Institute of Chemistry, Skopje, Macedonia

Chemists


Vladimir Vasilevich MARKOVNIKOV

(mahr-kuv'nih-kuv), also spelled Markowinkoff



Born: December 22, 1838, Nizhny Novgorod, Russia; Died: February 1904, Moscow, Russia


Markovnikov studied under Butlerov in Kazan and St. Petersburg. After graduation in 1860 he went to Germany for two years where he studied under Erlenmeyer and Kolbe. He returned to Russia, and succeeded to Butlerov's professorship at the Kazan University. He also taught at Odessa and Moscow.

Markovnikov is best known for predicting the regiochemistry of addition reactions of hydrogen halides, sulfuric acid, water, ammonia, etc. to unsymmetrical alkenes. This is known as the Markovnikov Rule which he developed in 1869. Since he refused to publish in a foreign language, these findings were unknown outside of Russia until 1899. According to this rule, the electrophilic X- adds to the carbon atom with fewer hydrogen atoms, while the proton adds to the carbon atom with more hydrogen atoms bonded to it. Thus, hydrogen chloride (HCl) adds to propene, CH3-CH=CH2 to produce 2-chloropropane CH3CHClCH3 rather than the isomeric 1-chloropropane CH3CH2CH2Cl. The rule is useful in predicting the molecular structures of products of addition reactions. Why hydrogen bromide exhibited both Markovnikov as well as reversed-order, or anti-Markovnikov, addition, however, was not understood until Morris Selig Kharasch offered an explanation in 1933.

He also contributed to the structures of cyclic molecules. It was thought that only six-atom rings can exist, but Markovnikov broadened this view by preparing rings with four carbon atoms in 1879 and then seven carbon atoms in 1889.

Markovnikov also showed that butyric and isobutyric acids have the same chemical formula but different structures; i.e., they are isomers.


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Created by Zoran Zdravkovski and Kiro Stojanoski

February 18, 1997, last updated February 18, 1997.

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