The Logic Behind Markovnikov's Rule: Was It an Inspired Guess? …No

Vladimir Vasil′evich Markovnikov (1837–1904) was a Russian chemist whose graduate research at Kazan Imperial University from 1860–1869 gave us, among other things, one of the most enduring empirical rules in organic chemistry. Markovnikov's Rule for electrophilic addition was first published in the inaugural volume of the Journal of the Russian Chemical Society (Zh. Russ. Khim. O‐va.), but it was not until a year later when it was published in German that it received attention internationally. The rule itself was worded differently from the most common modern versions, in that it is expressed in terms of the electronegative part of the adding reagent. It has been suggested that this rule was the result of an inspired guess, but a careful examination of Markovnikov's graduate dissertations reveals a very different picture. In the dissertations, there is a careful build‐up of logic from which the rule itself, as defined by Markovnikov, emerges naturally. Markovnikov's Rule was most decidedly not an inspired guess. Based on Markovnikov's 1870 Annalen paper, many western authors have viewed his rule as a relatively unimportant addendum to a paper on isobutyric acid derivatives, and some have suggested that the rule itself was simply an inspired guess. In this Essay, based on an analysis of his work on the structure of the double bond in his graduate dissertations, the argument is made that it was not.