Reactions of Alkenes

The rule states that with the addition of a protic acid HX to an asymmetric alkene, the acid hydrogen (H) gets attached to the carbon with more hydrogen substituents, and the halide (X) group gets attached to the carbon with more alkyl substituents. Alternatively, the rule can be stated that the hydrogen atom is added to the carbon with the greatest number of hydrogen atoms while the X component is added to the carbon with the least number of hydrogen atoms.[3]

The same is true when an alkene reacts with water in an addition reaction to form an alcohol which involve formation of carbocations. The hydroxyl group (OH) bonds to the carbon that has the greater number of carbon–carbon bonds, while the hydrogen bonds to the carbon on the other end of the double bond, that has more carbon–hydrogen bonds.

The chemical basis for Markovnikov's Rule is the formation of the most stable carbocation during the addition process. The addition of the hydrogen ion to one carbon atom in the alkene creates a positive charge on the other carbon, forming a carbocation intermediate. The more substituted the carbocation, the more stable it is, due to induction and hyperconjugation. The major product of the addition reaction will be the one formed from the more stable intermediate. Therefore, the major product of the addition of HX (where X is some atom more electronegative than H) to an alkene has the hydrogen atom in the less substituted position and X in the more substituted position.
   • [IUPAC Nomenclature of Alkene][Naming...