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Mesoporous silica nanoparticles in an efficient solvent-free transamidation of carboxamides with amines: an exhibition of a green recyclable nanocatalyst

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Abstract

A protocol is described for an efficient transamidation of amides with amines in the presence of mesoporous silica nanoparticles (MSNs). The latter is used as a green, heterogeneous, and recyclable nanocatalyst, under solvent-free conditions. Following this protocol, a wide range of aromatic, aliphatic, and cyclic/acyclic primary or secondary amines are used in synthesis of a series of amides with good to excellent yields (65–96%). MSNs is characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), small-angle powder X-ray diffraction (XRD), nitrogen adsorption-desorption analysis, and FT-IR spectroscopy. The metal/solvent-free condition, easy work up, high purity of the products, recyclability, and environmentally-friendly nature of the catalyst are the attractive features of this methodology.

An efficient transamidation of carboxamides was achieved via the use of mesoporous nanoparticles as green nanocatalyst. The metal/solvent-free condition, easy work up, high purity of the products, recyclability, and environmentally-friendly nature of the catalyst are the attractive features of this methodology.

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References

  • Ali MA, Siddiki SMAH, Kon K, Shimizu K (2014) Fe 3+-exchanged clay catalyzed transamidation of amides with amines under solvent-free condition. Tetrahedron Lett 55:1316–1319

    Article  Google Scholar 

  • Allen CL, Atkinson BN, Williams JMJ (2012) Transamidation of primary amides with amines using hydroxylamine hydrochloride as an inorganic catalyst. Angew Chemie Int Ed 51:1383–1386

    Article  Google Scholar 

  • Becerra-Figueroa L, Ojeda-Porras A, Gamba-Sánchez D (2014) Transamidation of carboxamides catalyzed by Fe (III) and water. J Org Chem 79:4544–4552

    Article  Google Scholar 

  • Carey JS, Laffan D, Thomson C, Williams MT (2006) Analysis of the reactions used for the preparation of drug candidate molecules. Org Biomol Chem 4:2337–2347

    Article  Google Scholar 

  • Chandra D, Das SK, Bhaumik A (2010) A fluorophore grafted 2D-hexagonal mesoporous organosilica: excellent ion-exchanger for the removal of heavy metal ions from wastewater. Microporous Mesoporous Mater 128:34–40

    Article  Google Scholar 

  • Chen ZW, Jiang HF, Pan XY, He ZJ (2011) Practical synthesis of amides from alkynyl bromides, amines, and water. Tetrahedron 67:5920–5927. https://doi.org/10.1016/j.tet.2011.06.045

    Article  Google Scholar 

  • Deming TJ (2007) Synthetic polypeptides for biomedical applications. Prog Polym Sci 32:858–875

    Article  Google Scholar 

  • Dineen TA, Zajac MA, Myers AG (2006) Efficient transamidation of primary carboxamides by in situ activation with N, N-dialkylformamide dimethyl acetals. J Am Chem Soc 128:16406–16409

    Article  Google Scholar 

  • Durgaiah C, Naresh M, Swamy P, Srujana K, Rammurthy B, Narender N (2016) Transamidation of carboxamides with amines over nanosized zeolite beta under solvent-free conditions. Catal Commun 81:29–32

    Article  Google Scholar 

  • Eldred SE, Stone DA, Gellman SH, Stahl SS (2003) Catalytic transamidation under moderate conditions. J Am Chem Soc 125:3422–3423

    Article  Google Scholar 

  • Firouzi A, Atef F, Oertli AG, Stucky GD, Chmelka BF (1997) Alkaline lyotropic silicate-surfactant liquid crystals. J Am Chem Soc 119:3596–3610

    Article  Google Scholar 

  • Fu R, Yang Y, Chen Z, Lai W, Ma Y, Wang Q, Yuan R (2014) Microwave-assisted heteropolyanion-based ionic liquids catalyzed transamidation of non-activated carboxamides with amines under solvent-free conditions. Tetrahedron 70:9492–9499

    Article  Google Scholar 

  • García-Álvarez R, Crochet P, Cadierno V (2013) Metal-catalyzed amide bond forming reactions in an environmentally friendly aqueous medium: nitrile hydrations and beyond. Green Chem 15:46–66

    Article  Google Scholar 

  • Ghosh K, Molla RA, Iqubal MA, Islam SM (2015) A mesoporous organosilica grafted Pd catalyst (MOG-Pd) for efficient base free and phosphine free synthesis of tertiary butyl esters via tertiary-butoxycarbonylation of boronic acid derivatives without using carbon monoxide. Green Chem 17:3540–3551

    Article  Google Scholar 

  • Ghosh SC, Li CC, Zeng HC, Ngiam JSY, Seayad AM, Chen A (2014) Mesoporous niobium oxide spheres as an effective catalyst for the transamidation of primary amides with amines. Adv Synth Catal 356:475–484

    Article  Google Scholar 

  • Hoerter JM, Otte KM, Gellman SH, Stahl SS (2006) Mechanism of AlIII-catalyzed transamidation of unactivated secondary carboxamides. J Am Chem Soc 128:5177–5183

    Article  Google Scholar 

  • Koh K, Wong-Foy AG, Matzger AJ (2009) A porous coordination copolymer with over 5000 m2/g BET surface area. J Am Chem Soc 131:4184–4185

    Article  Google Scholar 

  • Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359:710–712

    Article  Google Scholar 

  • Lam KF, Yeung KL, Mckay G (2007) Selective mesoporous adsorbents for and cu 2+ separation. Microporous Mesoporous Mater 100:191–201

    Article  Google Scholar 

  • Muskawar PN, Thenmozhi K, Bhagat PR (2015) Designing of thermally stable amide functionalized benzimidazolium perchlorate ionic liquid for transamidation of primary carboxamides. Appl Catal A Gen 493:158–167

    Article  Google Scholar 

  • Nasresfahani Z, Kassaee MZ, Nejati-Shendi M, Eidi E, Taheri Q (2016) Mesoporous silica nanoparticles (MSNs) as an efficient and reusable nanocatalyst for synthesis of β-amino ketones through one-pot three-component Mannich reactions. RSC Adv 6:32183–32188

    Article  Google Scholar 

  • Nguyen TB, Ermolenko L, Tran HDME, Al Mourabit A (2014) Hydrogen bond organocatalysis of benzotriazole in transamidation of carboxamides with amines. Heterocycles 88:403–416

    Article  Google Scholar 

  • Nguyen TB, Sorres J, Tran MQ, Ermolenko L, al-Mourabit A (2012) Boric acid: a highly efficient catalyst for transamidation of carboxamides with amines. Org Lett 14:3202–3205

    Article  Google Scholar 

  • Ogata N (1959) Studies on polymerization and depolymerization of ε-caprolactam polymer VII. On the amide interchange reaction. Die Makromol Chemie 30:212–224

    Article  Google Scholar 

  • Pathare SP, Jain AKH, Akamanchi KG (2013) Sulfated tungstate: a highly efficient catalyst for transamidation of carboxamides with amines. RSC Adv 3:7697–7703

    Article  Google Scholar 

  • Ramón RS, Bosson J, Díez-González S et al (2010) Au/Ag-cocatalyzed aldoximes to amides rearrangement under solvent-and acid-free conditions. J Org Chem 75:1197–1202

    Article  Google Scholar 

  • Rao SN, Mohan DC, Adimurthy S (2013) L-proline: an efficient catalyst for transamidation of carboxamides with amines. Org Lett 15:1496–1499. https://doi.org/10.1021/ol4002625

    Article  Google Scholar 

  • Rao SN, Mohan DC, Adimurthy S (2014) Chitosan: an efficient recyclable catalyst for transamidation of carboxamides with amines under neat conditions. Green Chem 16:4122–4126

    Article  Google Scholar 

  • Rao SN, Chandra Mohan D, Adimurthy S (2015) H-β-zeolite catalyzed transamidation of carboxamides, phthalimide, formamides and thioamides with amines under neat conditions. RSC Adv 5:95313–95317. https://doi.org/10.1039/C5RA16933J

    Article  Google Scholar 

  • Roughley SD, Jordan AM (2011) The medicinal chemist’s toolbox: an analysis of reactions used in the pursuit of drug candidates. J Med Chem 54:3451–3479

    Article  Google Scholar 

  • Shimizu Y, Morimoto H, Zhang M, Ohshima T (2012) Microwave-assisted deacylation of unactivated amides using ammonium-salt-accelerated transamidation. Angew Chemie Int Ed 51:8564–8567

    Article  Google Scholar 

  • Slowing II, Trewyn BG, Giri S, Lin VS-Y (2007) Mesoporous silica nanoparticles for drug delivery and biosensing applications. Adv Funct Mater 17:1225–1236. https://doi.org/10.1002/adfm.200601191

    Article  Google Scholar 

  • Starkov P, Sheppard TD (2011) Borate esters as convenient reagents for direct amidation of carboxylic acids and transamidation of primary amides. Org Biomol Chem 9:1320–1323

    Article  Google Scholar 

  • Suchý M, Elmehriki AAH, Hudson RHE (2011) A remarkably simple protocol for the N-formylation of amino acid esters and primary amines. Org Lett 13:3952–3955

    Article  Google Scholar 

  • Tamura M, Tonomura T, Shimizu K, Satsuma A (2012) Transamidation of amides with amines under solvent-free conditions using a CeO 2 catalyst. Green Chem 14:717–724

    Article  Google Scholar 

  • Thale PB, Borase PN, Shankarling GS (2016) Transamidation catalysed by a magnetically separable Fe 3 O 4 nano catalyst under solvent-free conditions. RSC Adv 6:52724–52728

    Article  Google Scholar 

  • Valeur E, Bradley M (2009) Amide bond formation: beyond the myth of coupling reagents. Chem Soc Rev 38:606–631

    Article  Google Scholar 

  • Vanjari R, Allam BK, Singh KN (2013) Hypervalent iodine catalyzed transamidation of carboxamides with amines. RSC Adv 3:1691–1694

    Article  Google Scholar 

  • Walcarius A, Mercier L (2010) Mesoporous organosilica adsorbents: nanoengineered materials for removal of organic and inorganic pollutants. J Mater Chem 20:4478–4511

    Article  Google Scholar 

  • Xu K, Hu Y, Zhang S, Zha Z, Wang Z (2012) Direct amidation of alcohols with N-substituted formamides under transition-metal-free conditions. Chem Eur J 18:9793–9797

    Article  Google Scholar 

  • Yedage SL, D’silva DS, Bhanage BM (2015) MnO 2 catalyzed formylation of amines and transamidation of amides under solvent-free conditions. RSC Adv 5:80441–80449

    Article  Google Scholar 

  • Zhang M, Imm S, Bähn S, Neubert L, Neumann H, Beller M (2012) Efficient copper (II)-catalyzed transamidation of non-activated primary carboxamides and ureas with amines. Angew Chemie Int Ed 51:3905–3909

    Article  Google Scholar 

  • Zweifel T, Naubron JV, Grützmacher H (2009) Catalyzed dehydrogenative coupling of primary alcohols with water, methanol, or amines. Angew Chemie - Int Ed 48:559–563. https://doi.org/10.1002/anie.200804757

    Article  Google Scholar 

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Authors and Affiliations

  1. Department of Chemistry, Tarbiat Modares University, P.O. Box 14155-175, Tehran, Iran

    Esmaiel Eidi, Mohamad Z. Kassaee & Zahra Nasresfahani

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  1. Esmaiel Eidi
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  2. Mohamad Z. Kassaee
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  3. Zahra Nasresfahani
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Correspondence to Mohamad Z. Kassaee.

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The authors declare that they have no conflict of interest.

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Mohamad Z. Kassaee is a visiting scholar (sabbatical)

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Eidi, E., Kassaee, M.Z. & Nasresfahani, Z. Mesoporous silica nanoparticles in an efficient solvent-free transamidation of carboxamides with amines: an exhibition of a green recyclable nanocatalyst. J Nanopart Res 20, 99 (2018). https://doi.org/10.1007/s11051-018-4195-5

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  • DOI: https://doi.org/10.1007/s11051-018-4195-5

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