IJOC  Vol.1 No.3 , September 2011
Pineapple Juice as a Natural Catalyst: An Excellent Catalyst for Biginelli Reaction
Abstract: An efficient and greener synthesis of a series of dihydropyrimidinone (DHPMs) derivatives were accomplished via three-component one-pot cyclocondensation between substituted aryl aldehydes, diketone/ke- toester and urea. This solvent free approach is totally nonpolluting having several advantages such as shorter reaction time, mild reaction conditions, simple workup and reduced environmental impact.
Cite this paper: nullS. Patil, S. Jadhav and S. Mane, "Pineapple Juice as a Natural Catalyst: An Excellent Catalyst for Biginelli Reaction," International Journal of Organic Chemistry, Vol. 1 No. 3, 2011, pp. 125-131. doi: 10.4236/ijoc.2011.13019.

[1]   E. Ramesh and R. Raghunathan, “Microwave-Assisted K-10 Montmorillonite Clay-Mediated Knoevenagel Hetero-Diels-Alder Reactions: A Novel Protocol for the Synthesis of Polycyclic Pyrano[2,3,4-kl]xanthene Derivatives,” Synthetic Communications, Vol. 39, No. 4, 2009, pp. 613-625. doi:10.1080/00397910802417825

[2]   D. Habibi and O. Marvi, “Montmorillonite KSF and Montmorillonite K-10 Clays as Efficient Catalyst for the Solventless Synthesis a Bismaleimides and Bisphthlimides Using Microwave Irradiation,” Arkivoc, (XIII), 2006, pp. 8-15.

[3]   M. Zahouily, B. Mounir, H. Charki, A. Mezdar, B. Bahlaouan and M. Ouammou, “Investigation of the Basic Catalytic Activity of Natural Phosphates in the Michael Condensation,” Arkivoc, (XIII), 2006, pp. 178-186.

[4]   M. Zahouily, B. Bahlaouan, A. Rayadh and S. Sebti, “Natural Phosphate and Potassium Fluoride Doped Natural Phosphate: Efficient Catalysts for the Construction of a Carbon-Nitrogen Bond,” Tetrahedron Letters, Vol. 45, No. 12, 2004, pp. 4135-4138.

[5]   E. Genin, P. Y. Toullec, P. Marie, S. Antoniotti, C. Brancour, J. P. Genêt and V. Michelet, “Gold Catalysis in Organic Synthesis: Efficient Intramolecular Cyclization of γ-Acetylenic Carboxylic Acids to 5-Exo-Alkylidene- Butyrolactones,” Arkivoc, (V), 2007, pp. 67-78.

[6]   Y. Riadi, R. Mamouni, R. Azzalou, R. Boulahjar, Y. Abrouki, M. El. Haddad, S. Routier, G. Guillaumet and S. Lazar, “Animal Bone Meal as an Efficient Catalyst for Crossed-Aldol Condensation,” Tetrahedron Letters, Vol. 51, No. 51, 2010, pp. 6715-6717. doi:10.1016/j.tetlet.2010.10.056

[7]   D. Arthey, “Fruit and Vegetable Product,” In: M. D. Ranken, R. C. Kill and C. G. J. Baker, Eds., Food Industries Manual, Chapman & Hall, London, 1995, p. 151.

[8]   A. P. Bartolomé, P. Rupérez and C. Fúster, “Pineapple Fruit: Morphological Characteristics, Chemical Composition and Sensory Analysis of Red Spanish and Smooth Cayenne Cultivars,” Food Chemistry, Vol. 53, No. 1, 1995, pp. 75-79. doi:10.1016/0308-8146(95)95790-D

[9]   J. A. Duke, “Handbook of Energy Crops,” Unpublished, 1983.

[10]   J. A. Samson, “Tropical Fruits,” 2nd Edition, Longman Inc., New York, 1986.

[11]   S. K. Adhikari, W. P. Harkare, K. P. Govindan, K. C. Chikkappaji, S. Saroja and A. M. Nanjundaswamy, “Deacidification of Fruit Juices by Electrodialysis. Part II,” Indian Journal of Technology, Vol. 25, 1987, pp. 24.

[12]   P. Biginelli, “Derivati Aldeiduredici Degli Eteri Acetile Dossal-Acetico,” Gazzetta Chimica Italiana, Vol. 23, 1893, pp. 360-416.

[13]   G. C. Rovnyak, S. D. Kimall, B. Beyer, G. Cucinotta, J. D. DiMarco, J. Gougoutas, A. Hedberg, M. Malley and J. P. McCarthy, “Calcium Entry Blockers and Activators: Conformational and Structural Determinants of Dihydropyrimidine Calcium Channel Modulators,” Journal of Medicinal Chemistry, Vol. 38. No. 1, 1995, pp. 119-129. doi:10.1021/jm00001a017

[14]   K. S. Atwal, G. C. Rovnyak, J. Schwartz, S. Moreland, A. Hedberg, J. Z. Gougoutas, M. F. Malley and D. M. Floyd, “Dihydropyrimidine Calcium Channel Blockers: 2-He- terosubstituted 4-Aryl-1,4-Dihydro-6-Methyl-5-Pyrimidi- necarboxylic Acid Esters as Potent Mimics of Dihydropyridines,” Journal of Medicinal Chemistry, Vol. 33, No. 5, 1990, pp. 1510-1515. doi:10.1021/jm00167a035

[15]   K. S. Atwal, G. C. Rovnyak, S. D. Kimball, D. M. Floyed, B. N. Moreland, S. Swanson, J. Z. Gougoutas, J. Schwartz, K. M. Smillie and M. F. Malley, “Dihydropyrimidine Calcium Channel Blockers. II. 3-Substituted- 4-Aryl-1,4-Dihydro-6-Methyl-5-Pyrimidinecarboxylic A- cid Esters as Potent Mimics of Dihydropyridines,” Journal of Medicinal Chemistry, Vol. 33, No. 9, 1990, pp. 2629-2635. doi:10.1021/jm00171a044

[16]   J. J. Baldwin, D. A. Claremon and D. E. McClure, “5- Acetyl-3,4,5,6-Tetrahydro-4-Oxo-2,6-Methano-2H-1,3,5- Benzothiazocine(benzodiazocine)-11-Carboxylates Useful as Calcium Channel Blockers,” US Patent No. 4609494, 1986.

[17]   J. J. Baldwin, S. M. Ptizenberger and D. E. McClure, “Substituted Pyrimidines Useful as Calcium Channel Blockers,” US Patent No. 4675321, 1987.

[18]   K. S. Atwal, “1,2,3,4-Tetrahydro-6-Substituted-4-Aryl- 3-(Substitutedsfonyl)-2-Thioxo(oroxo)-5-Pyrimidinecar- Boxylic Acids and Esters and Method of Using Them to Lower Blood Pressure,” US Patent No. 4684656, 1987.

[19]   H. Cho, M. Ueda, K. Shima, A. Mizuno, M. Hayashimatsu, Y. Ohnaka, Y. Takeuchi, M. Hamaguchi, K. Aisaka, T. Hidaka, M. Kawai, M. Takeda, T. Ishihara, K. Funahashi, F. Satoh, M. Morita and T. Noguchi, “Dihydropyrimidines: Novel Calcium Antagonists with Potent and Long-Lasting Vasodilative and Anti-Hypertensive Activity,” Journal of Medicinal Chemistry, Vol. 32, No. 10, 1989, pp. 2399-2406. doi:10.1021/jm00130a029

[20]   T. Boumoud, B. Boumoud, S. Rhouati, A. Belfaitah, A. Deache and P. Mosset, “A Novel Catalyst for One-Pot Synthesis of Substituted 3,4-Dihydropyrimidin-2-(1H)- ones via Biginelli Reaction Under Solvent-Free Conditions,” Acta Chimica Slovenica, Vol. 55, 2008, pp. 617- 622.

[21]   T. Boumoud, B. Boumoud, S. Rhouati, A. Belfaitah, A. Deache and P. Mosset, “An Efficient and Recycling Catalyst for the One-Pot Three-Component Synthesis of Substituted 3,4-Dihydropyrimidin-2(1H)-ones,” E-Jour- nal of Chemistry, Vol. 5, No. 4, 2008, pp. 688-695.

[22]   J. Lu, Y. Bai, Z. Wang, B. Yang and H. Ma, “One-Pot Synthesis of 3,4-Dihydropyrimidin-2(1H)-Ones Using Lanthanum Chloride as a Catalyst,” Tetrahedron Letters, Vol. 41, No. 47, 2000, pp. 9075-9078. 7doi:10.1016/S0040-4039(00)01645-2

[23]   M. B. Deshmukh, P. V. Anbhule, S. D. Jadhav, A. R. Mali, S. S. Jagtap and S. A. Deshmukh, “An Efficient, Simple, One Pot Synthesis of Dihydropyrimidine-2(1H)- Ones Using Phosphorus Pentoxide,” Indian Journal of Chemistry, Vol. 46B, No. 9, 2007, pp. 1545-1548.

[24]   D. Shobha, M. A. Chari, P. Sadanandam and K. Mukkanti, “Dichloro Dicyano Quinone (DDQ) as Coupling Reagent for High Yield Synthesis of 3,4-Dihydro- Pyrimidin-2-(1H)-Ones,” Journal of Heterocyclic Chemistry, Vol. 45, 2008, pp. 1225-1227.

[25]   N. Y. Fu, M. L. Pang, Y. F. Yuan and J. T. Wang, “Indium(III)tribromide: An Excellent Catalyst for Biginelli Reaction,” Chinese Chemical Letters, Vol. 10, 2002, pp. 921-922.

[26]   B. Gangadasu, P. Narender, B. C. Raju and V. J. Rao, “Calcium Chloride Catalyzed Three Component, One-Pot Condensation Reaction: An Efficient Synthesis of 3,4- Dihy-Dropyrimidin-2(1H)-Ones,” Indian Journal of Che- mistry, Vol. 45B, No. 6, 2006, pp. 1259-1263.

[27]   G. Aridoss and Y. T. Jeong, “A Convenient One-Pot Biginelli Reaction Catalyzed by Y(OAc)3: An Improved Protocol for the Synthesis of 3,4-Dihydropyrimidin- 2(1H)-Ones and Their Sulfur Analogues,” Bulletin of the Korean Chemical Society, Vol. 31, No. 4, 2010, pp. 863- 868. doi:10.5012/bkcs.2010.31.04.863

[28]   M. A. Pasha, N. R. Swamy and V. P. Jayshankara, “One Pot Synthesis of 3,4-Dihydropyrimidin-2(1H)-Ones/-Thi- Ones Catalysed by Zinc Chloride: An Improved Procedure for the Biginelli Reaction Using Microwaves under Solvent Free Condition,” Indian Journal of Chemistry, Vol. 44B, No. 3, 2005, pp.823-826.

[29]   S. L. Jain, V. B. Sharma and B. Sain, “Ruthenium-Catalyzed Biginelli Condensation: A Simple and Efficient One-Pot Synthesis of 3,4-Dihydropyrimidin- 2(1H)-ones under Mild Reaction Conditions,” Journal of Heterocyclic Chemistry, Vol. 43, No. 3, 2006, pp. 777- 779. doi:10.1002/jhet.5570430339

[30]   I. Suzuki, Y. Suzumura and K. Takeda, “Metal Triflimide as a Lewis Acid Catalyst for Biginelli Reactions in Water,” Tetrahedron Letters, Vol. 47, 2006, pp. 7861-7864. doi:10.1016/j.tetlet.2006.09.019

[31]   T. Jin, S. Zhang, T. Li, “p-Toluenesulfonic Acid-Cata- lyzed Efficient Synthesis Of Dihydropyrimidines: Improved High Yielding Protocol For The Biginelli Reaction,” Synthetic Communications, Vol. 32, 2002, pp. 1847-1851.

[32]   S. K. Kundu, A. Majee and A. Hajra, “Environmentally Benign Aqueous Zinc Tetrafluoroborate-Catalyzed One- Pot Biginelli Condensation at Room Temperature,” Indian Journal of Chemistry, Vol. 48B, No. 3, 2009, pp. 408-412.

[33]   H. Adrienn, H. Zolta′n and V. Ilona, “Convenient One-Pot Heterogeneous Catalytic Method for the Preparation of 3,4-Dihydropyrimidin-2(1H)-ones,” Synthetic Communications, Vol. 36, 2006, pp. 129-136.

[34]   H. N. Karade, M. Sathe and M. P. Kaushik, “Synthesis of 4-Aryl Substituted 3,4-Dihydropyrimidinones Using Silica-Chloride under Solvent Free Conditions,” Molecules, Vol. 12, 2007, pp. 1341-1351.

[35]   S. Hashem and J. Mahboubeh, “Al2O3/MeSO3H: A Novel and Recyclable Catalyst for One-Pot Synthesis of 3,4- Dihydropyrimidinones or Their Sulfur Derivatives in Biginelli Condensation,” Synthetic Communications, Vol. 39, 2009, pp. 958-979.

[36]   F. Bigi, S. Carloni, B. Fraullanti, R. Maggi and G. Sartori, “A Revision of the Biginelli Reaction under Solid Acid Catalysis. Solvent-Free Synthesis of Dihydropyrimidines over Montmorillonite KSF,” Tetrahedron Letters, Vol. 40, No. 17, 1999, pp. 3465-3468. doi:10.1016/S0040-4039(99)00424-4

[37]   V. R. Rani, N. Srinivas, M. R. Kishan, S. J. Kulkarni and K. V. Raghavan, “Zeolite-Catalyzed Cyclocondensation Reaction for the Selective Synthesis of 3,4- Dihydropyrimidin-2(1H)-Ones,” Green Chemistry, Vol. 3, No. 6, 2001, pp. 305-306. doi:10.1039/b107612b

[38]   V. Singh, S. Kaur, R. Ratti, G. L. Kad and J. Singh, “Acidic Task Specific Ionic Liquid Catalyzed Synthesis of Dipyrimidinones,” Indian Journal of Chemistry, Vol. 49B, No. 5, 2010, pp. 611-616.

[39]   W. Y. Chen, S. D. Qin and J. R. Jin, “Efficient Biginelli Reaction Catalyzed by Sulfamic Acid or Silica Sulfuric Acid under Solvent-Free Conditions,” Synthetic Commu- nications, Vol. 37, 2007, pp. 47-52.

[40]   S. Ramalingam and P. Kumar, “Yttria-Zirconia-Based Lewis Acid Catalysis of the Biginelli Reaction: An Efficient One-Pot Synthesis of 3,4-Dihydropyrimidin-2-(1H)- Ones,” Synthetic Communications, Vol. 39, 2009, pp. 1299-1309.

[41]   T. B. Shah, A. Gupte, M. R. Patel, V. S. Chaudhari, H. Patel and V. C. Patel, “Synthesis and in Vitro Study of Biological Activity of Heterocyclic N-Mannich Bases,” Indian Journal of Chemistry, Vol. 48B, No. 1, 2009, pp. 88-96.