RESEARCH ARTICLE

 

Reduction of α,β-unsaturated ketones using a Zn/NiCl₂ system in aqueous media in the presence of anionic and cationic surfactants

 

 

Hocine Ilikti^*; Tayeb Benabdallah; Kamel Bentayeb; Adil A. Othman; Zoubir Derriche

Organic Chemistry and Electrochemistry Laboratory, Department of Chemistry, Faculty of Science, University of Science and Technology, Oran-Mohamed Boudiaf-USTO-MB, BP:1505 El M'Naouar, Oran 31000, Algeria

 

 

---

ABSTRACT

The reduction of aromatic and aliphatic α,β-unsaturated ketones, namely acetophenone (1) and (-)-carvone (3) with a Zn/NiCl₂ system in H₂OorH₂O/EtOH media in the absence or presence of anionic and cationic surfactants have been investigated and have shown remarkable results. The anionic sodium dodecyl sulphate (SDS), the cationic cetyltrimethylammonium bromide (CTAB) and the non-micelle-forming didodecyldimethylammonium bromide (DDAB) surfactants were utilized. The reduction of acetophenone in H₂O medium gave only a low yield of 1-phenyl ethanol (2) in comparison with the yields which resulted when a H₂O/EtOH medium was employed. The yields increased relatively in a H₂O medium in the presence of cationic surfactants which showed a gradual increase at low concentrations following different patterns and sharp increases at 60 °C and pH 9. The reduction of (-)-carvone (3) with the same system in H₂O medium gave relatively higher yields than that of acetophenone. In the presence of cationic surfactants CTAB and DDAB in aqueous medium the total reduction yield increased appreciably and sometimes reached 100 % in the presence of DDAB at a concentration of 0.98 X 10^-2 mol L^-1 at 60 °C. The effects of pH, combined metallic salts and different surfactant concentrations on the reduction of (-)-carvone have been also investigated. This paper focuses on the application of surfactants in the reduction of α,β-enones by metal/metallic chloride/H₂O systems in the absence of organic solvents. This method displays regioselectivity and stereoselectivity. This method may also be considered as a contribution to the antipollution process by means of the elimination of organic solvents from the chemical process.

Keywords: Zinc/nickel chloride/H₂O, reduction, hydrogenation, surfactants, sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), didodecyldimethylammonium bromide (DDAB)

---

 

 

Full text available only in pdf format.

 

Acknowledgement

Thanks to Ms Z. Khiati (USTO) for assistance with the graphs, figures and tables.

 

References and Notes

1 C. Petrier and J-L. Luche, Tetrahedron Lett., 1987, 28, 2347-2350.         [ Links ]

2 C. Petrier, J-L. Luche, S. Lavaitte and C. Morat, J. Org. Chem., 1980, 54, 5313-5317.         [ Links ]

3 C. Petrier, S. Lavaitte and C. Morat, J. Org. Chem., 1990, 55, 1664-1667.         [ Links ]

4 M. Hazarika and N. Barua, Tetrahedron Lett, 1989, 30, 6567-6570.         [ Links ]

5 (a) F. Alonso and M. Yus, Tetrahedron, 1998, 54, 1921-1928; (b) Y Moglie, F. Alonso, C. Vitale, M. Yus and G. Radivoy, Tetrahedron, 2006, 62, 2812-2819.         [ Links ]

6 M. Baruah, A. Boruah, D. Prajapati, J. Sondhu and A. Ghosh, Tetrahedron Lett., 1996, 37, 4559-4560.         [ Links ]

7 (a) F. Alonso and M.Yus, Tetrahedron Lett, 1996, 37, 6925-6928; (b) G. Radivoy, F. Alonso and M.Yus, Tetrahedron, 1999, 55, 14479-14490.         [ Links ]

8 F. Alonso and M. Yus, Tetrahedron Lett, 1997, 38, 149-152.         [ Links ]

9 (a) M.S. Bezbarua, G. Bez and N.C. Berua, Chem. Lett., 1999, 325-326; (b) G. Radivoy, F. Alonso, Y. Moglie, C.Vitale and M.Yus, Tetrahedron, 2005, 61, 3892-3894.         [ Links ]

10 H. Ilikti, N. Rekik and M. Thomalla, J. Appl. Electrochem., 2002, 32, 603-609.         [ Links ]

11 (a) H. Ilikti, N. Rekik and M. Thomalla, J. Appl. Electrochem., 2004, 34, 127-136; (b) F. Alonso, I. Belskaya and M. Yus, Tetrahedron, 2005, 61, 11771-11835.         [ Links ]

12 A.A. Othman, H. Ilikti and S. Boukreris, unpublished work.         [ Links ]

13 R.A. Mackay and J. Texter (eds.), Electrochemistry in Colloids and Dispersions, VCH, New York, USA, 1992, p. 546.         [ Links ]

14 M. Thomalla, in J. Texter (ed.), Reaction and Synthesis in Surfactant Systems, Marcel Dekker, New York, USA, 2001, p. 295.         [ Links ]

15 J. Cosyns and G. Martino, Hydrogénation des Hydrocarbures, in Génie des Procédés, volume J3 (L. Badguerahanian and J. Jauvert eds.), Editions Technique de l'Ingénieur, Paris, France, 1993, pp. 1-17.         [ Links ]

16 (a) L. Fieser andM. Fieser, in Reagents for Organic Synthesis, vol. 1, John Wiley and Sons, New York, USA, 1967, p. 1278; (b) B. Aylett, in Comprehensive Inorganic Chemistry, vol. 3, J.C. Blair, H.J. Emeléus, R.S. Nyholm and A.F. Trotman-Dickensen (eds.), Pergamon Press, Oxford, UK, 1973, p. 196.         [ Links ]

17 D.R. Lide (ed.), CRC Handbook of Chemistry and Physics, 76th edn., CRC Press, Boca Raton, FL, USA, 1995, p. 42.         [ Links ]

 

 

Received 19 July 2007
Revised 14 November 2007
Accepted 13 January 2008

 

 

* To whom correspondence should be addressed. E-mail: ilikti@yahoo.fr