MARKOVNIKOV, VLADIMIR VASILEVICH

(b. Knyaginino, Nizhegorodskaya [now Gorki Region], Russia, 25 December 1837 [or 22 December 1838]; d. Moscow, Russia, 11 February 1904)

chemistry.

Markovnikov was the son of an officer. In 1856 he entered Kazan University, where he was attracted to chemistry, which was taught by Butlerov. After graduating from the university in 1860 he became Butlerov’s assistant in teaching inorganic and analytical chemistry. In his master’s thesis, “Ob izomerii organicheskikh soedineny” (“On the Isomerism of Organic Compounds”; Kazan, 1865); in a number of other works; and especially in his doctoral thesis, “Materialy po voprosu o vzaimnom vlianii atomov v khimicheskikh soedineniakh” (“Materials on the Question of the Mutual Influence of Atoms in Chemical Compounds”; Kazan, 1869), he developed the theory of chemical structure experimentally and theoretically. From 1865 to 1867 he was in Germany, spending most of his time in the laboratories of Erlenmeyer at Heidelberg and of Kolbe at Leipzig. After his return he became assistant to, and then succeeded, Butlerov in the chair of chemistry at Kazan University. In 1871, however, protesting the arbitrariness of the administration, he resigned. Markovnikov was immediately invited to the University of Odessa, and in 1873 to Moscow University. There he improved the teaching of chemistry, set up a new chemical laboratory according to his own plans, and created his own school of chemists. His students included I. A. Kablukov, M. I. Konovalov, N. Y. Demyanov, D. N. Pryanishnikov, A. E. Chichibabin, A. A. Yakovkin, and N. M. Kizhner. In 1893, after Markovnikov had served his term in the chair of chemistry, he yielded it to N. D. Zelinsky but retained a part of the laboratory.

An important turning point in Markovnikov’s scientific career occurred in Moscow: he shifted his attention mainly to practical chemical research, and thus was reproached for betraying pure science. He devoted almost twenty-five years to the study of the hydrocarbons of Caucasian petroleum and to the chemistry of alicyclic hydrocarbons —“naphthenes,” as he called them. But the range of Markovnikov’s research also included the composition of the salts of the southern Russian bitter-salt lakes and the Caucasian sources of mineral waters, and methods and materials for testing railroad ties.

Markovnikov also studied the history of chemistry. He took the initiative in the publication of the Lomonosovskogo sbornika (“Lomonosov Collection”; Moscow, 1901), which included material on the history of Russian chemical laboratories; and he himself wrote a detailed sketch of the laboratories of Moscow University.

The most important results which Markovnikov obtained in his work on the theory of structure and the chemistry of petroleum and alicyclic compounds were the following. He tested certain conclusions, important in the first stage of structural theory, concerning the existence of isomers in a series of fatty acids (for example, butyric and isobutyric acid, the identity of “acetone” acid, obtained by G. Städeler in 1859 from “the mixture of acetone, hydrogen cyanide, and diluted hydrochloric acid,” with isobutyric acid). Developing Butlerov’s theory of the mutual influence of atoms, Markovnikov introduced certain “rules.”

The rule for the substitution reaction in its general form states that with an unsymmetrical olefin, where two possible modes of addition are open, the reaction ordinarily follows a course such that the hydrogen becomes attached to the carbon atom of the olefin that already has the greater number of hydrogen atoms. Thus:

CH₃CH = CH₂ + HBr → CH₃CHBrCH₃.

Markovnikov recognized that tertiary hydrogen atoms and hydrogen atoms in the α position to a carboxyl group are more active than hydrogen atoms in other positions. This also indicated to him at what point in a molecule destructive oxidation would take place. Markovnikov also first stated the rule that when molecules of water or hydrogen halide are obtained from alcohols or alkylhalides, the separation occurs between them and the two neighboring atoms of hydrogen.

An example from Markovnikov’s doctoral thesis is:

This rule, as Markovnikov showed, can be used to determine the structure of unsaturated compounds. The formation of compounds of the hydrogen halides or water with an unsymmetrical olefin occurs so that the halogen or hydroxyl radical adds to the carbon of the ethylenic bond with the lesser number of hydrogen atoms while the hydrogen adds to the carbon with the larger number of hydrogen atoms. This is known in textbooks as the Markovnikov rule. Markovnikov explained the mechanism of the reactions of isomerization, similar to the transition of isobutyl alcohol to tertiary isobutyl alcohol by reference to such reactions of separation and addition. He also stated rules relating to monomolecular isomerization and certain other reactions, stressing their dependence on the conditions.

In 1872, two years before van’t Hoff’s stereochemical representation (tetrahedral) of the carbon atom, Markovnikov showed the necessity of developing a theory of chemical structure by studying the relation between chemical interaction and the “physical position” of atoms in space; and in 1876 he stated that “the relative distribution of atoms in a molecule should be expressed by chemical formulas.”

Markovnikov was one of the first to understand the importance of studying the composition of petroleum hydrocarbons for practical uses. For example, he and his colleagues showed, contrary to the current opinion, that oil from the Caucasus contained derivtives of cyclopentane and aromatic hydrocarbons along with derivatives of cyclohexane. He discovered the existence of azeotropic mixtures of both these types of hydrocarbons. Markovnikov proposed a method for obtaining aromatic nitro derivatives by means of direct nitration of petroleum fractions.

Markovnikov’s contribution to the chemistry of alicyclic compounds consists, first, in his experimental refutation of the prevailing opinion that the carbocyclic compounds could have only six-atom nuclei. In 1879 he synthesized the derivative of a four-mem-bered cycle, and ten years later (at the same time as W. H. Perkin, Jr.) the derivative of a seven-membered cycle. In 1892 Markovnikov proposed the isomerization of a seven-membered cycle into the six-membered one and laid the basis for the study of mutual transformations of alicycles. Markovnikov also made the first classifications of alicyclic compounds in 1892.

BIBLIOGRAPHY

I. Original Works. Many of Markovnikov’s writings are in Izbrannye trudy (“Selected Works”), A. F. Platé and G. V. Bykov, eds., in the series Klassiki Nauki (“Classics of Science”; Moscow, 1955), with a 448-title biblio. of Markovnikov’s works in the appendix, pp. 835–889.

Among his articles are “Zur Geschichte der Lehre über die chemische Structur,” in Zeitschrift für chemite, n.s. 1 (1865), 280–287; “Ueber die Acetonsäure,” in Annalen der Chemie und Pharmacie, 146 (1868), 339–352; “Ueber die Abhängigkeit der verschiedenen Vertretbarkeit des Radicalwasserstoffs in den isomeren Buttersäuren,” ibid., 153 (1870), 228–259; “Tetrylenndicarbonsäure (Homoitakon säure),” ibid., 208 (1881), 333–349, written with G. Krestovnikov; “Recherches sur le pétrole caucase,” in Annales de chimie et de physique, 6th ser., 2 (1884), 372–484, written with V. Ogloblin; “Die aromatischen Kohlenwasserstoffe des Kaukasischen Erdöhls,” in Justus Liebig’s Annalen der Chemie, 234 (1886), 89–115; and “Die Naphtene und deren Derivate in dem allgemeinen System der organischen Verbindungen,” in Journal für praktische Chemie, 2nd ser., 45 (1892), 561–580, and 46 (1892), 86–106.

Some of Markovnikov’s correspondence is in “Pisma V. V. Markovnikov k A. M. Butlerov” (“Letters of V. V. Markovnikov to A. M. Butlerovu”), in Pisma russkikh khimikou k A. Butlerovu (“Letter of Russian Chemists to A. M. Butlerov”), vol. IV in the series Nauchnoe Nasledstvo (“Scientific Heritage”, Moscow, 1961), pp. 212–289.

II. Secondary Literature. There is a collection entitled Pamyati Vladimira Vasilevicha Markovnikova (“In Memory of Vladimir Vasilevich Markovnikov” Moscow, 1905).

See also H. Decker, “Wladimir Wasiliewitsch Markownikow,” in Berichts der Deutschen chemischen Gesellschaft, 38 (1906), 4249–4259; H. M. Leicester, “Vladimir vasil’e vich Markovnikov,” in Journal of Chemical Education,18 (1941), 53–57; and “Kekulé, Butlerov, Markovnikov. Controversies on Chemical Structure From 1860 to 1870,” in Kekulé Centennial, no. 61 in the series Advances in Chemistry (Washington, D.C., 1966). pp. 13–23; A. F. Platé and G. V. Bykov, “Ocherk zhizni i deyatelnosti V. V. Markovnikova” (“A Sketch of the lIfe and Work of V. V. Markovnikov”), in Markovnikov’s Izbrannye trudy pp. 719–777; and A. F. platé, G. V. Bykov, and M. S. Eventova, Vladimir Vasilevich Markounikov. Ocherk Zhizni i deyatelnosti. 1837–1904 (“Vladimir Vasilevich Markovnikov. A Sketch of His Life and Work,” Moscow, 1962).

G. V. Bykov