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Mechanistic Insight into Methacrolein Formation from Formaldehyde and Propionaldehyde

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Abstract

Aldol condensation is a very important reaction in forming new C = C bond, and is an attractive way to extend the carbon chain of a molecule. In this research, diethylammonium acetate was used as an acid–base bifunctional catalyst to facilitate the formation of methacrolein via cross aldol condensation between formaldehyde and propionaldehyde. A conversion of 99.9% of propionaldehyde with a 97.4% selectivity to methacrolein (MAL) was achieved. Isotopic tracing experiments were used to propose a possible reaction mechanism. To verify the reactive pathway, we used isotopically labelled substrates. In addition, we attempted to trap the relevant reaction intermediate by decreasing the reaction temperature.

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References

  1. Kim KC, Moschetta EG, Jones CW, Jang SS (2016) Molecular dynamics simulations of aldol condensation catalyzed by alkylamine-functionalized crystalline silica surfaces. J Am Chem Soc 138(24):7664–7672

    Article  CAS  Google Scholar 

  2. Arvela PM, Shcherban N, Lozachmeur C, Eränen K et al (2019) Aldol condensation of cyclopentanone with valeraldehyde over metal oxides. Catal Lett 149:1383–1395

    Article  Google Scholar 

  3. Deshpande RM, Diwakar MM, Mahajan AN, Chaudhari RV (2004) Biphasic catalysis for a selective oxo-Mannich tandem synthesis of methacrolein. J Mol Catal A: Chem 211:49–53

    Article  CAS  Google Scholar 

  4. Mironov GS, Farberov MI (1964) Industrial methods of synthesis of α, β-unsaturated aldehydes and ketones. Usp Khim 33:649–663

    Article  CAS  Google Scholar 

  5. Basu K, Richards J, Paquette LA (2004) Mono- and bis-acrolein derivatives by reliable and efficient one-step methylenation of aldehyde precursors. Synthesis 2004:2841–2844

    Article  Google Scholar 

  6. Erkkila A, Pihko PM (2007) Rapid organocatalytic aldehyde-aldehyde condensation reactions. Eur. J. Org. Chem 2007:4205–4216

    Article  Google Scholar 

  7. Pihko Petri M, Majander I, Erkkila A (2010) Enamine catalysis. Topics Curr. Chem 291:29–75

    Article  CAS  Google Scholar 

  8. Erkkila A, Pihko Petri M (2006) Mild organocatalytic alpha-methylenation of aldehydes. J Org Chem 71:2538–2541

    Article  Google Scholar 

  9. Wang YN, Yan RY, Lv ZP, Wang H, Wang L, Li ZX, Zhang SJ (2016) Lanthanum and cesium-loaded SBA-15 catalysts for MMA synthesis by aldol condensation of methyl propionate and formaldehyde. Catal Lett 146:1808–1818

    Article  CAS  Google Scholar 

  10. Liu B, Wu SJ, Yu XF, Guan JQ, Kan QB (2011) Optimizing the matching between the acid and the base of cooperative catalysis to inhibit dehydration in the aldol condensation. J Colloid Interf Sci 362:625–628

    Article  CAS  Google Scholar 

  11. F. Tanaka, C.F. Barbas, III, Aldol and Mannich-type reactions. Enantioselective Organocatalysis, 19–55 (2007).

  12. Yu J, Jensen AD, Wang L, Li C, Zhang S (2020) Catalytic synthesis of methacrolein via the condensation of formaldehyde and propionaldehyde with L-proline. Green Chem 22:4222–4230

    Article  CAS  Google Scholar 

  13. Casas J, Sunden H, Cordova A (2004) Direct organocatalytic asymmetric α-hydroxymethylation of ketones and aldehydes. Tetrahedron Lett 45:6117–6119

    Article  CAS  Google Scholar 

  14. Wang G, Li Z, Fan L, Li C, Zhang S (2019) Sec-amine grafted D301 resin catalyzed fixed-bed process for continuous preparation of methacrolein via Mannich reaction. Chem Eng J (Amsterdam, Neth) 370:625–636

    CAS  Google Scholar 

  15. Ishikawa T, Uedo E, Okada S, S. (1999) Saito, Pyrrolidine-catalyzed homo-aldol condensation reactions of aldehydes. Synlett 1999:450–452

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by National Key Research and Development Program of China (2017YFA0206803), and National Natural Science Foundation of China (21676277). Thanks to Mayfair Kung and Harold H. Kung for repairing the paper.

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Authors and Affiliations

  1. Key Laboratory of Green Process and Engineering, State Key Laboratory of Multiphase Complex Systems, Key Laboratory of Ionic Liquids Clean Process, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, P. R. China

    Ruiyi Yan, Hongguo Tang, Yinge Bai & Mengyue Li

  2. Heze University, Heze City, 274015, P. R. China

    Zhaopo Lv

  3. School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo City, 25500, P. R. China

    Yuchao Li

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  1. Ruiyi Yan
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  2. Zhaopo Lv
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Correspondence to Ruiyi Yan.

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Yan, R., Lv, Z., Tang, H. et al. Mechanistic Insight into Methacrolein Formation from Formaldehyde and Propionaldehyde. Catal Lett 152, 799–805 (2022). https://doi.org/10.1007/s10562-021-03679-5

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  • DOI: https://doi.org/10.1007/s10562-021-03679-5

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