Allylic Substitution

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We noted earlier that benzylic and allylic sites are exceptionally reactive in free radical halogenation reactions. Since carbon-carbon double bonds add chlorine and bromine in liquid phase solutions, radical substitution reactions by these halogens are often carried out at elevated temperature in the gas phase (first equation below). Formation of the ionic π-complexes that are intermediates in halogen addition is unfavorable in the absence of polar solvents, and entropy generally favors substitution over addition.

The brominating reagent, N-bromosuccinimide (NBS), has proven useful for achieving allylic or benzylic substitution in CCl₄ solution at temperatures below its boiling point (77 ºC). One such application is shown in the second equation.

The predominance of allylic substitution over addition in the NBS reaction is interesting. The N–Br bond is undoubtedly weak (probably less than 50 kcal/mol) so bromine atom abstraction by radicals should be very favorable. The resulting succinimyl radical might then establish a chain reaction by removing an allylic hydrogen from the alkene. One problem with this mechanism is that NBS is very insoluble in CCl₄, about 0.006 mole / liter at reflux. Although it is possible that the allylic bromination occurs at a solid-liquid interface, evidence for another pathway has been obtained. In the non-polar solvent used for these reactions, very low concentrations of bromine may be generated from NBS. This would serve as a source of bromine atoms, which would abstract allylic hydrogens irreversibly (an exothermic reaction) in competition with reversible addition to the double bond. The HBr produced in this way is known to react with NBS, giving a new bromine molecule and succinimide, as shown here. Ionic addition of bromine to the double bond would be very slow in these circumstances (CCl₄ is a nonpolar solvent).

HBr + (CH₂CO)₂NBr → Br₂ + (CH₂CO)₂NH

This mechanism is essentially the same as that for the free radical halogenation of alkanes, with NBS serving as a source of very low concentrations of bromine. Unsymmetrical allylic radicals will react to give two regioisomers. Thus, 1-octene on bromination with NBS yields a mixture of 3-bromo-1-octene (ca. 18%) and 1-bromo-2-octene (82%) - both cis and trans isomers.

RCH₂CH=CH₂ + (CH₂CO)₂NBr → RCHBrCH=CH₂ + RCH=CHCH₂Br + (CH₂CO)₂N

Contributors

William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry