Effective Acetylation of Hydroxyl Compound with RuIII(OTf)2 Salen Modified SiO2–Fe3O4 Magnetically Recycling Catalyst

Document Type : Research Article

Authors

1 Shahid Ahmadi Roshan Research Center, Abadeh, Fars, Iran.

2 Department of Chemical Engineering, Iranshahr Branch, Islamic Azad University, Iranshahr, Iran.

Abstract

This study presents the successful synthesis of Ru(OTf)2 on amino-functionalized Schiff base SiO2@Fe3O4, which serves as a rapid and effective catalyst for the acetylation of primary alcohols. Notably, the catalyst demonstrates selectivity by preventing the acetylation of secondary and tertiary alcohols, as well as phenols, when used with acetic anhydride. The characterization of the Fe3O4@SiO2/Schiff-base/Ru(III) magnetic nanoparticles (MNPs) was conducted using various analytical techniques, including Fourier Transform Infrared Spectroscopy (FT-IR), UV-Visible Spectroscopy (UV-Vis), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray Spectroscopy (EDX), and Vibrating Sample Magnetometry (VSM). Remarkably, the catalyst, at a concentration of 0.1 mmol, exhibited excellent acetylation activity with acetic anhydride in a significantly reduced time frame. The acetylation of phenols also yielded the desired acetates with efficiencies ranging from 87% to 93% in 3 to 9 minutes. Importantly, this catalyst can be reused multiple times without a loss of catalytic activity, and its straightforward recovery and reusability align well with the principles of green chemistry.

Keywords

References

[1] Wuts, P.G., Greene, T.W., 2006. Greene's protective groups in organic synthesis. John Wiley & Sons.
[2] Arnodo, D., De Nardo, E., Ghinato, S., Baldino, S., Blangetti, M., Prandi, C., 2023. A mild, efficient and sustainable tetrahydropyranylation of alcohols promoted by acidic natural deep eutectic solvents. ChemSusChem, 16(3), e202202066. https://doi.org/10.1002/cssc.202202066
[3] Rahmanzadeh, A., Daneshvar, N., Shirini, F., Tajik, H., 2021. Comparison of the efficiency of two dicationic ionic liquids catalysts based on perchloric acid for the protection of alcohols. Journal of the Iranian Chemical Society, 18(12), 3295–3302. https://doi.org/10.1007/s13738-021-02267-z
[4] Mehdigholami, S., Koohestanian, E., 2024. Protection of hydroxy groups as trimethylsilyl ethers catalyzed by recyclable magnetically Schiff-base complexes of ruthenium using HMDS. Chemical and Process Engineering: New Frontiers, 45(1), 52. https://doi.org/10.24425/cpe.2023.147411
[5] Mehdigholami, S., Koohestanian, E., 2023. Fe3O4@SiO2/AEPTMS/Fe(OTf)3: An efficient superparamagnetic nanocatalyst for the protecting of alcohols. Journal of Particle Science and Technology, 9(1), 1–9. https://doi.org/10.22104/jpst.2023.6188.1224
[6] Rahmatpour, A., Alinejad, S., Donyapeyma, G., 2022. Noncross-linked polystyrene nanoencapsulation of ferric chloride: A novel and reusable heterogeneous macromolecular Lewis acid catalyst toward selective acetylation of alcohols, phenols, amines, and thiols. Journal of Organometallic Chemistry, 961, 122264. https://doi.org/10.1016/j.jorganchem.2022.122264
[7] Barot, Y., Mishra, S., Anand, V., Mishra, R., 2023. Iron containing di-cationic ionic liquid [DIL]2+[2FeCl4]2− as a highly efficient catalyst for the acylation of alcohols, phenols and amines. Catalysis Communications, 182, 106739. https://doi.org/10.1016/j.catcom.2023.106739
[8] Ghosh, S., Purkait, A., Jana, C.K., 2020. Environmentally benign decarboxylative N-, O-, and S-acetylations and acylations. Green Chemistry, 22(24), 8721–8727. https://doi.org/10.1039/D0GC03731A
[9] Patil, S.M., Ingale, A.P., Pise, A.S., Bhondave, R.S., 2022. Novel cobalt-supported silica-coated ferrite nanoparticles applicable for acylation of amine, phenol, and thiols derivatives under solvent-free condition. ChemistrySelect, 7(26), e202201590. https://doi.org/10.1002/slct.202201590
[10] Chia, P.W., Chee, P.S., Mazlan, N.W., Yong, F.S.J., Rozaini, M.Z.H., Kan, S.Y., 2020. Acetylation of alcohols and amines catalyzed by onion peel ash under a base- and solvent-free condition. Songklanakarin Journal of Science and Technology, 42, 602–607. https://doi.org/10.14456/sjst-psu.2020.76
[11] Kalla, R.M.N., Chakali, R., Raju, C.N., 2024. Protection of aldehydes and hydroxy compounds with acetic anhydride in the presence of sulfonic acid functionalized ionic liquid. Organic Communications, 17(1), 1–7. https://doi.org/10.25135/acg.oc.161.2312.2995
[12] Dey, A.K., Majhi, S., 2023. Samarium(III) triflate in organic synthesis: a mild and efficient catalyst. Chemistry Select, 8(18), 202300156. https://doi.org/10.1002/slct.202300156
[13] Farhadi, S., Panahandehjoo, S., 2010. Spinel-type zinc aluminate (ZnAl2O4) nanoparticles prepared by the co-precipitation method: A novel, green and recyclable heterogeneous catalyst for the acetylation of amines, alcohols and phenols under solvent-free conditions. Applied Catalysis A: General, 382(2), 293–302. https://doi.org/10.1016/j.apcata.2010.05.005
 
[14] Khaligh, N.G., 2012. Preparation, characterization and use of poly(4-vinylpyridinium) perchlorate as a new, efficient, and versatile solid-phase catalyst for acetylation of alcohols, phenols and amines. Journal of Molecular Catalysis A: Chemical, 363, 90–100. https://doi.org/10.1016/j.molcata.2012.05.021
[15] Farhadi, S., Jahanara, K., 2014. ZnAl2O4@SiO2 nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent-free conditions. Chinese Journal of Catalysis, 35(3), 368–375. https://doi.org/10.1016/S1872-2067(12)60758-X
[16] Hlatshwayo, X.S., Ndolomingo, M.J., Bingwa, N., Meijboom, R., 2021. Molybdenum-modified mesoporous SiO2 as an efficient Lewis acid catalyst for the acetylation of alcohols. RSC Advances, 11(27), 16468–16477. https://doi.org/10.1039/D1RA02134F
[17] Raczuk, E., Dmochowska, B., Samaszko-Fiertek, J., Madaj, J., 2022. Different Schiff bases—structure, importance and classification. Molecules, 27(3), 787. https://doi.org/10.3390/molecules27030787
[18] Whiteoak, C.J., Salassa, G., Kleij, A.W., 2012. Recent advances with π-conjugated salen systems. Chemical Society Reviews, 41(2), 622–631. https://doi.org/10.1039/C1CS15170C
[19] Kumagai, Y., Takabe, R., Nakazono, T., Shoji, M., Isobe, H., Yamaguchi, K., Wada, T., 2024. Water oxidation utilizing a ruthenium complex featuring a phenolic moiety inspired by the oxygen-evolving centre (OEC) of photosystem II. Sustainable Energy & Fuels, 8(5), 905–913. https://doi.org/10.1039/D3SE01610B
[20] Bühler, J., Muntwyler, A., Roithmeyer, H., Adams, P., Besmer, M.L., Blacque, O., Tilley, S.D., 2024. Immobilised ruthenium complexes for the electrooxidation of 5-hydroxymethylfurfural. Chemistry – A European Journal, 30(19), e202304181. https://doi.org/10.1002/chem.202304181
[21] Xu, Z.C., Ma, X.R., Zhang, L.J., Chen, H.T., Qing, D.M., Li, R.T., Wang, R.R., 2024. Antifungal activity of ruthenium(II) complex combined with fluconazole against drug-resistant Candida albicans in vitro and its anti-invasive infection in vivo. Journal of Inorganic Biochemistry, 255, 112522. https://doi.org/10.1016/j.jinorgbio.2024.112522
[22] Halder, S., Naskar, S., Jana, D., Kanrar, G., Pramanik, K., Ganguly, S., 2024. Ruthenium complexes of redox non-innocent aryl-azo-oximes for catalytic α-alkylation of ketones and synthesis of 2-substituted quinolines. New Journal of Chemistry, 48(18), 8181–8194. https://doi.org/10.1039/D4NJ00391H
[23] Morozkov, G.V., Abel, A.S., Lyssenko, K.A., Roznyatovsky, V.A., Averin, A.D., Beletskaya, I.P., Bessmertnykh-Lemeune, A., 2024. Ruthenium(II) complexes with phosphonate-substituted phenanthroline ligands as reusable photoredox catalysts. Dalton Transactions, 53(2), 535–551. https://doi.org/10.1039/D3DT02936K
[24] Azadi, S., Sardarian, A.R., Esmaeilpour, M., 2023. Nano Cr(III) Schiff-base complex supported on magnetic Fe3O4@SiO2: Efficient, heterogeneous, and recoverable nanocatalyst for chemoselective synthesis of 1,2-disubstituted benzimidazoles. Monatshefte für Chemie – Chemical Monthly, 154(8), 887–903. https://doi.org/10.1007/s00706-023-03100-4
[25] Azadi, S., Sardarian, A.R., Esmaeilpour, M., 2021. Magnetically recoverable Schiff base complex of Pd(II) immobilized on Fe3O4@SiO2 nanoparticles: An efficient catalyst for the reduction of aromatic nitro compounds to aniline derivatives. Monatshefte für Chemie – Chemical Monthly, 152(7), 809–821. https://doi.org/10.1007/s00706-021-02787-7
[26] Kalhor, M., Banibairami, S., Mirshokraie, S.A., 2018. Ni@zeolite-Y nanoporous: A valuable and efficient nanocatalyst for the synthesis of N-benzimidazole-1,3-thiazolidinones. Green Chemistry Letters and Reviews, 11(3), 334–344. https://doi.org/10.1080/17518253.2018.1499968
[27] Somwanshi, S.B., Somvanshi, S.B., Kharat, P.B., 2020. Nanocatalyst: A brief review on synthesis to applications. Journal of Physics: Conference Series, 1644(1), 012046. https://doi.org/10.1088/1742-6596/1644/1/012046
[28] Koohestanian, E., Mehdigholami, S., 2023. Synthesis of hematite nanoparticles by ball milling and the study of their magnetic properties and microstructure. Chemical Process Design, 2(2), 52–59. https://doi.org/10.22111/cpd.2024.47291.1030
[29] Veisi, H., Pirhayati, M., Mohammadi, P., Tamoradi, T., Hemmati, S., Karmakar, B., 2023. Recent advances in the application of magnetic nanocatalysts in multicomponent reactions. RSC Advances, 13(30), 20530–20556. https://doi.org/10.1039/D3RA01208E
[30] McKittrick, M.W., Jones, C.W., 2003. Toward single-site functional materials: Preparation of amine-functionalized surfaces exhibiting site-isolated behavior. Chemistry of Materials, 15(5), 1132–1139. https://doi.org/10.1021/cm020952z
[31] Dawn, R., et al., 2022. Origin of magnetization in silica-coated Fe3O4 nanoparticles revealed by soft X-ray magnetic circular dichroism. Brazilian Journal of Physics, 52(3), 99. https://doi.org/10.1007/s13538-022-01102-x
[32] Azadi, S., et al., 2024. Antifungal activity of Cu(II) magnetic nanoparticles against pathogenic Candida species. Scientific Reports, 1–13. https://doi.org/10.1038/s41598-024-56512-5
[33] Gonzalez-Carrillo, G., Gonzalez, J., Emparan-Legaspi, M.J., Lino-Lopez, G.J., Aguayo-Villarreal, I.A., Ceballos-Magaña, S.G., Muñiz-Valencia, R., 2020. Propylsulfonic acid grafted on mesoporous siliceous FDU-5 material: A high TOF catalyst for the synthesis of coumarins via Pechmann condensation. Microporous and Mesoporous Materials, 307, 110458. https://doi.org/10.1016/j.micromeso.2020.110458
Chemical Process Design
Volume 4, Issue 2
December 2025
Pages 38-49

Files

Share

How to cite

Statistics