Chapter 6

Nucleophilic substitution Reactions

 

Structure Function Correlation With R Group

  • R group plays vital role on the rate of reaction .
  • R group may have steric, electronic and neighboring group effect.
  • Steric hindrance may slow the rate of reaction, as nucleophile adds to the carbon centre in the rate determining step.
  • In the transition state, the incoming nucleophile(Nuc) and leaving group(LG) are 90° to the R group. Larger R groups can result in increased strain leading to slower reaction rates.
Bulkier R Group increase steric hindrance
  • A bulkier adjacent group may deflect the trajectory of the nucleophile away from the linear approach.
Sterained Transition state due to adjacent group steric effect
  • electron withdrawing nature of groups having sp2 carbon(vinyl and phenyl)makes the adjacent carbon more electrophilic and hence reactivity towards nucleophile increases.

 

Example:    
  Higher rate for nucleophilic substitution at allyl and benzyl system.