Nucleophilic substitution in halogenoalkanes

  • The mechanism for this reaction is nucleophilic substitution
  • Hydroxide ions act as nucleophiles (a species with a negative charge or a lone pair of electrons that can be donated to form a covalent bond with a positive or 𝛿+ carbon atom)
  • Common nucleophiles also include halide ions (Cl), cyanide ions (CN), ammonia (NH3) and water molecules

Let’s look at this mechanism in a little more detail ….

  1. The hydroxide ion is attracted to the 𝛅+ carbon atom (the C-Br bond is polar because bromine is slightly more electronegative than carbon, but becomes more polarised as the hydroxide ion approaches). 
  2. The OH ion attacks from the opposite side to the bromine and uses a lone pair of electrons to begin to form bond with the carbon atom.
  1. At the same time as the OH- is attacking, the bromine begins to leave, taking the pair of electrons from the C-Br bond with it.
  1. There is a short-lived, unstable transition state in which both the O and the Br are partially bonded to the carbon.
  1. Bromine leaves as an ion.  The product molecule is inverted (turned inside out like an umbrella) compared with the original halogenoalkane reactant – this is a direct result of the direction of attack of the OH.

Note:

The nucleophile always attacks the 𝛅+ carbon from the side opposite to the C-X bond because the empty molecular orbital which accepts the incoming electron pair from the nucleophile is orientated along the C-X bond axis.