Chapter 8: Nucleophilic Substitution

Stability:
The general stability order of simple alkyl carbocations is: (most stable) 3^o > 2^o > 1^o > methyl (least stable)

This is because alkyl groups are weakly electron donating due to hyperconjugation and inductive effects. Resonance effects can further stabilise carbocations when present.

Structure:
 

Alkyl carbocations are sp2 hybridised, planar systems at the cationic C centre.  The p-orbital that is not utilised in the hybrids is empty and is often shown bearing the positive charge since it represents the orbital available to accept electrons.

Reactivity:

As they have an incomplete octet, carbocations are excellent electrophiles and react readily with nucleophiles. Alternatively, loss of H+ can generate a p bond.  The electrostatic potential diagrams clearly show the cationic center in blue, this is where the nucleophile will attack.

Rearrangements:
Carbocations are prone to rearrangement via 1,2-hyride or 1,2-alkyl shifts provided it generates a more stable carbocation. For example:

Notice that the "predicted" product is only formed in 3% yield, and that products with a different skeleton dominate.  The reaction proceeds via protonation to give the better leaving group which departs to give the 2o carbocation shown.  A methyl group rapidly migrates taking its bonding electrons along, giving a new skeleton and a more stable 3o carbocation which can then lose H+ to give the more stable alkene as the major product.

2o carbocation to 3o carbocation

This is an example of a 1,2-alkyl shift.  The numbers indicate that the alkyl group moves to an adjacent position.
Similar migrations of H atoms, 1,2-hydride shifts are also known.

Reactions involving carbocations:
1. Substitutions via S_N1 (see also Chapter 4)
2. Eliminations via E1 (Chapter 5)
3. Additions to alkenes (e.g. HX, H₃O⁺) (Chapter 6)
4. Additions to alkynes (e.g. HX, H₃O⁺) (Chapter 9)
5. Friedel-Crafts alkylations (Chapter 12)

© Dr. Ian Hunt, Department of Chemistry, University of Calgary