Markownikoff's Rule: Why Does it Happen?

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SUMMARY

Markownikoff's Rule explains the regioselectivity of electrophilic addition reactions, particularly in alkenes. The rule states that when HX (where X is a halogen) adds to an alkene, the hydrogen atom will attach to the carbon with the greater number of hydrogen substituents, leading to the formation of the more stable carbocation intermediate. For example, in the reaction of HCl with 1-Methyl-2-butene, the chlorine atom preferentially bonds to the more substituted carbon due to the stability of the resulting carbocation. This behavior is rooted in the principles of reaction mechanisms and carbocation stability.

PREREQUISITES
  • Understanding of electrophilic addition reactions
  • Familiarity with carbocation stability and classification (primary, secondary, tertiary)
  • Knowledge of reaction mechanisms in organic chemistry
  • Basic concepts of alkene reactivity and structure
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  • Study the mechanisms of electrophilic addition reactions in detail
  • Explore the concept of carbocation rearrangements and their implications
  • Investigate the role of reaction intermediates in organic reactions
  • Learn about other regioselectivity rules in organic chemistry, such as Anti-Markownikoff's Rule
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Organic chemistry students, chemistry educators, and researchers interested in reaction mechanisms and regioselectivity in electrophilic addition reactions.

Saoist
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looked in books/googled for info about this...i know what it IS, but don't understand why it happens. anyone?
 
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Originally it was based on empirical evidence (it was just the product that you got from certain reactions) and was used as a predictive tool. It can be rationilized by thinking about the intermediates of a reaction mechanism. If a carbocation is formed then it will be more stable at the more substituted carbon and therefore a nucleophile would be more likely to attack at that position.
 
Well, I ain't sure of this but consider a 1-Methyl-2-butene. When HCl adds across the double bond, Cl radical will attract the electrons of the C=C towards itself creating a partial +ve charge on the C atoms. This partial positive charge is handled better by a 3rd degree C atom than the 2nd degree C atom. Thus the -ve part of the addendum will go the the C with more substituents, which is the Markonikov's rule.
 

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