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Acta Chimica Sinica >

2025 , Vol. 83 >Issue 3: 212 - 220

DOI: https://doi.org/10.6023/A25010007

Article

Catalytic N-Alkylation of Benzyl Alcohol and Aniline on Nb2O5 Catalyst

  • Xinyu Xia ,
  • Shankai Hou ,
  • Yong Guo ,
  • Xiaohui Liu ,
  • Yanqin Wang
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  • Shanghai Key Laboratory of Functional Materials Chemistry, Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science of Technology, Shanghai 200237, China
†These authors contributed equally to this work
*E-mail:

Received date: 2025-01-04

  Online published: 2025-03-03

Supported by

National Natural Science Foundation of China(22072042); National Natural Science Foundation of China(21872050); National Natural Science Foundation of China(21403065); National Key Research and Development Program of China(2022YFC3902500)

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Abstract

The N-alkylation of alcohols over solid catalysts represents an environmentally benign approach for the synthesis of amine compounds. In this study, niobium oxide synthesized via a hydrothermal method was employed for the N-alkylation of benzyl alcohol with aniline. Compared to various metal oxides and conventional aluminum trichloride catalysts, niobium oxide demonstrated superior catalytic activity, achieving complete conversion of benzyl alcohol (100%) and a 65.2% yield of N-benzylaniline under optimized conditions (180 ℃, 1 MPa N2, 4 h). To elucidate the reaction pathway and mechanism of benzyl alcohol N-alkylation over niobium oxide, comprehensive investigations were conducted, including reaction kinetics, solvent polarity effects, steric hindrance studies, and carbocation-trapping experiments. Kinetic analysis revealed a reaction order of 1.04 for benzyl alcohol and 0.008 for aniline, indicating a first-order overall reaction predominantly governed by the alcohol. Solvent polarity significantly influenced the reaction outcome: in toluene (a polar solvent), the yield remained stable at 65.0%, while in nonpolar solvents (cyclohexane and dodecane), the yields drastically decreased to 3.2% and 4.4%, respectively. This highlights the critical role of polar media in stabilizing carbocation intermediates. Steric effects were evaluated using diphenylmethanol as a bulky substrate, which surprisingly yielded 77% of the target product, suggesting minimal steric hindrance under the SN1 mechanism. Definitive evidence for carbocation intermediate was obtained through experiments with 1-phenylcyclopropylmethanol, where only products derived from rearranged carbocations were detected. These results demonstrated that the reaction proceeds via the SN1 mechanism involving carbocations generated from benzyl alcohol. Furthermore, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis of benzyl alcohol and aniline revealed that niobium oxide activates the C—O bond of benzyl alcohol and the N—H bond of aniline, facilitating the formation of carbocations and the cleavage of the N—H bond of aniline, thereby exhibiting good catalytic activity for benzyl alcohol N-alkylation. The niobium oxide catalyst also exhibited exceptional stability, maintaining its activity even after six cycles. This study not only provides a comprehensive mechanistic understanding of Nb2O5-catalyzed N-alkylation but also establishes a green and practical strategy for sustainable amine synthesis.

Key words： Nb2O5; benzyl alcohol; aniline; N-alkylation; SN1

Cite this article

Xinyu Xia , Shankai Hou , Yong Guo , Xiaohui Liu , Yanqin Wang . Catalytic N-Alkylation of Benzyl Alcohol and Aniline on Nb2O5 Catalyst[J]. Acta Chimica Sinica, 2025 , 83(3) : 212 -220 . DOI: 10.6023/A25010007

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