Allyl

An allyl group is a substituent with the structural formula H₂C=CH-CH₂R, where R is the rest of the molecule. It consists of a methylene bridge (-CH₂-) attached to a vinyl group (-CH=CH₂).

Quotes

• Allylic radicals, cations, and anions are unusually stable. In Lewis terms, this stabilization is readily explained by electron delocalization. In a molecular-orbital description, the three interacting p orbitals form three new molecular orbitals: One is considerably lower in energy than the p level, another one stays the same, and a third is higher in energy.
  • K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 14 : Delocalized Pi Systems

• A consequence of delocalization is that resonance-stabilized allylic intermediates can readily participate in reactions of unsaturated molecules. (...) These conditions slow the ionic addition pathway sufficiently to allow a faster radical chain mechanism to take over, leading to radical allylic substitution.
  • K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 14 : Delocalized Pi Systems

• Conjugated dienes are electron rich and are attacked by electrophiles to give intermediate allylic cations on the way to 1,2- and 1,4-addition products. These reactions may be subject to kinetic control at relatively low temperatures. At relatively higher temperatures, the kinetic product ratios may change to thermodynamic product ratios, when such product formation is reversible.
  • K. Peter C. Vollhardt, Neil E. Schore (2011) Organic chemistry : structure and function 6th ed. Ch. 14 : Delocalized Pi Systems