USE OF ALUMINA IN PREPARATION OF OXIME: A PRECURSOR FOR BECKMANN REARRANGEMENT
Keywords:
Alumina, Beckmann Rearrangement, Column Chromatography, Ethanol, Hydroxylamine Hydrochloride, Oxime, Thin Layer ChromatographyAbstract
Objective: Oxime is an important precursor for many reactions like Beckmann rearrangement, oxime ether preparation etc. Oxime is generally prepared in strong acidic [1], strong basic [2] medium. Even some methods involving mild basic medium [3] is also known. But these procedures involve hazardous chemicals like inorganic acid, inorganic base, organic bases like Pyridine [4], Hy amine [5] etc. Some green methodologies have been also developed but that also involves expensive reagents like Bi2O3 [6] etc. Inthis context, this work has been carried out to develop a new methodology for oxime preparation.
Methods: Different oxims have been prepared in heating condition using water-ethanol medium and alumina as a base. Products have been isolated by column chromatography using 200 mesh silica gel followed by fractional crystallization. Products were verified by melting point analysis.
Results: Four different aromatic oxims have been prepared in excellent yield and in an economically viable condition.
Conclusion: Here preparation of oxime in a mild basic medium has been reported. Alumina (Al2O3) is pretty cheap and not mentionable hazardous and it has been used here for the first time in synthesis of oxime.
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References
Weissermer K, Arpe HJ. Industrial organic chemistry. Berlin: Springer Verlag; 1978. p. 225-8.
Damljanović I, Vukićević M, Vukićević RD. A Simple synthesis of oximes. Monatshefte Fur Chem 2006;137:301-5.
Sharghi H, Hosseini M. Solvent-free and one-step beckmann rearrangement of ketones and aldehydes by zinc oxide. Synthesis 2002;1057-9. Doi: 10.1055/s-2002-28520. [Article in Press].
Rahman MM, Halim ME, Ahmed SM, Akhter K, Romman UKR, Ahmed MG. Studies on the conversion of ketones of heterocyclic spiro compounds having barbituric acid moieties into oxime derivatives. Bangladesh J Sci Ind Res 2013;48(1):7-12.
Lad UP, Kulkarni MA, Patil RS. Synthesis of oximes in aqueous medium using hyamine as an ecofriendly catalyst at ambient temperature. Rasayan J Chem 2010;3(3):425-8.
Saikia L, Baruah JM, Thakur AJ. A rapid, convenient, solventless green approach for the synthesis of oximes using grindstone chemistry. Org Med Chem Lett 2011;1:12.
Beckmann E. Isonitroso compounds. Ber Dtsch Chem Ges 1886;19:988-93.
Aghapour G, Amirabadi M. A facile and high efficient synthesis of nitriles from aldoximes and primary amides with a mixture of triphenylphosphine/2, 3-dichloro-5, 6-dicyanobenzoquinone (PPh₃/DDQ) under neutral conditions. Indian J Chem 2007;46B:649-52.
Chiang YH. Reaction and mechanism of the chlorination of oximes in commercial chloroform and methylene chloride. J Org Chem 1971;36(15):2146.
Smith PA, Robertson JE. Some factors affecting the site of alkylation of oxime salts. J Am Chem Soc 1962;84(7):1197.
Dave PR, Forohar F, Axenrod T, Das KK, Qi L, Watnick C, et al. Facile preparation of 3,7-diazabicyclo[3.3.0]octane and 3,7,10-triheterocyclic [3.3.3]propellane ring systems from 1,5-diazacyclooctane 3,7-derivatives. J Org Chem 1996;61(25):8897-903.
Shinada T, Yoshihara K. A facile method for the conversion of oximes to ketones and aldehydes by the use of activated MnO2. Tetrahedron Lett 1995;36(37):6701-4.
Ley JP, Bertram HJ. Hydroxy-or Methoxy-substituted benzaldoximes and benzaldehyde-O-alkyloximes as tyrosinase inhibitors. Bioorgan Med Chem 2001;9(7):1879-85.