Synthesis and Computational Investigation of Antioxidants Prepared by Oxidative Depolymerization of Lignin and Aldol Condensation of Aromatic Aldehydes.
ChemSusChem
; 16(12): e202300208, 2023 Jun 22.
Article
en En
| MEDLINE
| ID: mdl-37040093
ABSTRACT
Novel antioxidants are synthesized by CuSO4 -catalyzed oxidative depolymerization of lignin to form aromatic aldehydes followed by aldol condensation with methyl ethyl ketone (MEK). Aldol condensation greatly improves the antioxidation ability of lignin depolymerized products. Three lignin monomeric aromatic aldehydes, - p-hydroxybenzaldehyde, vanillin, and syringaldehyde - are further employed for aldol condensation with MEK, resulting in successful synthesis of new antioxidants 1-(4-hydroxyphenyl)pent-1-en-3-one (HPPEO), 1-(4-hydroxy-3-methoxyphenyl)pent-1-en-3-one (HMPPEO), and 1-(4-hydroxy-3,5-dimethoxyphenyl)pent-1-en-3-one (HDMPPEO), respectively. Kinetic modeling illustrates that p-hydroxybenzaldehyde has the highest rate of reaction with MEK, followed by vanillin and then syringaldehyde, which is probably affected by the presence of methoxy groups. The syringaldehyde-derived product (HDMPPEO) displays the best antioxidation ability. As revealed by density functional theory calculations, electron-donating groups, such as methoxy, and conjugated side chains effectively improve the antioxidation ability. A hydrogen atom transfer (HAT) mechanism tends to occur in nonpolar solvents, whereas a sequential proton-loss electron transfer (SPLET) mechanism is favored in polar solvents. This work thus can inspire new pathways for valorization of lignin to produce high value-added products.
Palabras clave
Texto completo:
1
Colección:
01-internacional
Banco de datos:
MEDLINE
Asunto principal:
Lignina
/
Antioxidantes
Idioma:
En
Revista:
ChemSusChem
Asunto de la revista:
QUIMICA
/
TOXICOLOGIA
Año:
2023
Tipo del documento:
Article
País de afiliación:
China