Skip to main content
SpringerLink
Log in

Studies on the mechanochemical Knoevenagel condensation of fluorinated benzaldehyde derivates

  • Mechanochemical Synthesis
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

The mechanochemical Knoevenagel condensation of three fluorinated benzaldehyde derivates and malononitrile was investigated. The reactions were performed under solvent- and catalyst-free conditions and resulted in highly crystalline products after crystallization from a viscous phase in the milling jar. The quality of the obtained crystals was sufficient for single-crystal X-ray diffraction circumventing a recrystallization step. To gain more information on the reaction, progress was investigated in situ using time-resolved Raman spectroscopy. The results show a direct conversion of the reactants.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Scheme 1
Figure 1
Figure 2
Figure 3

Similar content being viewed by others

References

  1. James SL, Adams CJ, Bolm C, Braga D, Collier P, Friscic T, Grepioni F, Harris KD, Hyett G, Jones W, Krebs A, Mack J, Maini L, Orpen AG, Parkin IP, Shearouse WC, Steed JW, Waddell DC (2012) Mechanochemistry: opportunities for new and cleaner synthesis. Chem Soc Rev 41(1):413–447. https://doi.org/10.1039/c1cs15171a

    Article  Google Scholar 

  2. Boldyreva E (2013) Mechanochemistry of inorganic and organic systems: what is similar, what is different? Chem Soc Rev 42(18):7719–7738. https://doi.org/10.1039/c3cs60052a

    Article  Google Scholar 

  3. Stolle A, Szuppa T, Leonhardt SE, Ondruschka B (2011) Ball milling in organic synthesis: solutions and challenges. Chem Soc Rev 40(5):2317–2329. https://doi.org/10.1039/c0cs00195c

    Article  Google Scholar 

  4. Braga D, Grepioni F, Maini L, Prosperi S, Gobetto R, Chierotti MR (2010) From unexpected reactions to a new family of ionic co-crystals: the case of barbituric acid with alkali bromides and caesium iodide. Chem Commun 46(41):7715–7717. https://doi.org/10.1039/C0CC02701D

    Article  Google Scholar 

  5. Chadwick K, Davey R, Cross W (2007) How does grinding produce co-crystals? Insights from the case of benzophenone and diphenylamine. CrystEngComm 9(9):732–734. https://doi.org/10.1039/B709411F

    Article  Google Scholar 

  6. Fischer F, Scholz G, Batzdorf L, Wilke M, Emmerling F (2015) Synthesis, structure determination, and formation of a theobromine: oxalic acid 2: 1 cocrystal. CrystEngComm 17(4):824–829. https://doi.org/10.1039/C4CE02066A

    Article  Google Scholar 

  7. Brahmachari G (2016) Design for carbon–carbon bond forming reactions under ambient conditions. RSC Adv 6(69):64676–64725. https://doi.org/10.1039/c6ra14399g

    Article  Google Scholar 

  8. Mittapalli S, Sravanakumar Perumalla D, Nangia A (2017) Mechanochemical synthesis of N-salicylidene-aniline: thermosalient effect of polymorphic crystals. IUCrJ 4(Pt 3):243–250. https://doi.org/10.1107/S2052252517004043

    Article  Google Scholar 

  9. Štrukil V, Igrc MD, Fábián L, Eckert-Maksić M, Childs SL, Reid DG, Duer MJ, Halasz I, Mottillo C, Friščić T (2012) A model for a solvent-free synthetic organic research laboratory: click-mechanosynthesis and structural characterization of thioureas without bulk solvents. Green Chem. https://doi.org/10.1039/c2gc35799b

    Google Scholar 

  10. Braga D, Giaffreda SL, Grepioni F, Pettersen A, Maini L, Curzi M, Polito M (2006) Mechanochemical preparation of molecular and supramolecular organometallic materials and coordination networks. Dalton Trans 10(10):1249–1263. https://doi.org/10.1039/B516165G

    Article  Google Scholar 

  11. Wilke M, Kabelitz A, Zimathies A, Rademann K, Emmerling F (2017) Crystal structure and in situ investigation of a mechanochemical synthesized 3D zinc N-(phosphonomethyl)glycinate. J Mater Sci 52(20):12013–12020. https://doi.org/10.1007/s10853-017-1121-7

    Article  Google Scholar 

  12. Al-Terkawi AA, Scholz G, Buzanich AG, Reinsch S, Emmerling F, Kemnitz E (2017) Ca- and Sr-tetrafluoroisophthalates: mechanochemical synthesis, characterization, and ab initio structure determination. Dalton Trans 46(18):6003–6012. https://doi.org/10.1039/c7dt00734e

    Article  Google Scholar 

  13. Hulvey Z, Furman JD, Turner SA, Tang M, Cheetham AK (2010) Dimensionality trends in metal–organic frameworks containing perfluorinated or nonfluorinated benzenedicarboxylates. Cryst Growth Des 10(5):2041–2043. https://doi.org/10.1021/cg100121n

    Article  Google Scholar 

  14. Crawford DE, Miskimmin CKG, Albadarin AB, Walker G, James SL (2017) Organic synthesis by Twin Screw Extrusion (TSE): continuous, scalable and solvent-free. Green Chem 19(6):1507–1518. https://doi.org/10.1039/c6gc03413f

    Article  Google Scholar 

  15. Kaupp G (2003) Solid-state molecular syntheses: complete reactions without auxiliaries based on the new solid-state mechanism. CrystEngComm. https://doi.org/10.1039/b303432a

    Google Scholar 

  16. Trotzki R, Hoffmann MM, Ondruschka B (2008) Studies on the solvent-free and waste-free Knoevenagel condensation. Green Chem. https://doi.org/10.1039/b801661e

    Google Scholar 

  17. Wada S, Suzuki H (2003) Calcite and fluorite as catalyst for the Knövenagel condensation of malononitrile and methyl cyanoacetate under solvent-free conditions. Tetrahedron Lett 44(2):399–401. https://doi.org/10.1016/S0040-4039(02)02431-0

    Article  Google Scholar 

  18. Haferkamp S, Fischer F, Kraus W, Emmerling F (2017) Mechanochemical Knoevenagel condensation investigated in situ. Beilstein J Org Chem 13:2010–2014. https://doi.org/10.3762/bjoc.13.197

    Article  Google Scholar 

  19. Kaupp G, Reza Naimi-Jamal M, Schmeyers J (2003) Solvent-free Knoevenagel condensations and Michael additions in the solid state and in the melt with quantitative yield. Tetrahedron 59(21):3753–3760. https://doi.org/10.1016/S0040-4020(03)00554-4

    Article  Google Scholar 

  20. Naimi-Jamal MR, Hamzeali H, Mokhtari J, Boy J, Kaupp G (2009) Sustainable synthesis of aldehydes, ketones or acids from neat alcohols using nitrogen dioxide gas, and related reactions. Chemsuschem 2(1):83–88. https://doi.org/10.1002/cssc.200800193

    Article  Google Scholar 

  21. Mack J, Shumba M (2007) Rate enhancement of the Morita–Baylis–Hillman reaction through mechanochemistry. Green Chem 9(4):328–330. https://doi.org/10.1039/b612983h

    Article  Google Scholar 

  22. Qareaghaj OH, Mashkouri S, Naimi-Jamal MR, Kaupp G (2014) Ball milling for the quantitative and specific solvent-free Knoevenagel condensation + Michael addition cascade in the synthesis of various 2-amino-4-aryl-3-cyano-4H-chromenes without heating. RSC Adv 4(89):48191–48201. https://doi.org/10.1039/c4ra06603k

    Article  Google Scholar 

  23. Sheldrick G (2008) A short history of SHELX. Acta Crystallogr Sect A 64(1):112–122. https://doi.org/10.1107/S0108767307043930

    Article  Google Scholar 

  24. Timofeeva TV, Nesterov VN, Antipin MY, Clark RD, Sanghadasa M, Cardelino BH, Moore CE, Frazier DO (2000) Molecular modeling and experimental study of non-linear optical compounds: monosubstituted derivatives of dicyanovinylbenzene. J Mol Struct 519(1):225–241. https://doi.org/10.1016/S0022-2860(99)00305-1

    Article  Google Scholar 

  25. Antipin MY, Nesterov VN, Jiang S, Borbulevych OY, Sammeth DM, Sevostianova EV, Timofeeva TV (2003) X-ray crystal structures, molecular mechanics and quantum chemical calculations, and calculations of the nonlinear optical polarizabilities in the series of monohalogen substituted derivatives of dicyanovinylbenzene. J Mol Struct 650(1–3):1–20. https://doi.org/10.1016/S0022-2860(02)00468-4

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Bundesanstalt für Materialforschung und -prüfung, Richard-Willstätter-Straße 11, 12489, Berlin, Germany

    Sebastian Haferkamp, Werner Kraus & Franziska Emmerling

Authors
  1. Sebastian Haferkamp
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Werner Kraus
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Franziska Emmerling
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Franziska Emmerling.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Haferkamp, S., Kraus, W. & Emmerling, F. Studies on the mechanochemical Knoevenagel condensation of fluorinated benzaldehyde derivates. J Mater Sci 53, 13713–13718 (2018). https://doi.org/10.1007/s10853-018-2492-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-018-2492-0

Keywords

Search

Navigation