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Catalytic N-Alkylation of Amines with Primary Alcohols over Halide Clusters

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Abstract

Piperidine was reacted with methanol under a hydrogen stream in the presence of (H3O)2[(W6Cl8)Cl6]·6H2O supported on silica gel. When the temperature was raised above 200 °C, the catalytic activity of the cluster appeared. Piperidine N-methylation proceeded yielding N-methylpiperidine in 95% selectivity at 350 °C. The corresponding halide clusters of niobium, molybdenum, and tantalum supported on silica gel also catalyzed the reaction. Primary alcohols such as ethanol and 1-propanol produced the corresponding N-alkyl products of piperidine; however, secondary and tertiary alcohols did not. Selective N-methylation of pyrrolidine, hexamethyleneimine, butylamine, and aniline also proceeded. Thus, the clusters catalyzed alkylation of aliphatic, alicyclic, and aromatic amines with primary alcohols. A Brønsted acid site attributable to a hydroxo ligand, which is formed on the cluster complex by thermal activation, is proposed as the active site of the catalyst.

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Authors and Affiliations

  1. The Institute of Physical and Chemical Research (RIKEN), Wako, Saitama, 351-0198, Japan

    Satoshi Kamiguchi, Ikuko Takahashi, Sayoko Nagashima, Atsushi Nakamura & Teiji Chihara

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  1. Satoshi Kamiguchi
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  2. Ikuko Takahashi
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  3. Sayoko Nagashima
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  4. Atsushi Nakamura
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  5. Teiji Chihara
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Correspondence to Teiji Chihara.

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Kamiguchi, S., Takahashi, I., Nagashima, S. et al. Catalytic N-Alkylation of Amines with Primary Alcohols over Halide Clusters. J Clust Sci 18, 935–945 (2007). https://doi.org/10.1007/s10876-007-0153-6

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  • DOI: https://doi.org/10.1007/s10876-007-0153-6

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