Skip to main content
SpringerLink
Log in

Green Formylation of Alcohols Catalyzed by Magnetic Nanoparticles of the Core–Shell Fe3O4@SiO2-SO3H

  • Research Paper
  • Published:
Iranian Journal of Science and Technology, Transactions A: Science Aims and scope Submit manuscript

Abstract

The immobilized sulfonic acid on silica-layered magnetite was successfully synthesized and characterized using Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction spectroscopy, scanning electron microscopy and thermogravimetric analyses. The prepared Fe3O4@SiO2-SO3H MNPs were used as an efficient solid acidic nanocatalyst toward successful formylation of structurally diverse aliphatic and benzylic primary/secondary alcohols using formic acid under oil bath conditions (60 °C). The product, formyl esters, was obtained in 76–92% yields within 1–20 min. The sulfonated nanocatalyst was easily recovered by an external magnetic field and reused for five consecutive cycles without significant loss of its catalytic activity.

Graphical Abstract

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.

Institutional subscriptions

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

References

  • Abu-Reziq R, Alper H, Wang D, Post ML (2006) Metal supported on dendronized magnetic nanoparticles: highly selective hydroformylation catalysts. J Am Chem Soc 128:5279–5282

    Article  Google Scholar 

  • Baghbanian SM, Farhang M (2014) CuFe2O4 nanoparticles: a magnetically recoverable and reusable catalyst for the synthesis of coumarins via Pechmann reaction in water. Synth Commun 44:697–706

    Article  Google Scholar 

  • Boudart M (1995) Turnover rates in heterogeneous catalysis. Chem Rev 95:661–666

    Article  Google Scholar 

  • Corma A (2003) State of the art and future challenges of zeolites as catalysts. J Catal 216:298–312

    Article  Google Scholar 

  • Corma A, Garcia H, Llabres i Xamena FX (2010) Engineering metal organic frameworks for heterogeneous catalysis. Chem Rev 110:4606–4655

    Article  Google Scholar 

  • Esmaeilpour M, Sardarian AR (2014) Dodecylbenzenesulfonic acid as an efficient, chemoselective and reusable catalyst in the acetylation and formylation of alcohols and phenols under solvent-free conditions at room temperature. Iran J Sci Tech Trans A 38:175–186

    Google Scholar 

  • Gawande MB, Pandey RK, Jayaram RV (2012) Role of mixed metal oxides in catalysis science-versatile applications in organic synthesis. Catal Sci Technol 2:1113–1125

    Article  Google Scholar 

  • Gawande MB, Branco PS, Varma RS (2013) Nano-magnetite (Fe3O4) as a support for recyclable catalysts in the development of sustainable methodologies. Chem Soc Rev 42:3371–3393

    Article  Google Scholar 

  • Gelbard G (2005) Organic synthesis by catalysis with ion-exchange resins. Ind Eng Chem Res 44:8468–8498

    Article  Google Scholar 

  • George SM (1995) Introduction: heterogeneous catalysis. Chem Rev 95:475–476

    Article  Google Scholar 

  • Gilanizadeh M, Zeynizadeh B (2018a) Synthesis and characterization of the immobilized Ni-Zn-Fe layered double hydroxide (LDH) on silica coated magnetite as a mesoporous and magnetically reusable catalyst for the preparation of benzylidenemalononitriles and bisdimedones (tetraketones) under green conditions. New J Chem. https://doi.org/10.1039/c8nj00788h

    Google Scholar 

  • Gilanizadeh M, Zeynizadeh B (2018b) Binary copper and iron oxides immobilized on silica-layered magnetite as a new reusable heterogeneous nanostructure catalyst for the Knoevenagel condensation in water. Res Chem Intermed. https://doi.org/10.1007/s11164-018-3475-0

    Google Scholar 

  • Habibi MH, Tangestaninejad S, Mirkhani V, Yadollahi B (2001) Novel catalytic acetylation and formylation of alcohols with potassium dodecatungstocobaltatetrihydrate (K5CoW12O40·3H2O). Tetrahedron 57:8333–8337

    Article  Google Scholar 

  • Hagiwara H, Morohashi K, Sakai H, Suzuki T, Ando M (1998) Acetylation and formylation of alcohols with triphenylphosphine and carbon tetrabromide in ethyl acetate or ethyl formate. Tetrahedron 54:5845–5852

    Article  Google Scholar 

  • Hattori H (1995) Heterogeneous basic catalysis. Chem Rev 95:537–558

    Article  Google Scholar 

  • Heitbaum M, Glorius F, Escher I (2006) Asymmetric heterogeneous catalysis. Angew Chem Int Ed 45:4732–4762

    Article  Google Scholar 

  • Iranpoor N, Shekarriz M (1999) Catalytic esterification of alcohols, carboxylic acids and transesterification reactions with cerium(IV) triflate. Bull Chem Soc Jpn 72:455–458

    Article  Google Scholar 

  • Iranpoor N, Firouzabadi H, Zolfigol MA (1998) Selective acetylation of primary alcohols: acetyl and formyl transfer reactions with copper(II) salts. Synth Commun 28:1923–1934

    Article  Google Scholar 

  • Ishihara K, Kubota M, Kurihara H, Yamamoto H (1996) Scandium trifluoromethanesulfonate as an extremely active Lewis acid catalyst in acylation of alcohols with acid anhydrides and mixed anhydrides. J Org Chem 61:4560–4567

    Article  Google Scholar 

  • Khazaei A, Rostami A, Mantashlo F (2010) p-Toluenesulfonyl chloride as a new and effective catalyst for acetylation and formylation of hydroxyl compounds under mild conditions. Chin Chem Lett 21:1430–1434

    Article  Google Scholar 

  • Kocienski PJ (1994) Protecting Groups. Thieme, Stuttgart, New York

    Google Scholar 

  • Li GY, Jiang YR, Huang KL, Ding P, Yao LL (2008) Kinetics of adsorption of Saccharomyces cerevisiaemandelated dehydrogenase on magnetic Fe3O4-chitosan nanoparticles. Colloids Surf A 320:11–18

    Article  Google Scholar 

  • Liu X, Ma Z, Xing J, Liu H (2004) Preparation and characterization of amino-silane modified superpara-magnetic silica nanospheres. J Magn Magn Mater 270:1–6

    Article  Google Scholar 

  • Lopez JA, González F, Bonilla FA, Zambrano G, Gómez ME (2010) Synthesis and characterization of Fe3O4 magnetic nanofluid. Rev LatinAm Metal Mat 30:60–66

    Google Scholar 

  • Lu AH, Salabas EL, Schuth F (2007) Magnetic nanoparticles: synthesis, protection, functionalization, and application. Angew Chem Int Ed 46:1222–1244

    Article  Google Scholar 

  • Mirkhani V, Tangestaninejad S, Moghadam M, Yadollahi B, Alipanah L (2004) Cerium polyoxometalate as a reusable catalyst for acetylation and formylation of alcohols. Monatsh Chem 135:1257–1263

    Article  Google Scholar 

  • Mizuno N, Misono M (1998) Heterogeneous catalysis. Chem Rev 98:199–218

    Article  Google Scholar 

  • Mohammadpoor-Baltork I, Aliyan H, Khosropour AR (2001) Bismuth(III) salts as convenient and efficient catalysts for the selective acetylation and benzoylation of alcohols and phenols. Tetrahedron 57:5851–5854

    Article  Google Scholar 

  • Orita A, Tanahashi C, Kakuda A, Otera J (2000) Highly efficient and versatile acylation of alcohols with Bi(OTf)3 as catalyst. Angew Chem Int Ed 39:2877–2879

    Article  Google Scholar 

  • Othman MR, Helwani Z, Martunus Fernando WJN (2009) Synthetic hydrotalcites from different routes and their application as catalysts and gas adsorbents: a review. Appl Organomet Chem 23:335–346

    Article  Google Scholar 

  • Polshettiwar V, Luque R, Fihri A, Zhu H, Bouhrara M, Basset JM (2011) Magnetically Recoverable Nanocatalysts. Chem Rev 111:3036–3075

    Article  Google Scholar 

  • Procopiou PA, Baugh SPD, Flack SS, Inglis GGA (1998) An extremely powerful acylation reaction of alcohols with acid anhydrides catalyzed by trimethylsilyltrifluoromethanesulfonate. J Org Chem 63:2342–2347

    Article  Google Scholar 

  • Ram RN, Meher NK (2002) Selective formylation of alcohols in the presence of phenols with chloral. Tetrahedron 58:2997–3001

    Article  Google Scholar 

  • Shirini F, Zolfigol MA, Mallakpour B (2005) Mild and efficient procedure for acetylation and formylation of alcohols in the presence of Mg(HSO4)2. Russ J Org Chem 41:625–626

    Article  Google Scholar 

  • Shirini F, Zolfigol MA, Safari A (2006) Efficient acetylation and formylation of alcohols in the presence of Zr(HSO4)4. J Chem Res 3:154–156

    Article  Google Scholar 

  • Shirini F, Marjani K, Taherpour-Nahzomi H, Zolfigol MA (2007) Silica triflate as an efficient reagent for the chemoselective formylation of alcohols. Phosphorus Sulfur Silicon 182:1245–1251

    Article  Google Scholar 

  • Shirini F, Seddighi M, Mamaghani M (2014) Brönsted acidic ionic liquid supported on rice husk ash (RHA-[pmim]HSO4): a highly efficient and reusable catalyst for the formylation of amines and alcohols. RSC Adv 4:50631–50638

    Article  Google Scholar 

  • Shokouhimehr M, Piao Y, Kim J, Jang Y, Hyeon T (2007) A magnetically recyclable nanocomposite catalyst for olefin epoxidation. Angew Chem Int Ed 46:7039–7043

    Article  Google Scholar 

  • Shylesh S, Schünemann V, Thiel WR (2010) Magnetically separable nanocatalysts: bridges between homogeneous and heterogeneous catalysis. Angew Chem Int Ed 49:3428–3459

    Article  Google Scholar 

  • Smith K (1992) Solid Supports and Catalysts in Organic Synthesis. Ellis Horwood, New York

    Google Scholar 

  • Wuts PGM, Greene TW (2006) Protective Groups in Organic Synthesis, 4th edn. Wiley, New York

    Book  Google Scholar 

  • Zhang Y, Zeng GM, Tang L, Huang DL, Jiang XY, Chen YN (2007) A hydroquinone biosensor using modified core–shell magnetic nanoparticles supported on carbon paste electrode. Biosens Bioelectron 22:2121–2126

    Article  Google Scholar 

  • Zhang DH, Li GD, Li JX, Chen JS (2008) One-pot synthesis of Ag-Fe3O4 nanocomposite: a magnetically recyclable and efficient catalyst for epoxidation of styrene. Chem Commun 29:3414–3416

    Article  Google Scholar 

  • Zolfigol MA, Chehardoli G, Dehghanian M, Niknam K, Shirini F, Khoramabadi-Zad A (2008) Silica sulfuric acid and Al(HSO4)3: as efficient catalysts for the formylation of alcohols by using ethyl formate under heterogeneous conditions. J Chin Chem Soc 55:885–889

    Article  Google Scholar 

Download references

Acknowledgements

The authors gratefully acknowledged the financial support of this work by the research council of Urmia University.

Author information

Authors and Affiliations

  1. Faculty of Chemistry, Urmia University, Urmia, 5756151818, Iran

    Masumeh Gilanizadeh, Behzad Zeynizadeh & Elahe Gholamiyan

Authors
  1. Masumeh Gilanizadeh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Behzad Zeynizadeh
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Elahe Gholamiyan
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Masumeh Gilanizadeh.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOC 1549 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gilanizadeh, M., Zeynizadeh, B. & Gholamiyan, E. Green Formylation of Alcohols Catalyzed by Magnetic Nanoparticles of the Core–Shell Fe3O4@SiO2-SO3H. Iran J Sci Technol Trans Sci 43, 819–827 (2019). https://doi.org/10.1007/s40995-018-0594-9

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40995-018-0594-9

Keywords

Search

Navigation