Microwave-Assisted Oxidation of Cyclohexanecarboxamide by Di-Tertiary-Butyl Chromate in Organic Media: Synthesis and Characterization of Products

Microwave irradiation has emerged as a transformative technique in organic synthesis, enabling rapid and energy-efficient chemical transformations. This study investigates the oxidative potential of di-tert-butyl chromate (TBC) in the oxidation of cyclohexanecarboxamide, aiming to develop a faster, sustainable alternative to traditional thermal reflux methods. The oxidation was explored across three distinct organic solvent systems: tetrahydrofuran (THF), 1,4-dioxane, and dichloromethane (DCM). Reaction mixtures were prepared by combining substrate solutions with TBC at standardized stoichiometric ratios. Synthesis was conducted using microwave irradiation for precisely calibrated periods (44–110 s). The resulting coordination complexes were characterized through elemental analysis, Fourier-transform infrared (FTIR) spectroscopy, and thermal analyses, including differential thermal analysis (DTA) and thermogravimetric analysis (TGA). The microwave-assisted approach demonstrated significant kinetic enhancement, reducing reaction times from several hours to under two minutes. Solvent-dielectric synergy was observed, with THF providing the highest efficiency and yield. Characterization confirmed the formation of stable binuclear Cr₂O₃ cores stabilized by a homologous series of dicarboxylate ligands. Mass loss patterns from TGA/DTA further validated the empirical formulations and structural stability of the synthesized complexes. Our findings demonstrate that this microwave-assisted methodology aligns with the principles of green chemistry by minimizing reaction time and energy expenditure. This study provides an efficient and sustainable synthetic route for the oxidation of cyclohexanecarboxamide, offering a versatile template for the development of higher-order chromium (III) coordination frameworks.

Microwave-assisted synthesis; Di-tert-butyl chromate; Cyclohexanecarboxamide; Green chemistry; Binuclear chromium complexes

1. Kappe, C. O. "Microwave-Assisted Chemistry." In "Microwave-Assisted Organic Synthesis," pp. 1-19. Springer, 2013. [Google Scholar] [Crossref]

2. De la Hoz, A., et al. (2011). Microwave-Assisted Organic Synthesis: A Critical Review. Tetrahedron, 67(2), 283-303. [Google Scholar] [Crossref]

3. Swami, S., et al. (2025). "Recent advances in microwave-assisted synthesis: a green approach toward sustainable development." RSC Adv., 15, 2361. [Google Scholar] [Crossref]

4. Singh, M. S., & Singh, A. K. (2019). Microwave-Induced Organic Reactions: A Review. Journal of Chemical Research, 43(10), 557-562. [Google Scholar] [Crossref]

5. The twelve principles of Green Chemistry’ United States Environmental Protection Agency. 2006 Retrieved. [Google Scholar] [Crossref]

6. Lahoz, Antonio De, Diaz-Ortiz, Angel and Prieto, Pilar, Microwave assisted green organic synthesis in alternative energy sources for green chemistry, 2016 pp. 1-33. [Google Scholar] [Crossref]

7. Sajini, T., & Joseph, J. (2025). "Microwave-assisted synthesis of nanomaterials: a green chemistry perspective and sustainability assessment." RSC Sustainability, 3, 4911-4935. [DOI: 10.1039/D5SU00584A] [Google Scholar] [Crossref]

8. Banerjee, S., et al. (2025). "Revolutionizing organic synthesis through green chemistry: metal-free, bio-based, and microwave-assisted methods." Front. Chem., 13. [DOI: 10.3389/fchem.2025.1656935] [Google Scholar] [Crossref]

9. Spencer, P., "Method of Treating Foodstuffs," US Patent 2,495,429, 1950. [Google Scholar] [Crossref]

10. Gedye, R., Smith, F., Westaway, K., Ali, H., Baldisera, L., Laberge, L., & Rousell, J. (1986). The use of microwave ovens for rapid organic synthesis. Tetrahedron Letters, 27(3), 279-282. [Google Scholar] [Crossref]

11. Gedye, R. N., & Wei, J. B. (1998). Microwave-assisted organic synthesis: A review. Canadian Journal of Chemistry, 76(5), 525-532. [Google Scholar] [Crossref]

12. Gedye, R. N., & Rank, W. (1999). Microwave-assisted organic synthesis in solvent-free conditions. Journal of Chemical Research, Synopses, (10), 542-543. [Google Scholar] [Crossref]

13. Lindstrom, P., Tierney, J., Wathey, B. and Westman, J. "Microwave Assisted Organic Synthesis-a Review," Tetrahedron, vol. 57, no. 45, pp. 9225-9283, 2001. [Google Scholar] [Crossref]

14. Katre, Sangita; Study of oxidation of chromic acid with chromium complexes by classical and green approach; Der Chemica Sinicia,2014, 5 (6) Pelagia Research Library, pp 48-50. [Google Scholar] [Crossref]

15. Cyclohexanecarboxamide – Wikidata https://share.google/ACf6pecKFWFbiA2Qg. [Google Scholar] [Crossref]

16. Wheeler, J.M., "Ditertiary Butyl Chromate: A Versatile Oxidant," Journal of Chemical Research, vol. 2001, no. 10, pp. 432-433, 2001. [Google Scholar] [Crossref]

17. Oppenaur, R.V. and Oberrauch, H. "Oxidation of Amines with Di-tert-butyl Chromate," Journal of the American Chemical Society, vol. 71, no. 10, pp. 3421-3424, 1949. [Google Scholar] [Crossref]

18. Nair, A., et al. (2025). "Role of Biomolecules in Modifying the Structural and Optical Properties of Chromium (VI) Complexes." IJSRCP, 5(2), 009-018. [Google Scholar] [Crossref]

19. Blomenhofer, M.; Ganzleben, S.; Hanft, D.; Schmidt, H. W. "Cyclohexanecarboxamides as Highly Efficient Nucleating Agents for Polypropylene." Macromolecules, 2005, 38(9), 3688–3695. [Google Scholar] [Crossref]

20. Kristiansen, M.; Tervoort, T.; Smith, P. "Synergistic Nucleation of Poly(propylene) by Cyclohexanecarboxamide Derivatives." Polymer, 2003, 44(19), 5885–5891. [Google Scholar] [Crossref]

21. Mohammadi, A. Z.; Garmabi, H. "Effect of Cyclohexanecarboxamide Derivatives on the Crystallization Kinetics and Morphology of Polypropylene." Journal of Applied Polymer Science, 2011, 121(4), 2322–2330. [Google Scholar] [Crossref]

22. Scherer, O.; Knauf, W. “N-Cyclohexylcarboxamides: A New Class of Systemic Fungicides.” Pesticide Science, 1974, 5(2), 155–160. [Google Scholar] [Crossref]

23. Smith, P. J.; Taylor, R. J.; Jones, A. M. "Cyclohexyl-substituted Amides as Hydrophobic Mimics in Protease Inhibition." Bioorganic & Medicinal Chemistry Letters, 1996, 6(12), 1483–1488. [Google Scholar] [Crossref]

24. Canceill, J.; Gabard, J.; Schierer, O. "Synthesis and Anticonvulsant Activity of Some Cyclohexanecarboxamide Derivatives." European Journal of Medicinal Chemistry, 1980, 15(3), 221–225. [Google Scholar] [Crossref]

25. Paprocka, R., et al. (2025). "Synthesis, Evaluation of Biological Activity, and Structure–Activity Relationships of New Amidrazone Derivatives Containing Cyclohexane Systems." Molecules, 30(8), 1853 [Google Scholar] [Crossref]

26. Wallis, E. S.; Lane, J. F. "The Hofmann Rearrangement." Organic Reactions, 1946, 3, 267–306. [Google Scholar] [Crossref]

27. Sigel, H.; Martin, R. B. "Coordinating Properties of the Amide Group." Chemical Reviews, 1982, 82(4), 385–426. [Google Scholar] [Crossref]

28. Steiman, T. J., & Uyeda, C. (2015). "Reagents for Reductive Transition Metal Catalysis." Chemical Science, 6, 2327–2337. [Google Scholar] [Crossref]

29. Zeng, X. (2013). "Recent Advances in Chromium-Catalyzed Carbon–Carbon Bond-Forming Reactions." Chemical Society Reviews, 42(13), 5658–5671. [Google Scholar] [Crossref]

30. Katre, Sangita and Pandey, H.O. A Green approach to oxidation of succinic acid by chromium (VI) based complexes functioning as oxidant in International Journal of green chemistry and Bioprocess 2013 3(3) pp.3032. [Google Scholar] [Crossref]

31. Katre, Sangita D. Recent Advances in the Oxidation Reactions of Organic Compounds using Chromium (VI) Reagents in Res.J.Chem.Environ. Vol. 24 (1) January (2020). [Google Scholar] [Crossref]

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