Triphenylphosphine Catalysed Facile Multicomponent Synthesis of 2-Amino-3-Cyano-6-Methyl-4-Aryl-4H-Pyrans

Document Type: Research Article

Authors

1 Research Department of Chemistry, Bioactive Organic Molecule Synthetic Unit, C. Abdul Hakeem College, Melvisharam - 632 509, Tamil Nadu, INDIA

2 School of Chemistry, Damghan University, 36715-364, Damghan, I.R. IRAN

3 C.abdul Hakeem College, Melvisharam - 632 509. India

Abstract

Triphenyl phosphine(PPh3), an efficient and reusable catalyst, catalysed the synthesis of 2-amino-3-cyano-6-methyl-4-aryl-4H-pyran-5-ethylcarboxylate derivatives by one-pot condensation of aromatic aldehydes, malononitrile and ethyl acetoacetate in EtOH-H2O (1:1) at reflux conditions. The results show that aromatic aldehydes containing electron-donating groups or electron-withdrawing groups could react smoothly to give the corresponding products in good
to excellent yields.
Given the increasing levels of interest in green chemistry, the recyclability and reusability of the catalyst have been evaluated. It was also found that triphenyl phosphinecan be recycled at least four times without loss of activity. This method has the advantages of high yield,mild reaction conditions, environmentally benign methodology and short reaction time.

Keywords

Main Subjects


[1] Domling A., Ugi I., Multicomponent Reactions with Isocyanides, Angew. Chem. Int. Ed., 39: 3168-3210 (2000).

[2] Yaghoub S., Mohammad F., Four-Component Reaction between Ethyl benzoylacetate, Hydroxylamine, Aldehydes and Malononitrile: Synthesis of Isoxazol-5(2H)-ones, Iran. J. Chem. Chem. Eng. (IJCCE), 35(2): 9-13 (2016).

[3] Saeedi M., Jeiroudi M., Ma’mani L., Mahdavi M., Alipour E., Shafiee, A.,  Foroumadi A. R., Brønsted Acidic Phosphonium based Ionic liquid functionalized SBA-15 [HO3S-PhospIL@SBA-15]: Green, Recyclable, and Efficient Catalyst for the Synthesis of Pyrano[3,2-c]chromenone Derivatives,  Iran. J. Chem. Chem. Eng. (IJCCE) 34(4): 39-45 (2015).

[4] Zhang J., Hu X., Zhou  Z., Efficient and Eco-friendly Procedure for the Synthesis of 2-Amino-4H-Chromenes Catalyzed by Diammonium Hydrogen Phosphate,  Iran. J. Chem. Chem. Eng. (IJCCE), 34(4): 47-51 (2015).

[8] Wang J.L., Liu D., Zhang Z., Shan S., Han X.,  Srinvasula S.M., Croce C.M., Alnemeri E.S.,  Huang Z., Structure-based Discovery of an Organic Compound that binds Bcl-2 protein and induces Apoptosis of Tumor CellsProc. Natl. Acad. Sci. U.S.A.  97: 7124-7129 (2000).

[9] Mohr S.J., Chirigos M.A., Fuhrman F.S., Pryor J.W., Pyran Copolymer as an Effective Adjuvant to Chemotherapy Against a Murine Leukemia and Solid Tumor, Cancer Res., 35(12): 3750-3754 (1975).

[10] Suarez M., Salfran E., Verdecia Y., Ochoa E., Alba L., Martin N., Martinez R.,  Quinteiro M., Seoane C., Novoa H., Blaton N., Peeters O.M., Ranter C.D.,
X-Ray and Theoretical Structural Study of Novel 5,6,7,8-tetrahydrobenzo-4H-pyrans, Tetrahedron, 58(5): 953-960 (2002).

[11] Hafez E.A., Elnagdi M.H., Elagamey A.A., El-Taweel F.A., Nitriles in Heterocyclic Synthesis: Novel Synthesis of Benzo[c]coumarin and of Benzo[c]pyrano[3,2-c]quinoline Derivatives, Heterocycles, 26: 903-907 (1987).

[12] Pratap U. R., Jawale D.V., Netankar P. D., Mane R. A., Baker’s yeast Catalyzed One-Pot Three-Component Synthesis of Polyfunctionalized 4H-pyransTetrahedron Lett., 52(44): 5817–5819 (2011).

[13] Kumar D., Reddy V.B., Sharad S., Dube U., Kapur S., A Facile One-pot Green Synthesis and Antibacterial Activity of 2-Amino-4H-pyrans and 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-chromenes, Eur.  J. Med. Chem., 44(9): 3805-3809 (2009).

[14] Hekmatshoar, R., Majedi, S., Bakhtiari, K., Sodium Selenate Catalyzed Simple and Efficient Synthesis of Tetrahydro Benzo[b]pyran DerivativesCatal. Commun. 9(2): 307-310 (2008).

[15] Nemouchi S., Boulcina R.,  Carboni B., Debache A., Phenylboronic Acid as an Efficient and Convenient Catalyst for a Three-component Synthesis of Tetrahydrobenzo[b]pyrans, C. R. Chimie., 15(2): 394-397 (2012).

[16] Behbahani F.K., Alipour A., One-Pot Synthesis of 2-Amino-4H-Pyrans and 2-Amino-Tetrahydro-4H-Chromenes Using L-Proline, GU J. Sci., 28(3): 387-393 (2015).

[17] Bodaghifard M. A., Ahadi N., One-pot Synthesis of Tetrahyrobenzo[b]pyran and Dihydropyrano[c]chromene Derivatives Using Ammonium Alum in Green Media, Bulg. Chem. Commun., 47(2): 603-606 (2015).

[18] Debache A., Amimour M., Belfaitah A., Rhouati S., Carboni B., A One-pot Biginelli Synthesis of 3,4-Dihydropyrimidin-2-(1H)-ones/thiones Catalyzed by Triphenylphosphine as Lewis Base, Tetrahedron Lett., 49(42): 6119-6121 (2008).

[19] Debache A., Ghalem W., Boulcina R.,Belfaitah A., Rhouati S., Carboni B., An Efficient One-step Synthesis of 1,4-Dihydropyridines via a Triphenylphosphine-catalyzed Three-component Hantzsch Reaction under Mild Conditions,Tetrahedron Lett.,  50(37): 5248 - 5250 (2009).

[20] Ghashang M., Mansoor S.S., Aswin K., Use of Silica Gel-Supported Aluminium Chloride as Reusable Catalyst for Expeditious Synthesis of a Novel Series of 11-Amino-12-aryl-hexahydro-5-oxa-6,13-diazaindeno[1,2-b]anthracene Derivatives, Res. Chem. Intermed., 41: 6665-6686 (2015)

[21] Aswin K., Mansoor S.S., Logaiya K., Sudhan S.P. N., Triphenylphosphine: An Efficient Catalyst for the Synthesis of 4,6-Diphenyl-3,4-Dihydropyrimidine-2(1H)-thione under Thermal conditions, J. King Saud Univ - Sci.,  26(2): 141-148 (2014).

[27] Anastas P.T., Warner J.C., “Green Chemistry: Theory and Practice”, Oxford University Press, Oxford, 1998.

[28] Khaligh N.G., 4-(Succinimido)-1-butane Sulfonic Acid as a Bronsted Acid Catalyst for Synthesis of Pyrano[4,3-b]pyran Derivatives under Solvent-free Conditions, Chin. Chem. Lett., 26(1): 26–30 (2015)

[29] Gohani M., H. van Tonder J., C.B. Benzuidenhoudt, B., NaHSO4-SiO2: An Efficient Reusable Green Catalyst for Selective C-3 Propargylation of Indoles with Tertiary Propargylic Alcohols,  Iran. J. Chem. Chem. Eng. (IJCCE), 34(3): 11-17 (2015).