Allylic and benzylic bromination[edit]

Standard conditions for using NBS in allylic and/or benzylic bromination involves refluxing a solution of
NBS in anhydrous CCl4 with a radical initiator—usually azobisisobutyronitrile (AIBN) or benzoyl peroxide,
irradiation, or both to effect radical initiation.[5][6] The allylic and benzylic radical intermediates formed
during this reaction are more stable than other carbon radicals and the major products are allylic and
benzylic bromides. This is also called the Wohl–Ziegler reaction.[7][8]

The carbon tetrachloride must be maintained anhydrous throughout the reaction, as the presence of
water may likely hydrolyze the desired product.[9] Barium carbonate is often added to maintain
anhydrous and acid-free conditions.

In the above reaction, while a mixture of isomeric allylic bromide products are possible, only one is
created due to the greater stability of the 4-position radical over the methyl-centered radical.

Chapter 11 : Arenes and

Aromaticity
Benzylic systems

 As we saw in chapter 10, the positions adjacent to C=C in alkenes is referred to as the
allylic position. They often show enhanced reactivity compared to simple alkanes due to
the proximity of the adjacent π system.
 Similarly, the positions adjacent to a benzene ring, known as the benzylic position also
show enhanced reactivity compared to simple alkanes.

Students often confuse the term benzyl with phenyl, for example compare the location of the
bromine atoms in bromobenzene and benzyl bromide:

Highlight benzylic C

Highlight benzylic H

Highlight phenyl C

Highlight phenyl H
 Reset colours

Bromobenzene Benzyl bromide

(phenyl bromide)
Benzylic carbocations

The p system of a benzene ring can stabilise an adjacent carbocation by donating electron density
through resonance. Remember that delocalising charge is a stabilising effect.
Note that in the resonance forms of the benzylic cation, the positive charge is located on the
ortho and para positions of the benzene ring, but not the meta positions. This is reflected in the
resonance hybrid.
Due to the stability of these benzylic cations, they are readily formed as intermediates during
chemical reactions, for example SN1 reactions of benzylic halides. Note that 2-chloro-2-
phenylpropane is 600 times more reactive that the 2-methyl analogue.

Benzylic radicals

Benzyl radicals can also be stabilised by resonance in the same manner as shown above for
carbocations.

© Dr. Ian Hunt, Department

of Chemistry
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 Purdue: Chem 26605 (Lipton)

 Chapter 15. Reactions of Free Radicals and Radical Ions

15.2: Allylic and Benzylic Halogenation

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Table of contents
When halogens are in the presence of unsaturated molecules such as alkenes, the expected reaction is
addition to the double bond carbons resulting in a vicinal dihalide (halogens on adjacent carbons).
However, when the halogen concentration is low enough, alkenes containing allylic hydrogens undergo
substitution at the allylic position rather than addition at the double bond. The product is an allylic
halide (halogen on carbon next to double bond carbons), which is acquired through aradical chain
mechanism.

Why Substitution of Allylic Hydrogens?

As the table below shows, the dissociation energy for the allylic C-H bond is lower than the dissociation
energies for the C-H bonds at the vinylic and alkylic positions. This is because the radical formed when
the allylic hydrogen is removed is resonance-stabilized. Hence, given that the halogen concentration is
low, substitution at the allylic position is favored over competing reactions. However, when the halogen
concentration is high, addition at the double bond is favored because a polar reaction outcompetes the
radical chain reaction.

Radical Allylic Bromination (Wohl-Ziegler Reaction)

Preparation of Bromine (low concentration)
NBS (N-bromosuccinimide) is the most commonly used reagent to produce low concentrations of
bromine. When suspended in tetrachloride (CCl4), NBS reacts with trace amounts of HBr to produce a
low enough concentration of bromine to facilitate the allylic bromination reaction.
Allylic Bromination Mechanism
Step 1: Initiation
Once the pre-initiation step involving NBS produces small quantities of Br2, the bromine molecules are
homolytically cleaved by light to produce bromine radicals.

Step 2: Propagation
One bromine radical produced by homolytic cleavage in the initiation step removes an allylic hydrogen
of the alkene molecule. A radical intermediate is generated, which is stabilized by resonance. The
stability provided by delocalization of the radical in the alkene intermediate is the reason that
substitution at the allylic position is favored over competing reactions such as addition at the double
bond.

The intermediate radical then reacts with a Br2 molecule to generate the allylic bromide product and
regenerate the bromine radical, which continues the radical chain mechanism. If the alkene reactant is
asymmetric, two distinct product isomers are formed.

Step 3: Termination
The radical chain mechanism of allylic bromination can be terminated by any of the possible steps
shown below.
 Radical Allylic Chlorination
Like bromination, chlorination at the allylic position of an alkene is achieved when low concentrations of
Cl2 are present. The reaction is run at high temperatures to achieve the desired results.

Industrial Uses
Allylic chlorination has important practical applications in industry. Since chlorine is inexpensive, allylic
chlorinations of alkenes have been used in the industrial production of valuable products. For example,
3-chloropropene, which is necessary for the synthesis of products such as epoxy resin, is acquired
through radical allylic chlorination (shown below).

Problems (Answers are attached as a file)

1. Cyclooctene undergoes radical allylic bromination. Write out the complete mechanism including
reactants, intermediates and products.
2. Predict the two products of the allylic chlorination reaction of 1-heptene.
3. What conditions are required for allylic halogenation to occur? Why does this reaction outcompete
other possible reactions such as addition when these conditions are met?
4. Predict the product of the allylic bromination reaction of 2-benzylheptane. (Hint: How are benzylic
hydrogens similar to allylic hydrogens?)
5. The reactant 5-isopropyl-1-hexene generates the products 3-bromo-5-isopropyl-1-hexene and 1-bromo-
5-isopropyl-2-hexene. What reagents were used in this reaction?

References
1. Djerassi, Carl. "Brominations with N-Bromosuccinimide and Related Compounds - The Wohl-Ziegler
Reaction." Chemical Reviews 43 (1948):271-314.
2. Easton, Christopher J., Alison J. Edwards, Stephen B. McNabb, Martin C. Merrett, Jenny L. O'Connell,
Gregory W. Simpson, Jamie S. Simpson, and Anthony C. Willis. "Allylic halogenation of unsaturated
amino acids." Organic and Biomolecular Chemistry (2003). RSC Publishing. 9 June 2003. Royal Society of
Chemistry. 25 Feb. 2009.
3. Kent, Doug. Allylic Bromination. Chem 118B Workshop. Learning Skills Center. 3 Feb. 2009.
4. Li, Chao-Jun, and Tak-Hang Chan. Comprehensive Organic Reactions in Aqueous Media. New York:
Wiley-Interscience, 2007.
5. Vollhardt, Peter C., and Neil E. Schore. Organic Chemistry: Structure and Function. 5th ed. New York:
W.H. Freeman and Company, 2007.

Outside Links
 http://en.wikipedia.org/wiki/N-Bromosuccinimide#Preparation
 http://en.wikipedia.org/wiki/Wohl-Ziegler_reaction
 http://www.mhhe.com/physsci/chemistry/carey/student/olc/graphics/carey04oc/ref/ch10allylic.html

Further Reading

Carey 5th Ed Online

Radical halogenation of Allylic Systems

Chemtube3D

Allylic bromination

MasterOrganicChemistry

Allylic bromination

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
o 15.1: Free Radical Halogenation of Alkanes

 15.3 Radical Addition to Pi Systems

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SN Reactivity of Benzyl and Allyl Systems

Benzylic and allylic halides undergo both SN1 and SN2 reactions more readily than purely alkyl
halides.

The reason is the same in both cases: stabilization by the -orbitals of the double bond or
benzene ring. In the SN1 reaction the carbocation empty p orbital interacts:

In the SN2, it is the p orbital of the transition state.