TY - JOUR
T1 - Safe and direct conversion of 2,4-Dinitrotoluene into 1-Methyl-2,4-Cyclohexane-Diamine
T2 - A One-Pot hydrogenation reaction route catalyzed by Lithium-Modified γ-Al2O3-Supported ruthenium nanoclusters
AU - Wen, Xinglin
AU - Yang, Yonglu
AU - Pan, Yong
AU - Hu, Jitao
AU - Wan, Xiaoyue
AU - Yang, Yanhui
AU - Leveneur, Sébastien
AU - Jiang, Juncheng
N1 - Publisher Copyright:
© 2025
PY - 2025/12/1
Y1 - 2025/12/1
N2 - The hydrogenation of 2,4-dinitrotoluene (2,4-DNT) into 1-methyl-2,4-cyclohexanediamine (2,4-MCHD), a significant yet underutilized raw material for the synthesis of methylcyclohexane diisocyanate (HTDI) with exceptional properties, represents one of the most promising reactions for the development of diisocyanate chemical processes. In this study, we developed a highly efficient and stable heterogeneous catalytic system for the direct hydrogenation of 2,4-DNT to 2,4-MCHD using Li-modified γ-Al2O3 supported Ru nanoclusters (Li-modified-Ru/γ-Al2O3). Under mild reaction conditions, we successfully inhibited side reactions, such as deamination, achieving a selectivity exceeding 95% for 2,4-MCHD, while the conversion of 2,4-DNT surpassed 99%. Kinetic studies revealed that the hydrogenation of 2,4-DNT in this system occurs as a tandem reaction, with the hydrogenation of the benzene ring identified as the rate-determining step. Investigations into the structure–activity relationship indicated that the valence state of the Ru nanocluster, the acid-base properties of the catalyst, the modification by Li, and the synergistic effects of various elements within the catalyst are critical factors contributing to the high activity and stability of the Li-modified-Ru/γ-Al2O3 catalyst for the hydrogenation of 2,4-DNT to produce 2,4-MCHD. This work represents the first example of the direct hydrogenation of dinitroaromatic compounds to yield diamino aliphatic compounds and provides a solid foundation for understanding such reaction systems.
AB - The hydrogenation of 2,4-dinitrotoluene (2,4-DNT) into 1-methyl-2,4-cyclohexanediamine (2,4-MCHD), a significant yet underutilized raw material for the synthesis of methylcyclohexane diisocyanate (HTDI) with exceptional properties, represents one of the most promising reactions for the development of diisocyanate chemical processes. In this study, we developed a highly efficient and stable heterogeneous catalytic system for the direct hydrogenation of 2,4-DNT to 2,4-MCHD using Li-modified γ-Al2O3 supported Ru nanoclusters (Li-modified-Ru/γ-Al2O3). Under mild reaction conditions, we successfully inhibited side reactions, such as deamination, achieving a selectivity exceeding 95% for 2,4-MCHD, while the conversion of 2,4-DNT surpassed 99%. Kinetic studies revealed that the hydrogenation of 2,4-DNT in this system occurs as a tandem reaction, with the hydrogenation of the benzene ring identified as the rate-determining step. Investigations into the structure–activity relationship indicated that the valence state of the Ru nanocluster, the acid-base properties of the catalyst, the modification by Li, and the synergistic effects of various elements within the catalyst are critical factors contributing to the high activity and stability of the Li-modified-Ru/γ-Al2O3 catalyst for the hydrogenation of 2,4-DNT to produce 2,4-MCHD. This work represents the first example of the direct hydrogenation of dinitroaromatic compounds to yield diamino aliphatic compounds and provides a solid foundation for understanding such reaction systems.
KW - 1-Methyl-2
KW - 2, 4-Dinitrotoluene
KW - 4-Cyclohexanediamine
KW - Lithium-modified
KW - One-Pot Hydrogenation
KW - Ruthenium nanocluster
UR - http://www.scopus.com/inward/record.url?scp=105007042903&partnerID=8YFLogxK
U2 - 10.1016/j.fuel.2025.135847
DO - 10.1016/j.fuel.2025.135847
M3 - 文章
AN - SCOPUS:105007042903
SN - 0016-2361
VL - 401
JO - Fuel
JF - Fuel
M1 - 135847
ER -