5.3: Radical Reactions

Objectives

After completing this section, you should be able to

• give an example of a radical substitution reaction.
• identify the three steps (initiation, propagation and termination) that occur in a typical radical substitution reaction.
• write out the steps involved in a simple radical substitution reaction, such as the chlorination of methane.
• explain why the halogenation of an alkane is not a particularly useful method of preparing specific alkyl halides.

Key Terms

Make certain that you can define, and use in context, the key terms below.

• chain reaction
• initiation step
• propagation step
• radical substitution
• termination step

Study Notes

A radical substitution reaction is a reaction which occurs by a free radical mechanism and results in the substitution of one or more of the atoms or groups present in the substrate by different atoms or groups.

The initiation step in a radical chain reaction is the step in which a free radical is first produced. A termination step of a radical chain reaction is one in which two radicals react together in some way so that the chain can no longer be propagated.

While radical halogenation of very simple alkanes can be an effective synthetic strategy, it cannot be employed for larger more complex alkanes to yield specific alkyl halides, since the reactive nature of radicals always leads to mixtures of single- and multiple-halogenated products.

The Three Phases of Radical Chain Reactions

Because of their high reactivity, free radicals have the potential to be both extremely powerful chemical tools and extremely harmful contaminants. Much of the power of free radical species stems from the natural tendency of radical processes to occur in a chain reaction fashion. Radical chain reactions have three distinct phases: initiation, propagation, and termination.

The initiation phase describes the step that initially creates a radical species. In most cases, this is a homolytic cleavage event, and takes place very rarely due to the high energy barriers involved. Often the influence of heat, UV radiation, or a metal-containing catalyst is necessary to overcome the energy barrier.

Molecular chlorine and bromine will both undergo homolytic cleavage to form radicals when subjected to heat or light. Other functional groups which also tend to form radicals when exposed to heat or light are chlorofluorocarbons, peroxides, and the halogenated amide N-bromosuccinimide (NBS).

The propagation phase describes the 'chain' part of chain reactions. Once a reactive free radical is generated, it can react with stable molecules to form new free radicals. These new free radicals go on to generate yet more free radicals, and so on. Propagation steps often involve hydrogen abstraction or addition of the radical to double bonds.

Chain termination occurs when two free radical species react with each other to form a stable, non-radical adduct. Although this is a very thermodynamically downhill event, it is also very rare due to the low concentration of radical species and the small likelihood of two radicals colliding with one another. In other words, the Gibbs free energy barrier is very high for this reaction, mostly due to entropic rather than enthalpic considerations. The active sites of enzymes, of course, can evolve to overcome this entropic barrier by positioning two radical intermediates adjacent to one another.

Exercise \(\PageIndex{1}\)

Radical chlorination of alkanes are not useful due to uncontrolled substitution. Draw the mono-substituted products of Cl₂ reacting with 2-methylbutane.

Answer

Exercise \(\PageIndex{2}\)

Propose a radical mechanism for the following reaction:

Answer