Abstract
Oxidation of nine primary aliphatic alcohols by pyridinium bromochromate (PBC) leads to the formation of corresponding aldehydes. The reaction is of overall second order, and of first order with respect to the each reactant. The reaction is promoted by hydrogen ions; the hydrogen-ion dependence has the formk obs=c+d[H+]. The oxidation of [1, 1-2H2] ethanol (MeCD2OH) exhibited a substantial primary kinetic isotope effect. The reaction was studied in nineteen organic solvents and the effect of solvent was analysed using Taft's and Swein's multiparametric equations. The oxidation is susceptible to both the polar and steric effects of the substituents. A suitable mechanism has been proposed.
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Banerji K K 1978Bull. Chem. Soc. Jpn. 51 2732
Banerji K K 1983Indian J. Chem. B22 413
Banerji K K 1988J. Chem. Soc. Perkin Trans. 2 547
Bordwell F G 1972Acc. Chem. Res. 5 374
Exner O 1964Collect. Czech. Chem. Commun. 29 1094
Oxner O 1966Collect. Czech. Chem. Commun. 31 3222
Grover A, Varshney S and Banerji K K 1994Indian J. Chem. A33 622
Kamlet M J, Abboud J L H, Abraham M H and Taft R W 1983J. Org. Chem. 48 2877, and references cited therein
Kaplan L 1958J. Am. Chem. Soc. 80 2639
Kwart H and Nickle J H 1973J. Am. Chem. Soc. 95 4835
Littler J S 1971Tetrahedron 27 81
Narayanan N and Balasubramanian T R 1986Indian J. Chem. B25 229
Narayanan N and Balasubramanian T R 1991J. Chem. Res. (S) 336
Pavelich W A and Taft R W 1957J. Am. Chem. Soc. 79 4935
Perrin D D, Armstrong W L and Perrin D R 1966Purification of organic compounds (Oxford: Pergamon)
Swain C G, Swain M S, Powel A L and Alunni S 1983J. Am. Chem. Soc. 105 502
Wiberg K B 1963Physical organic chemistry (New York: Wiley) p. 415
Woodward R B and Hoffman R 1969Angew. Chem. Int. Ed. Eng. 8 781
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Aparna, P., Kothari, S. & Banerji, K.K. Kinetics and mechanism of the oxidation of primary aliphatic alcohols by pyridinium bromochromate. Proc. Indian Acad. Sci. (Chem. Sci.) 107, 213–220 (1995). https://doi.org/10.1007/BF02884439
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DOI: https://doi.org/10.1007/BF02884439