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Why are tertiary halogenalkanes more reactive than primary halogenalkanes?
020608

Corrie writes .....
 
Tertiary halogenoalkanes undergo substitution, e.g. by OH-, via a two-step reaction. The first, rate determing step, is the loss of the halogen as a halide ion, X-. This leaves a tertiary carbonium ion, R3C+.
 
Tertiary carbonium ions are more stable than primary carbonium ions (I won't go into why here), so the activation energy involved for this step is lower than it would be for a primary carbonium ion from a primary halogenoalkane. The primary halogenoalkane would react so slowly via this route that reaction via a different mechansim, requiring a nucleophilic species to assist in breaking the C-X bond, takes over. This is still a much slower process, so tertiary halogenoalkanes appear much more reactive to substitution reactions than primary ones - providing the halogen involved is the same!
 

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updated: 08 June 2008

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