Malaysian Journal of Analytical Sciences Vol 21 No 1 (2017): 13 - 19

DOI: http://dx.doi.org/10.17576/mjas-2017-2101-02

 

 

 

MgCl2 AS EFFICIENT AND INEXPENSIVE CATALYST FOR THE SYNTHESIS OF 1,4-DIHYDROPYRIDINE DERIVATIVES

 

(MgCl2 Sebagai Pemangkin Cekap dan Murah untuk Sintesis Terbitan 1,4-Dihidropiridina)

 

Siti Nur Aqlili Riana Mohd Asseri1, Sian Hui Tan1, Wan Nurul Khursyiah Wan Mohamad1, Seng Chee Poh1,

Poh Wai Chia1,2*, Su-Yin Kan3, Tse Seng Chuah4

 

1School of Marine Science and Environment

2Institute Marine Biotechnology

Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

3Faculty of Health Sciences,

Universiti Sultan Zainal Abidin, 21300 Kuala Terengganu, Terengganu, Malaysia

                4School of Food Science and Technology,

Universiti Malaysia Terengganu, 21030 Kuala Terengganu, Terengganu, Malaysia

 

*Corresponding author: pohwai@umt.edu.my

 

 

Received: 17 August 2016; Accepted: 25 October 2016

 

 

Abstract

The synthesis of 1,4-dihydropyridine (1,4-DHP) derivatives in the presence of alkaline earth metal chlorides was reported. Specifically, the MgCl2 catalyzed the synthesis of 1,4-DHP derivatives in good yields, ranging from 69 – 87%. The Mg2+ serves as the Lewis acid catalyst in the formation of 1,4-DHP and the proposed mechanism of the formation of 1,4-DHP was elaborated in this manuscript. There are many advantages employing MgCl2 as a catalyst in this study, including inexpensive, ubiquitous availability of this metal, simple filtration protocol, which has spark considerable interest in the use of this catalyst in promoting organic reactions.

 

Keywords:  alkaline earth metal, magnesium chloride; 1,4-dihydropyridine

 

Abstrak

Sintesis terbitan 1,4-dihidropiridina (1,4-DHP) dalam kehadiran logam alkali bumi dibincangkan dalam artikel ini. Secara khususnya, sintesis terbitan 1,4-DHP melalui pemangkin MgCl2 memberi peratusan hasil yang baik, dalam lingkungan 69 –87%. Ion Mg2+ bertindak sebagai pemangkin asid Lewis dalam pembentukan 1,4-DHP dan cadangan mekanisma terhadap pembentukan 1,4-DHP telah dihuraikan dalam manuskrip ini. Terdapat banyak kelebihan menggunakan MgCl2 sebagai pemangkin dalam kajian ini, termasuk kos yang murah, ketersediaan logam ini, protokol pengekstrakan yang mudah, yang mana ini telah mencetuskan minat yang besar dalam penggunaan pemangkin ini dalam pelbagai tindak balas organik.

 

Kata kunci:  logam alkali bumi, magnesium klorida, 1,4-dihydropiridin

 

References

1.       Stone, P. H., Antman, E. M., Muller, J. E. and Braunwald, E. (1980). Calcium channel blocking agents in the treatment of cardiovascular disorders. Part II: Hemodynamic effects and clinical applications. Annals of Internal Medicine, 93(6): 886 – 904.

2.       Shan, R., Velazquez, C. and Knaus, E. (2004). Syntheses, calcium channel agonist-antagonist modulation activities, and nitric oxide release studies of nitrooxyalkyl 1,4-dihydro-2,6-dimethyl-3-nitro-4-(2,1,3-benzoxadiazol-4-yl) pyridine-5-carboxylate racemates, enantiomers, and diastereomers. Journal of Medicinal Chemistry, 47(1): 254 – 261.

3.       Visentin, S., Rolando. B., Stilo. A. D., Frutterro, R., Novara, M., Carbone, E., Roussel, C., Vanthuyne, N. and Gasco, A. (2004). New 1,4-dihydropyridines endowed with NO-donor and calcium channel agonist properties. Journal of Medicinal Chemistry, 47(10): 2688 – 2693.

4.       Eharkar, P. S., Desai, B., Gaveria, H., Varu, B., Loriya, R., Naliapara, Y., Shah, A. and Kulkarni, V. M. (2002). Three-dimensional quantitative structure-activity relationship of 1,4-dihydropyridines as antitubercular agents. Journal of Medicinal Chemistry, 45(22): 4858 – 4867.

5.       Anniyappan, M., Muralidharan, D. and Perumal, P. T. (2002). Synthesis of Hantzsch 1,4- dihydropyridines under microwave irradiation. Synthetic Communications, 32(4): 659 – 663.

6.       Mekheimer, R. A., Hameed, A. A. and Sadek, K. U. (2008). Solar thermochemical reactions: four-component synthesis of polyhydroquinoline derivatives induced by solar thermal energy. Green Chemistry, 10(5): 592 – 593.

7.       Shaabani, A., Rezayan, A. H., Rahmati, A. and Sharifi, M. (2006). Ultrasound-accelerated synthesis of 1,4- dihydropyridines in an ionic liquid. Monatshefte fur Chemie, 137(1): 77 – 81.

8.       Legeay, J., Eyndeb, J.J.V. and Bazureau, J. P. (2005). Ionic liquid phase technology supported the three component synthesis of Hantzsch 1,4-dihydropyridines and Biginelli 3,4-dihydropyrimidin-2(1H)-ones under microwave dielectric heating. Tetrahedron, 61(52): 12386 – 12397.

9.       Sharma, S. D., Hazarika, P. and Konwar, D. (2008). A simple, green and one-pot four component synthesis of 1,4-dihydropyridines and their aromatization. Catalysis Communications, 9(5): 709 – 714.

10.    Maheswara, M., Siddaiah, V., Rao, Y. K., Yew-Min, T. and Sridhar, C. (2006). A simple and efficient one-pot synthesis of 1,4-dihydropyridine using heterogenous catalyst under solvent-free conditions. Journal of Molecular Catalysis A: Chemical, 260(1): 179 – 180.

11.    Miura, K., Nakagawa, T. and Hosomi, A. (2015). Metal chloride-promoted aldol reaction of α-dimethylsilylesters with aldehydes, ketones, and α-enones. Synlett, 12: 1917 – 1921.

12.    Shahnaz, K., Majid, M. H., Minou, K., Farahnaz, K. B. and Zohreh, D. (2008). A very high yielding and facile alkaline earth metals homogeneous catalysis of Biginelli reaction: An improved protocol. Green Chemistry, 1(2): 133 – 139.

13.    Yaragorla, S., Singh, G. and Pareek, A. (2015). Alkaline earth metal catalyzed, one-pot, multi-component approach for the synthesis of dihydropyridine, acridine and xanthene derivatives in water. Indian Journal of Chemistry, 54: 1321 – 1326.

14.    Cotton, F. A., Wilkinson, G. and Gaus, O. L. (1995). Basic Inorganic Chemistry. J. Wiley & Sons. New York.

15.    Kobayashi, S. and Yamashita, Y. (2011). Alkaline earth metal catalysts for asymmetric reactions. Accounts of Chemical Research, 44(1): 58 – 71.

16.    Alexander, J. S. and Ruhlandt-Senge, K. (2002).  Not just heavy “Grignards”: Recent advances in the organometallic chemistry of the alkaline earth metals calcium, strontium and barium. European Journal of Inorganic Chemistry, 11: 2761 – 2774.

17.    Wang, S-X., Li, Z-L., Zhang J-C. and Li J-T. (2008). The solvent-free synthesis of 1,4-dihydropyridines under ultrasound irradiation without catalyst. Ultrasonics Sonochemistry, 15(5): 667 – 680.

18.    Reddy, B. Palakshi., Rajesh, K. and Vijayakumar, V. (2011).  Ionic Liquid [EMIM]OAc under ultrasonic irradiation towards Synthesis of 1,4-DHP's. Journal of the Chinese Chemical Society, 58(3): 384 – 388.

19.    Zolfigol, M. A., Salehi, P. and Safaiee, M. (2006).  An efficient and eco-friendly procedure for the synthesis of Hantzsch ethyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylates under mild and green conditions. Letters in Organic Chemistry, 3(2): 153 – 156.

20.    Kuraitheerthakumaran, A., Pazhamalai, S. and Gopalakrishnan, M. (2011). An efficient and solvent-free one-pot synthesis of 1,4-dihydropyridines under microwave irradiation. Chinese Chemical Letters, 22(10): 1199 – 1202.

21.    Yadav, D. K., Patel, R., Srivastava,V. P., Watal, G. and Yadav, L. D. S. (2011). LiBr as an efficient catalyst for one-pot synthesis of Hantzsch 1,4-dihydropyridines under mild conditions. Chinese Journal of Chemistry, 29(1): 118 – 122.

22.    Osnaya, R., Arroyo, G., Parada, L., Delgado, F., Trujillo, J., Salmón, M. and Miranda R. (2003). Biginelli vs Hantzsch esters study under infrared radiation and solventless conditions. Arkivoc, 11: 112 – 117.

23.    Bridgwood, K. L., Veitch, G. E. and Ley, S. V. (2008). Magnesium nitride as a convenient source of ammonia: Preparation of dihydropyridines. Organic Letters, 10(16): 3627 – 3629.

24.    Chang, C-C., Cao, S., Kang, S., Kai, L., Tian, X., Pandey, P., Dunne, S. F., Luan, C-H., Surmeier, D. J. and Silverman, R. B. (2010). Antagonism of 4-substituted 1,4-dihydropyridine-3,5-dicarboxylates toward voltage-dependent L-type Ca2+ channels Ca V 1.3 and Ca V 1.2. Bioorganic & Medicinal Chemistry, 18(9): 3147 – 3158.

25.    Sabitha, G., Arundhati, K., Sudhakar, K., Sastry, B. S. and Yadav, J. S. (2009). CeCl3·7H2O-catalyzed one-pot synthesis of Hantzsch 1,4-dihydropyridines at room temperature. Synthetic Communications, 39(16): 2843 – 2851.

 




Previous                    Content                    Next