Synthesis of Agomelatine by One-pot Catalytic Hydrogenation and Acetylation with NiO

Abstract

Nano-NiO and bulk NiO were prepared from Ni(AC)₂·4H₂O by coordination precipitation using aqueous ammonia and by a solid state reaction, respectively. The nickel oxide particles were characterized by X-ray Diffraction (XRD) and scanning electron microscopy (SEM). The results indicate that nano-sized NiO has a crystal phase with a standard face-centered cubic lattice structure, with a mean particle diameter of about 10 nm. The evaluation of the activity of nickel oxide nanoparticles in the catalytic hydrogenation of 7-methoxy-1-naphthylacetonitrile was carried out. The results demonstrate the efficient synthesis of the title compound by a one-pot catalytic hydrogenation and acetylation with NiO. The NiO nanoparticles displayed superior catalytic activity in the synthesis of agomelatine in the one-pot reaction.The total yield of agomelatine is over 81.8% with a purity of 99.2%, as determined by HPLC. The structure of agomelatine was confirmed by IR, MS, and 1H NMR analysis.

Keywords

nano-NiO / homogeneous precipitation method / catalytic hydrogenation / agomelatine / N-[2- (7-Methoxy-1-naphthyl)ethyl]acetamide / 7-Methoxy-1-naphthylacetonitrile

References

[1] Guardiola–Lemaitre B, De Bodinat C, Delagrange P, et al. Agomelatine: Mechanism of Action and Pharmacological Profile in Relation to Antidepressant Properties[J]. British Journal of Pharmacology, 2014, 171(15): 3 604-3 619.

[2] Taylor D, Paron C, Kapur S. The Maudsley Prescribing Guidelines in Psychiatry(12th Edition)[M], 2015

[3] Rüdiger H. New Approaches in the Management of Insomnia: Weighing the Advantages of Prolonged–release Melatonin and Synthetic Melatoninergic Agonists[J]. Neuropsychiatr Dis Treat, 2009, 5(1): 341-354.

[4] Ettaoussi M, Sabaouni A, Rami M, et al. Design, Synthesis and Pharmacological Evaluation of New Series of Naphthalenic Analogues as Melatoninergic (MT1/MT2) and Serotoninergic 5–HT2C Dual Ligands (I)[J]. European Journal of Medicinal Chemistry, 2012, 49(1): 310-323.

[5] Yous S, Andrieux J, Howell HE, et al. Novel Naphthalenic Ligands with High Affinity for the Melatonin Receptor[J]. Journal of Medicinal Chemistry, 1992, 35(8): 1 484-1 486.

[6] Kandagatla B, Reddy GM, Rao SC, et al. A Facile Synthesis of Melatonergic Antidepressant Agomelatine[J]. Tetrahedron Letters, 2012, 53(52): 7 125-7 127.

[7] Vujjini SK, Datla KR, Badarla KR, et al. Total Synthesis of Agomelatine via Friedel–Crafts Acylation Followed by Willgerodt–Kindler Reaction[J]. Tetrahedron Letters, 2014, 55(29): 3 885-3 887.

[8] Priebbenow DL, Bolm Carsten. Recent Advances in the Willgerodt–Kindler Reaction[J]. Chemical Society Reviews, 2013, 42: 7 870-7 880.

[9] Souvie JC, Gonzalez Blanco I. Process for the Synthesis of (7–methoxy–1–naphthyl) Acetonitrile and Its Application in the Synthesis of Agomelatine: US, US 7999129 B2[P], 2011

[10] Tyagi OD, Lahiri S, Koilkonda P, et al. Process for Producing 1–[2–(dimethylamino)–1–(4–phenol) ethyl] Cyclohexanol[P]. , 2012 US8304578: WO.

[11] Bontempelli P, Jalenques X, Starck JB, et al. Novel Process for the Synthesis of Agomelatine: WO, 2010

[12] Liu Y, Chen L, Ji Y. Quantification and Structural Elucidation of Potential Impurities in Agomelatine Active Pharmaceutical Ingredient[J]. Journal of Pharmaceutical & Biomedical Analysis, 2013 81-82.

[13] Zhu J, Tian Q, Jian Z. Agomelatine and Pharmaceutical Compositions[ P], 2015

[14] Hongbing J, Huang Y, Qian Y, et al. Ni–mediated Liquid Phase Reduction of Carbonyl Compounds in the Presence of Atmospheric Hydrogen[ J], 2006 118-121.

[15] Ba–Abbad MM, Chai PV, Takriff MS, et al. Optimization of Nickel Oxide Nanoparticle Synthesis Through the Sol–gel Method Using Box–Behnken Design[J]. Materials & Design, 2015, 86(2015): 948-956.

[16] Danial AS, Saleh MM, Salih SA, et al. On the Synthesis of Nickel Oxide Nanoparticles by Sol–gel Technique and Its Electrocatalytic Oxidation of Glucose[J]. Journal of Power Sources, 2015, 293(2015): 101-108.

[17] An C, Wang R, Wang S, et al. A Low Temperature Composite–hydroxide Approach to NiO Nanocrystals [J]. Materials Research Bulletin, 2008, 43(10): 2 563-2 568.

[18] L J, X B, D L, et al. Preparation of Nanocrystalline NiO and Process Analysis[J]. Journal of Synthetic Crystals, 2007, 36(5): 1 045-1 051.