Abstract
In 1870–75 Markovnikov enunciatedan empirical Rule which generalized theregiochemical outcome of addition reactions tounsymmetrical alkenes. This Rule remaineduseful for about 75 years, until suchreactions came to be better understood inmechanistic terms. Thereafter the Rule couldbe deduced from principles of relativecarbocation stabilization and ceased to servean independent purpose. Nevertheless, mostorganic textbooks continue to cite it (oftenin a historically inaccurate, anachronisticway), thereby distracting student attentionfrom the underlying principles. This paperadvocates doing away with the Rule in organicchemistry textbooks and classrooms.
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REFERENCES
A. Baeyer, Ueber das Neurin. Annalen der Chemie und Pharmacie 142: 322–326, 1867.
J.P. Bays, S.T. Blumer, S. Baral-Tosh, D. Behar and P. Neta, Intramolecular Electron Transfer and Dehalogenation of Nitroaromatic Anion Radicals. Journal of the American Chemical Society 105: 320–324, 1983.
F. Bohlmann, N. Ottawa and R. Keller, Aufbau des Tetrahydro-chinolizons und des “Bispidins.” Liebigs Annalen der Chemie 587: 162–176, 1954.
H.C. Brown and B.C. Subba Rao, Hydroboration. I. The Reaction of Olefins with Sodium Borohydride-Aluminum Chloride. A Convenient Route to Organoboranes and the anti-Markownikoff Hydration of Olefins. Journal of the American Chemical Society 81: 6423–6428, 1959. See also H.C. Brown, Hydroboration. New York: Benjamin, 1962.
P.Y. Bruice, Organic Chemistry, 3rd edition, pp. 144–146. Englewood Cliffs, NJ: Prentice Hall, 2001.
A. Butlerov, Mittheilungen aus dem chemischen Universitätslaboratorium zu Kasan. 1) Ueber die Derivate von Trimethylcarbinol (von tertiärem Pseudobutylalkohol). Isomerie der gesättigten Kohlenwasserstoffe C4H10 und der Butylene C4H8. Isobutylalkohol (der primäre Pseudobutylalkohol oder Pseudopropylcarbinol). Annalen der Chemie und Pharmacie 144: 1–32, 1867.
J.B. Conant and A.H. Blatt, The Chemistry of Organic Compounds, 4th edition, pp. 59–61. New York: Macmillan, 1952.
H. Decker, Wladimir Wasiliewitsch Markownikow. Berichte der deutschen chemischen Gesellschaft 38: 4249–4262, 1906.
L.F. Fieser and M. Fieser, Organic Chemistry, pp. 61–62 Boston: D.C. Heath, 1944.
M.A. Fox and J.K. Whitesell, Organic Chemistry, 2nd edition, pp. 357–359. Sudbury, MA: Jones & Bartlett, 1997.
E.S. Gould, Mechanism and Structure in Organic Chemistry, pp. 516–519. New York: Holt, Rinehart & Winston, 1959.
L. Henry, On the Products of Addition of Propylene to Hypochlorous Acid. Comptes rendus 79: 1203, 1874.
J. Hine, Physical Organic Chemistry, p. 218. New York: McGraw-Hill, 1956.
J.M. Hornback, Organic Chemistry, pp. 404–406, 424–425. Pacific Grove, CA: Brooks/Cole, 1998.
C.K. Ingold, Structure and Mechanism in Organic Chemistry, pp. 646–658. Ithaca: Cornell University Press, 1953.
N. Isenberg and M. Grdinic, A Modern Look at Markovnikov's Rule and the Peroxide Effect. Journal of Chemical Education 46: 601–605, 1969.
G. Jones, The Markovnikov Rule. Journal of Chemical Education 38: 297–300, 1961.
M. Jones, Jr., Organic Chemistry, 2nd edition, pp. 323–332, 341–342. New York: Norton, 2000.
G. Kaupp and D. Matthies, Organische Gas-Festkörper-Reaktionenmit Stilbenen, Chalkonen, und Enamiden. Chemische Berichte 120: 1897–1903, 1987.
P. Laszlo, Organic Reactions – Simplicity and Logic, pp. 443, 447, 480. New York: Wiley, 1995.
M.S. Kharasch and O. Reinmuth, The Electron in Organic Chemistry. II. Bonds of the Ethylene Type and Factors Influencing Directed Addition Thereat. Journal of Chemical Education 8: 1703–1747, 1931.
M.S. Kharasch, E.T. Margolis and F.R. Mayo, The Peroxide Effect in the Addition of Reagents to Unsaturated Compounds. XIII. The Addition of Hydrogen Bromide to Butadiene. Journal of Organic Chemistry 1: 393–404, 1936.
H.M. Leicester, Vladimir Vasil'evich Markovnikov. Journal of Chemical Education 18: 53–57, 1941.
D.E. Lewis, The University of Kazan – Provincial Cradle of Russian Organic Chemistry: Part I. Nikolai Zinin and the Butlerov School. Journal of ChemicalEducation 71: 39–42, 1994; Part II: Aleksandr Zaitsev and his Students. ibid. 71: 93–97, 1994.
E.T. McBee and W.R. Hausch, Synthesis of Halobutanes. Industrial and Engineering Chemistry 39: 418–420, 1947; per Chemical Abstracts 41: 3747a, 1947.
E.N. Marvell and A.O. Geiszler, The Rearrangement of Some Disubstituted Cyclic Ketones: An Unusual Dienone-Phenol Rearrangement. Journal of the American Chemical Society 74: 1259–1263, 1952.
J. McMurry, Organic Chemistry, 5th edition, pp. 209–210. New York: Brooks/Cole, 2000.
V. Markovnikov, Untersuchungen aus dem chemischen Laboratorium des Prof. Kolbe. LVI. Ueber die Acetonsäure. Annalen der Chemie und Pharmacie 146: 339–352, 1868.
V. Markovnikov, Mittheilungen aus dem chemischen Laboratorium zu Kasan. I. Ueber die Abhängigkeit der verschiedenen Vertretbarkeit des Radicalwasserstoffs in den isomeren Buttersäuren. Annalen der Chemie und Pharmacie 81: 228–259, 1870.
V. Markovnikov, Sur les lois qui régissent les reactions de l'addition direct. Comptes rendus 81: 668–671, 728–730, 776–779, 1875.
F.R. Mayo and C. Walling, The Peroxide Effect in the Addition of Reagents to Unsaturated Compounds and in Rearrangement Reactions. Chemical Reviews 27: 351–412, 1940.
A. Michael, Ueber einige Gesetze und deren Anwendung in der Organischen Chemie. Journal für Praktische Chemie [2] 60: 286–384, 1899.
P.C. Myhre and G.D. Andrews, Electrophilic “Additions” of Strong Acids to 3,3,3-Trifluoropropene. Journal of the American Chemical Society 92: 7596–7597, 1970.
R.T. Morrison and R.N. Boyd, Organic Chemistry, 6th edition, pp. 327–331, 336. Englewood Cliffs NJ: Prentice Hall, 1992.
T.A. Newton, TheMisuse ofMarkovnikov'sRule. Journal of Chemical Education 64: 531–532, 1987.
E. Rothstein, D.J. Stanbank and R. Whiteley, Experiments with Thioacetals and Related Substances. Part IV. Anionotropic Rearrangements of gem-Bisalkylthio-propenes and-butenes. Journal of the Chemical Society [C]: 746–752, 1968.
E. Schmidt, Ueber die Einwirkung von Jodwasserstoff und Bromwasserstoff auf Neurin and Cholin. Liebigs Annalen der Chemie 267: 300–318, 1892.
J.R. Shelton and L.-H. Lee, Addition of Halogens and Halogen Compounds to Allylic Chlordes. I. Addition of Hydrogen Halides. Journal of Organic Chemistry 23: 1876–1880, 1958.
T.W.G. Solomons and C.B. Fryhle, Organic Chemistry, 7th edition, pp. 324–329. New York: Wiley, 2000.
J. Tierney, Markovnikov's Rule: What Did He Say and When Did He Say it? Journal of Chemical Education 65: 1053–1054, 1988.
K.P.C. Vollhardt and N.E. Schore, Organic Chemistry, Structure and Function, 3rd edition, pp. 490–501. New York: W. H. Freeman, 1999.
L.G. Wade, Jr., Organic Chemistry, 4th edition, pp. 332–335, 346–347. Englewood Cliffs, NJ: Prentice Hall, 1999.
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Kerber, R.C. Markovnikov's Rule in History and Pedagogy. Foundations of Chemistry 4, 61–72 (2002). https://doi.org/10.1023/A:1014479921278
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DOI: https://doi.org/10.1023/A:1014479921278