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Simultaneous activation of aldehydes and methylamine liberation by 4,4ʹ-trimethylenedipiperidine in the solid-state synthesis of N-methyl imines

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Abstract

The commercially available 4,4ʹ-trimethylenedipiperidine (TMDP) was used in the solid state to activate various aldehydes and controlled the libration of methyl amine for preparing the corresponding N-methyl imines. It was indicated that TMDP could play multiple roles simultaneously in this reaction, including (a) a bifunctional base with a predicted pKa ~ 11 and a good scavenger of acid, (b) a catalyst able to form strong hydrogen bonding and chemical interactions with aldehyde functional group through hemiaminal and/or iminium intermediate, and (c) liberating methyl amine from its salt viz. methylammonium chloride. TMDP could be regenerated by neutralization. It was also regenerated by heating at 70 °C, which is reported for the first time according to the best of our knowledge. The regenerated reagent was stable regarding its chemical structure, and there was no significant loss in the catalytic efficiency even after several runs. The mechanism was investigated by performing several control reactions and studying the FTIR and NMR spectra in the solid-state synthesis. The current work demonstrated TMDP as a safe and greener promoter-acid scavenger for organic transformations compared with toxic, flammable, volatile liquid secondary amines such as piperidine.

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Acknowledgements

The authors are also grateful to all staff members in the Analytical and Testing Center of Nanotechnology & Catalysis Research Center for their partial support.

Funding

This work was supported by Research Grant IF008-2023 from Nippon Sheet Glass Foundation for Materials Science and Engineering, Japan, and ST018-2022 from UM International Collaboration Grant, Universiti Malaya, Malaysia.

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Authors and Affiliations

  1. Nanotechnology and Catalysis Research Center, Institute for Advanced Studies (IAS), University of Malaya, 50603, Kuala Lumpur, Malaysia

    Lia Zaharani, Mohd Rafie Johan & Nader Ghaffari Khaligh

  2. Department of Biomedicine, Faculty of Biology, Bielefeld University, 33615, Bielefeld, Germany

    Mahta Ghafarikhaligh

  3. Department of Chemistry, University of the Western Cape, Bellville, Cape Town, 7535, South Africa

    Salam Titinchi

Authors
  1. Lia Zaharani
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  2. Mahta Ghafarikhaligh
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  3. Salam Titinchi
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  4. Mohd Rafie Johan
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  5. Nader Ghaffari Khaligh
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Contributions

LZ: Methodology, Investigation, Formal analysis, Data collection; MG: Methodology, Formal analysis, Data collection; ST: Resources, Visualization, Writing-original draft; MRJ: Supervision; NGK: Conceptualization, Data curation, Validation, Visualization, Resources, Supervision, Project administration, Writing-original draft, Writing-review & editing.

Corresponding author

Correspondence to Nader Ghaffari Khaligh.

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Zaharani, L., Ghafarikhaligh, M., Titinchi, S. et al. Simultaneous activation of aldehydes and methylamine liberation by 4,4ʹ-trimethylenedipiperidine in the solid-state synthesis of N-methyl imines. Res Chem Intermed 49, 3519–3538 (2023). https://doi.org/10.1007/s11164-023-05045-z

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