free conditions to selectively produce 3,4-methylenedioxypropiophenone (MDP1P), a key intermediate for the manufacture of active ingredients used in insecticide formulations with a volume of production of roughly 3000 t/y. Interestingly, Aquivion-based catalysts allows to work in mild reaction conditions (i. e. 80 °C), obtaining MDP1P yields as high as 44 % after only 1 h of reaction (selectivity 83 %). A detailed study of the AP reactivity demonstrated its tendency to promote oligomerization reactions that, as confirmed by ex-situ and in-situ FT-ATR analyses, caused the deactivation of the catalyst forming surficial carbonaceous residues. In this context, a fast oxidation of the resin surface organic residues using a diluted HNO3 (or H2O2) solution was proven to be an efficient method to regenerate the catalyst, which can be reused for several reaction cycles. The results obtained in preliminary scale-up tests were basically unaffected by the reaction volume (up to 800 mL), paving the way for possible future applications of the process.File | Dimensione | Formato | |
---|---|---|---|
ChemSusChem - 2023 - Schiaroli - Superacid Resin‐Based Heterogeneous Catalysts for the Selective Acylation of 1.pdf
accesso aperto
Tipo:
Versione (PDF) editoriale
Licenza:
Licenza per Accesso Aperto. Creative Commons Attribuzione - Non commerciale - Non opere derivate (CCBYNCND)
Dimensione
1.75 MB
Formato
Adobe PDF
|
1.75 MB | Adobe PDF | Visualizza/Apri |
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.