Authors
1 Chemistry Division, School of Advanced Sciences, VIT University, India-600 127+Department of Medicinal Chemistry, GVK Biosciences Pvt. Ltd, India-500 076
2 Department of Medicinal Chemistry, GVK Biosciences Pvt. Ltd, India-500 076
3 Chemistry Division, School of Advanced Sciences, VIT University, India-600 127
Abstract
Nanoporous heterogeneous AlSBA-15 (x) type aluminosilicate catalyst with different nSi/nAl ratios (x = 41, 129, and 210) was synthesized using hydrothermal method. AlSBA-15 catalysts were characterized by XRD, N2 sorption, TPD-NH3, FT-IR, SEM and TEM. XRD analyses of AlSBA-15 catalysts confirmed the presence of well-ordered crystalline structure with p6mm symmetry. N2 isotherm of AlSBA-15 catalyst materials showed a type IV adsorption isotherm with H1 hysteresis loops. The specific surface area and specific pore volume of the AlSBA-15 catalysts are in the rage from 480 to 757 m2/g and from 0.65 to 0.95 cm3/g, respectively. SEM analysis of AlSBA-15 (41) revealed a worm-like particle morphology comprising particles in a size range of 3 μm with the co-existence of smaller particles of ca. 1 μm size. A distinct approach adopted for the synthesis of α-aminonitriles using heterogeneous nanoporous AlSBA-15 catalyst via Strecker reaction. This one-pot, three component system of amines (primary/secondary), carbonyl compounds (aldehydes/ketone) and TMSCN compounds proceed excellently in the presence of AlSBA-15 catalyst in water medium at room temperature (RT). The major advantages are excellent yield, short reaction time, high chemo-selectivity, simple experimental procedure, recyclability of the catalyst, easy work up procedure. This one-pot synthesis consists of two consecutive steps: (1) imine formation from amine and aldehyde/ketone and (2) cyano addition to imine. The findings suggest that catalyst is recyclable and can be reused up to six cycles.
Keywords
- Chaturvedi, D., A.K. Chaturvedi, P.K. Dwivedi and N. Mishra, 2013. A Novel Approach to the Synthesis of α-Aminonitriles Using Triphenyl-phosphine Dibromide under Solvent-Free Conditions. Synlett, 24(01): 33-36.
- Shafran, Y.M., V.A. Bakulev and V.S. Mokrushin, 1989. Synthesis and properties of α-aminonitriles. Russian Chemical Reviews, 58(2): 148-162.
- Enders, D., and J.P. Shilvock, 2000. Some recent applications of α-amino nitrile chemistry. Chemical Society Reviews, 29(5): 359-373.
- Matier, W.L., D.A. Owens, W.T. Comer, D. Deitchman, H.C. Ferguson, R.J. Seidehamel and J.R. Young, 1973. Antihypertensive agents. Synthesis and biological properties of 2-amino-4-aryl-2-imidazolines. Journal of medicinal chemistry, 16(8): 901-908.
- Dyker, G., 1997. Amino acid derivatives by multicomponent reactions. Angewandte Chemie International Edition, 36(16): 1700-1702.
- Weinstock, L.M., P. Davis, B. Handelsman and R.J. Tull, 1967. General synthetic system for 1, 2, 5-thiadiazoles. The Journal of Organic Chemistry, 32(9): 2823-2829.
- Duthaler, R.O., 1994. Recent developments in the stereoselective synthesis of α-aminoacids. Tetrahedron, 50(6): 1539-1650.
- Nakamura, S., N. Sato, M. Sugimoto and T. Toru, 2004. A new approach to enantioselective cyanation of imines with Et2AlCN. Tetrahedron: Asymmetry, 15(9): 1513-1516.
- Harusawa, S., Y. Hamada, and T. Shioiri, 1979. Diethyl phosphorocyanidated (DEPC). A novel reagent for the classical Strecker's α-amino nitrile synthesis. Tetrahedron Letters, 20(48): 4663-4666.
- Abell, J.P. and H. Yamamoto, 2009. Dual-activation asymmetric Strecker reaction of aldimines and ketimines catalyzed by a tethered bis (8-quinolinolato) aluminium complex. Journal of the American Chemical Society, 131(42): 15118-15119.
- Sipos, S. and I. Jablonkai, 2009. One-pot synthesis of α-aminonitriles from alkyl and aryl cyanides: a Strecker reaction via aldimine alanes. Tetrahedron Letters, 50(16): 1844-1846.
- Li, Z., Y. Ma, J. Xu, J. Shi and H. Cai, 2010. One-pot three-component synthesis of α-aminonitriles using potassium hexacyanoferrate (II) as an eco-friendly cyanide source. Tetrahedron Letters, 51(30): 3922-3926.
- Enders, D. and J.P. Shilvock, 2000. Some recent applications of α-amino nitrile chemistry. Chemical Society Reviews, 29(5): 359-373.
- Vongvilai, P. and O. Ramstrom, 2009. Dynamic asymmetric multicomponent resolution: lipase-mediated amidation of a double dynamic covalent system. Journal of the American Chemical Society, 131(40): 14419-14425.
- Banphavichit, V., W. Mansawat, W. Bhanthumnavin and T. Vilaivan, 2004. A highly enantioselective Strecker reaction catalyzed by titanium-N-salicyl-β-aminoalcohol complexes. Tetrahedron, 60(46): 10559-10568.
- Prasad, B.B., A. Bisai and V.K. Singh, 2004. Trimethylsilyl cyanide addition to aldimines and its application in the synthesis of (S)-phenylglycine methyl ester. Tetrahedron letters, 45(52): 9565-9567.
- Evans, D.A., G.L. Carroll and L.K. Truesdale, 1974. Synthetic applications of trimethylsilyl cyanide. Efficient synthesis of beta-aminomethyl alcohols. The Journal of Organic Chemistry, 39(7): 914-917.
- Evans, D.A., L.K. Truesdale and G.L. Carroll, 1973. Cyanosilylation of aldehydes and ketones. A convenient route to cyanohydrin derivatives. Journal of the Chemical Society, Chemical Communications, (2): 55-56.
- Kobayashi, S., H. Ishitani and M. Ueno, 1997. Facile synthesis of α-amino nitriles using lanthanide triflate as a Lewis acid catalyst. Synlett, 1(01): 115-116.
- Paraskar, A.S. and A. Sudalai, 2006. Cu(OTf)2 or Et3N-catalyzed three-component condensation of aldehydes, amines and cyanides: a high yielding synthesis of α-aminonitriles. Tetrahedron letters, 47(32): 5759-5762.
- De, S.K. and R.A. Gibbs, 2004. Bismuth trichloride catalyzed synthesis of α-aminonitriles. Tetrahedron letters, 45(40): 7407-7408.
- De, S.K., 2005. RuCl3 Catalyzed One‐Pot Synthesis of α‐Aminonitriles. Synthetic communications, 35(5): 653-656.
- Kobayashi, S. and T. Busujima, 1998. Scandium triflate-catalyzed Strecker-type reactions of aldehydes, amines and tributyltin cyanide in both organic and aqueous solutions. Achievement of complete recovery of the tin compounds toward environmentally-friendly chemical processes. Chemical Communications, (9): 981-982.
- Karmakar, B. and J. Banerji, 2010. K2PdCl4 catalyzed efficient multicomponent synthesis of α-aminonitriles in aqueous media. Tetrahedron Letters, 51(20): 2748-2750.
- Narasimhulu, M., T.S. Reddy, K.C. Mahesh, S.M. Reddy, A.V. Reddy and Y. Venkateswarlu, 2007. Lanthanum (III) nitrate hexahydrate or gadolinium (III) chloride hexahydrate catalyzed one-pot synthesis of α-amino nitriles. Journal of Molecular Catalysis A: Chemical, 264(1): 288-292.
- Shen, Z.L., S.J. Ji, and T.P. Loh, 2008. Indium (III) iodide-mediated Strecker reaction in water: an efficient and environmentally friendly approach for the synthesis of α-aminonitrile via a three-component condensation. Tetrahedron, 64(35): 8159-8163.
- Pasha, M.A., H.M. Nanjundaswamy and V.P. Jayashankara, 2007. Cerium (III) Chloride: A Highly Efficient Reagent for the Synthesis of α‐Aminonitriles. Synthetic Communications, 37(24): 4371-4380.
- Raghu, M. and C. Sanjeeva Reddy, 2009. ZrCl4 promoted efficient one-pot synthesis of α-amino nitriles. Indian journal of chemistry. Sect. B: Organic chemistry, including medical chemistry, 48(2): 295-300.
- Li, Z., Y. Ma, J. Xu, J. Shi, and H. Cai, 2010. One-pot three-component synthesis of α-aminonitriles using potassium hexacyanoferrate (II) as an eco-friendly cyanide source. Tetrahedron Letters, 51(30): 3922-3926.
- Reddy, C. S. and M. Raghu, 2008. p-Toluenesulfonic acid catalyzed rapid and efficient protocol for one-pot synthesis of α-amino nitriles. Indian Journal Chemistry, 47B: 1572-1577.
- Thielemann, J.P., F. Girgsdies, R. Schlögl and C. Hess 2011. Pore structure and surface area of silica SBA-15: influence of washing and scale-up. Beilstein journal of nanotechnology, 2: 110-118.
- Chandrasekar, G., M. Hartmann and V. Murugesan, 2014. Immobilization of cytochrome c on the cylindrical mesoporous silica extrudates. Journal of nanoscience and nanotechnology, 14(3): 2606-2613.
- Melde, B.J., B.J. Johnson and P.T. Charles, 2008. Mesoporous silicate materials in sensing. Sensors, 8(8): 5202-5228.
- Bagherzade, G. and S. Aryanejad, 2016. Green One-pot Synthesis of α–aminonitriles by Nanocrystalline CeO2 as Heterogeneous Environmental Friendly Catalyst. Current Catalysis, 5(3): 220-227.
- Shekouhy, M., A. Moaddeli and A. Khalafi-Nezhad, 2016. Magnetic Fe3O4–BF3: highly efficient Lewis acid catalyst for the synthesis of α-aminonitriles. Research on Chemical Intermediates, 42(4): 3805-3827.
- Mansoor, S.S., K. Aswin, K. Logaiya and S.P.N. Sudhan, 2016. ZrOCl2·8H2O: an efficient and recyclable catalyst for the three-component synthesis of amidoalkyl naphthols under solvent-free conditions. Journal of Saudi Chemical Society, 20(2): 138-150.
- Maleki, A., R.F. Haji, M. Ghassemi and H. Ghafuri, 2017. Preparation and application of a magnetic organic-inorganic hybrid nanocatalyst for the synthesis of α-aminonitriles. Journal of Chemical Sciences, 129(4): 457-462.
- Prakash, G.S., T.E. Thomas, I. Bychinskaya, A.G. Prakash, C. Panja, H. Vaghoo and G.A. Olah, 2008. Efficient green synthesis of α-aminonitriles, precursors of α-amino acids. Green Chemistry, 10(10): 1105-1110.
- Gharib, A., N.N. Pesyan, L.V. Fard, and M. Roshani, 2014. ZnO Nanoparticle as Catalyst for Efficient Green Synthesis of Antiplatelet Drug (Clopidogrel). Journal of chemical engineering and chemistry research, 1(1): 1-5.
- Rafiee, E., A. Azad and M. Joshaghani, 2007. K5CoW12O40. 3H2O: Highly Efficient Heterogeneous Catalyst for the Synthesis of α-Aminonitriles. Letters in Organic Chemistry, 4(1): 60-63.
- Rafiee, E., S. Rashidzadeh, S. Eavani and M. Joshaghani, 2010. KSF-supported heteropoly acids catalyzed one-pot synthesis of α-aminonitriles. Bulletin of the Chemical Society of Ethiopia, 24(2): 209-215.
- Rafiee, E., S. Rashidzadeh, M. Joshaghani, H. Chalabeh and K. Afza, 2008. γ-Al2O3-Supported 12-Tungstosilicic Acid as an Efficient Heterogeneous Catalyst for the Synthesis of α-Aminonitrile. Synthetic Communications, 38(16): 2741-2747.
- Herrerias, C.I., X. Yao, Z. Li and C.J. Li, 2007. Reactions of C− H Bonds in Water. Chemical reviews, 107(6): 2546-2562.
- Babu, G. and P.T. Perumal, 2000. Synthetic applications of indium trichloride catalyzed reactions. ChemInform, 31(47).
- T. P. Loh, 2004. Science of Synthesis, (Ed. H. Yamamoto), Georg Thieme: Stuttgart, New York, USA, 413.
- Galletti, P., M. Pori and D. Giacomini, 2011. Catalyst‐Free Strecker Reaction in Water: A Simple and Efficient Protocol using Acetone Cyanohydrin as Cyanide Source. European Journal of Organic Chemistry, 2011(20): 3896-3903.
- Shen, Z.L., S.J. Ji, and T.P. Loh, 2008. Indium (III) iodide-mediated Strecker reaction in water: an efficient and environmentally friendly approach for the synthesis of α-aminonitrile via a three-component condensation. Tetrahedron, 64(35): 8159-8163.
- Das, B., G. Satyalakshmi and K. Suneel, 2009. Convenient and rapid synthesis of α-aminonitriles starting directly from nitro compounds in water. Tetrahedron Letters, 50(23): 2770-2773.
- Surendra, K., N.S. Krishnaveni, A. Mahesh and K.R. Rao, 2006. Supramolecular catalysis of Strecker reaction in water under neutral conditions in the presence of β-cyclodextrin. The Journal of organic chemistry, 71(6): 2532-2534.
- Vinu, A., G.S. Kumar, K. Ariga and V. Murugesan, 2005. Preparation of highly ordered mesoporous AlSBA-15 and its application to isopropylation of m-cresol. Journal of Molecular Catalysis A: Chemical, 235(1): 57-66.
- Kim, N.Y., J.S. Jung, J.S. Lee, E.H. Yang, G.H. Hong, S.S. Lim, and D.J. Moon, 2016. Synthesis and characterization of Al-modified SBA-15 for Fischer–Tropsch synthesis (FTS) reaction. Research on Chemical Intermediates, 42(1): 319-334.
- M. Gómez-Cazalilla, J.M. Mérida-Robles, A. Gurbani, E. Rodríguez-Castellón and A. Jiménez-López, 2007. Characterization and acidic properties of Al-SBA-15 materials prepared by post-synthesis alumination of a low-cost ordered mesoporous silica. Journal of Solid State Chemistry, 180(3): 1130-1140.
- Chandrasekar, G., M. Hartmann and V. Murugesan, 2014. Immobilization of cytochrome c on the cylindrical mesoporous silica extrudates. Journal of nanoscience and nanotechnology, 14(3): 2606-2613.
- Kumaran, G.M., S. Garg, K. Soni, M. Kumar, J.K. Gupta, L.D. Sharma, and G.M. Dhar, 2008. Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios. Microporous and Mesoporous Materials, 114(1): 103-109.
- Koekkoek, A. J., J.R. Van Veen, P.B. Gerrtisen, P. Giltay, P.C. Magusin and E.J. Hensen, 2012. Brønsted acidity of Al/SBA-15. Microporous and Mesoporous Materials, 151: 34-43.
- Pourmousavi, S.A. and H. Salahshornia, 2011. Efficient, Rapid and Solvent-free Cyanosilylation of Aldehydes and Ketones Catalyzed by SbCl3. Bulletin of the Korean Chemical Society, 32(5): 1575-1578.
- Estevez, V., V. Sridharan, S. Sabate, M. Villacampa and J.C. Menéndez, 2016. Three‐Component Synthesis of Pyrrole‐Related Nitrogen Heterocycles by a Hantzsch‐Type Process: Comparison between Conventional and High‐Speed Vibration Milling Conditions. Asian Journal of Organic Chemistry, 5(5): 652-662.
- Subhani, M.A., K.S. Müller, F. Koç and P. Eilbracht, 2009. A new one-pot hydroformylation/Strecker synthesis as a versatile synthetic tool for polyfunctional compounds and functionalization of dendrimers. Organic & biomolecular chemistry, 7(19): 4000-4008.
- Reddy, B.M., B. Thirupathi and M.K. Patil, 2009. Highly efficient promoted zirconia solid acid catalysts for synthesis of α-aminonitriles using trimethylsilyl cyanide. Journal of Molecular Catalysis A: Chemical, 307(1): 154-159.
- Karimi, B. and D. Zareyee, 2009. Solvent-free three component Strecker reaction of ketones using highly recyclable and hydrophobic sulfonic acid based nanoreactors. Journal of Materials Chemistry, 19(45): 8665-8670.
- Rajabi, F., S. Nourian, S. Ghiassian, A.M. Balu, M.R. Saidi J.C. Serrano-Ruiz and R. Luque, 2011. Heterogeneously catalysed Strecker-type reactions using supported Co (II) catalysts: Microwave vs. conventional heating. Green Chemistry, 13(11): 3282-3289.
- Saidi, M.R. and N. Azizi, 2004. A novel and efficient method for the synthesis of α-aminonitriles by the reaction of aminals with trimethylsilyl cyanide catalyzed by iodine. Journal of the Iranian Chemical Society, 1(2): 136-140.
- Reddy, S.S., B.R.P. Reddy and P.V.G. Reddy, 2015. Propylphosphonic anhydride (T3P®) catalyzed one-pot synthesis of α-aminonitriles. Chinese Chemical Letters, 26(6): 739-743.