Abstract
Due to intramolecular hydrogen bonding between the amino and nitro groups, o-nitroaniline is incapable of forming Schiff bases in the reactions with acetaldehyde and crotonaldehyde but is converted to quinoline derivative under Doebner–Miller reaction conditions via addition to the C=C double bond of the α,β-unsaturated aldehyde. Under analogous conditions, p-nitroaniline possessing a free amino group gives rise to the product of Doebner–Miller quinoline synthesis through intermediate formation of Schiff base dimer. The reaction of p-nitroaniline with benzaldehyde also yields the corresponding Schiff base, whereas o-nitroaniline is converted to N-benzyl derivative.
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References
Vatsuro, K.V. and Mishchenko, G.L., Imennye reaktsii v organicheskoi khimii. Spravochnik (Name Reactions in Organic Chemistry), Moscow: Khimiya, 1976, pp. 171, 374.
Claret, P.A., Comprehensive Organic Chemistry, Barton, D. and Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 4. Translated under the title Obshchaya organicheskaya khimiy., Moscow: Khimiya, 1985, vol. 8, p. 196.
Gilchrist, T.L., Heterocyclic Chemistry, Harlow, Essex, England: Longman Scientific & Technical, 1992, 2nd ed. Translated under the title Khimiya geterotsiklicheskikh soedinenii, Moscow: Mir, 1996, p. 185.
Heterocyclic Compounds, Elderfield, R.C., Ed., New York: Wiley, 1952, vol. 4. Translated under the title Geterotsiklicheskie soedineniy., Moscow: Inostrannaya Literatura, 1955, vol. 4, p. 539.
Khimicheskaya entsiklopediya (Chemical Encyclopedia., Moscow: Sovetskaya Entsiklopediya, 1990, vol. 2, p. 8.
Kratkaya khimicheskaya entsiklopediya (Brief Chemical Encyclopedia., Moscow: Sovetskaya Entsiklopediya, 1961, vol. 1, p. 1034.
Beyer, C., J. Prakt. Chem., 1886, vol. 33, p. 424.
Ardashev, B.I., Usp. Khim., 1954, vol. 23, p. 54.
Fokin, E.P. and Fomicheva, I.V., Zh. Org. Khim., 1970, vol. 6, p. 1282.
Beilsteins Handbuch der organischen Chemie, H, vol. 12, p. 717.
Denisov, V.Ya., Grishchenkova, T.N., and Grudneva, I.N., USSR Inventor’s Certificate no. 1 118 634, 1984; Byull. Izobret., 1984, no.38.
Beilsteins Handbuch der organischen Chemie, H, vol. 20, p. 394.
Dictionary of Organic Compounds, Heilbron, J. and Bunbury, H.M., Eds., New York: Oxford Univ. Press, 1965, 4th ed. Translated under the title Slovar’ organicheskikh soedinenii, Moscow: Inostrannaya Literatura, 1979, vol. 3, p. 86.
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Original Russian Text © V.Ya. Denisov, T.N. Grishchenkova, T.B. Tkachenko, S.V. Luzgarev, 2016, published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 12, pp. 1806–1812.
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Denisov, V.Y., Grishchenkova, T.N., Tkachenko, T.B. et al. Reaction of nitroanilines with aldehydes. Refinement of the Doebner–Miller reaction mechanism. Russ J Org Chem 52, 1797–1803 (2016). https://doi.org/10.1134/S1070428016120150
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DOI: https://doi.org/10.1134/S1070428016120150