Fundamentals of Organic ChemistryChemistryHaloalkanes and Haloarenes
Consider the following nucleophilic aromatic substitution reactions: (I) (II) (III) Choose the correct order of reactivity for these reactions.
Options
- A(I) > (II) > (III)
- B(II) > (III) > (I)
- C(I) = (II) = (III)
- D(I) < (II) < (III)
Correct answer
A. (I) > (II) > (III)
Step-by-step solution
The given reactions proceed via the nucleophilic aromatic substitution ( S_NAr ) mechanism. In an S_NAr reaction, the rate-determining step is the addition of the nucleophile to the halogen-bearing carbon to form a carbanion intermediate (Meisenheimer complex). The carbon-halogen bond breaking is not involved in this slow step. The reactivity is governed by the electron-withdrawing inductive effect ( -I effect) of the halogen, which increases the electrophilicity of the carbon atom and stabilizes the intermediate c