ChemActivity 20 Radical Halogenation of Alkanes 1

ChemActivity 20
Part A: Radical Halogenation Reactions
(How can we add a functional group to an un-functionalized alkane?)

Model 1: Polar and Non-polar Bond Breakage

= "double barbed" arrow (or full arrow) = "single barbed" arrow (or half arrow)

Polar Bond Breakage Non-polar Bond Breakage

Z Z Z Z Z Z Z Z

Y Z Y Z Y Z Y Z

for example: for example:

Br Br Br Br Br Br Br Br

H Br H Br H Br H Br

Critical Thinking Questions

1. Add formal charges, if necessary, to the example species in Model 1 (everything
below the words “for example.” )
2. A full arrow depicts the movement of a pair of electrons. What does a half arrow
depict?

3. Circle any radical species in Model 1. (A radical species is a species that has an
unpaired electron.)
Model 2: Showing Radical Bond Formation
new  bond made from two radical electrons

Rxn I Br Br Br Br

Rxn II Y Z Br Z
Y
Br

new  bond made from one radical electron and one electron from a breaking  bond
Critical Thinking Questions
4. Rxn II in Model 2 is one of two sigma bond forming reactions that could have taken
place with these two reactants. Use curved half-arrows to show the mechanism of a
reaction that yields Y—Br and Z radical from these same reactants.
 ChemActivity 20 Radical Halogenation of Alkanes 2

Model 3: Reactions of Bromine Radical with Various Alkanes

For each reaction below, the most likely products are shown.
H H H H

Rxn III Br H C C H Br H C C H

H H H H

H H H H H H

Rxn IV Br H C C C H Br H H C C C H

H H H H H

CH3 CH3
H3C H3C

Rxn V Br H2C C CH3 Br H H2C C CH3

Critical Thinking Questions

5. Label the carbon radicals in Model 3 as methyl, primary, secondary, tertiary, allyl or
benzyl.
a) Which carbon radical in Model 3 is closest to having an octet? Explain your
reasoning. (Recall that alkyl groups are electron donating.)

b) The following is a list of radicals from highest to lowest potential energy. Is

this list consistent with your conclusion in part a)? Explain.
highest V.E. H
CH3
1o

2o
3o or allyl
benzyl
X (halogen) lowest V.E.
c) Which reaction in Model 3 is most likely? Explain

Carbocations vs. Radicals: like carbocations, 3o radicals are lower in energy than 2o, etc.;
like carbocations, allyl and benzyl radicals are resonance stabilized;
HOWEVER, unlike carbocations, RADICALS DO NOT REARRANGE.

6. Add curved half arrows to Rxn III in Model 3 so as to illustrate the mechanism of
product formation.
a) As in Model 2, draw the other sigma bond forming reaction that could have
taken place in Rxn III, but did not. (Note: all 6 H’s of ethane are equivalent.)
 ChemActivity 20 Radical Halogenation of Alkanes 3

b) Construct an explanation for why Rxn III in Model 3 happens instead of the
reaction you drew in part a).

Model 4: Light Induced “Homolytic” Bond Cleavage

When a solution of Br2 is exposed to a strong light source a very small percentage of
the Br2 molecules break apart to form two bromine radicals.
Strong Light Br Br
Br Br (h)
Source

billions and billions (ratio of reactants to products) very few

“Strong Light Source” is usually abbreviated with the letters h.

Information
No evidence for methyl or 1o carbocations has been found to date. However, the
same is not true for methyl and 1o radicals: both are known. In fact there is evidence for
all of the following radicals (listed below from highest to lowest potential energy).
highest energy H CH3 2o 3o allyl benzyl X (halogen) lowest energy

Critical Thinking Questions

7. When a solution of Br2 and methane is exposed to a strong light source one of the
major products is CH3Br.

H H
(excess)
Br Br + other
H C H H C Br products
h
H H

Use curved arrows to show a reasonable multi-step mechanism for this reaction.
 ChemActivity 20 Radical Halogenation of Alkanes 4

Model 5: Collision Statistics

A reaction between two radicals may seem very likely from an energy standpoint
because in such a reaction two high P.E. species combine to form one low P.E. species.
for example:
rxn is very very downhill
H3C Br H3C Br
but statistically unlikely!!

However, radicals are so high in energy that they react with anything they “bump
into.” This means a radical has a short life-span and usually does not have time to “find”
another radical.
Critical Thinking Questions
8. Picture a crowded stadium with 100,000 people. Five of these people are violently
reactive and will start a fight with the first person they bump into-getting themselves
thrown out of the stadium. What are the chances that two of the five "violently
reactive people" get in a fight with one another? (Assume they enter at different
gates.)

9. The first two steps of the mechanism from CTQ 7 are drawn for you below.
reaction mixture after step 2
h
Br Br Br
step 1 Br
Br Br H
H
huge excess step 2 step 3
of Br2
H C H
H C H

H
H

a) Based on the information in Model 5, circle any step in your mechanism on

the previous page that has a low probability of occurring.

b) ·CH3 is like the "fighter" in the stadium analogy. It is a very reactive radical,
and it will react with the first thing it bumps into. What is the most prevalent
species in the reaction mixture ("stadium")? Add this species to the box
labeled "reaction mixture after step 2."

c) Show the mechanism of the statistically most likely reaction involving ·CH3
and draw the products of step 3. Notes: This reaction leads to CH3Br. There
are radical species left over at the end of step 3.
 ChemActivity 20 Radical Halogenation of Alkanes 5

Exercises for Part A

1. Along with the methyl radical, there is a Br radical in the box in CTQ 9. What
happens if Br radical reacts with the most abundant species in the reaction mixture
(Br-Br)? Draw this reaction and explain why it not very interesting.

1. Construct an explanation for why the solvents on the left are suitable for radical
halogenation reactions, but the solvents on the right are not. (Note that benzene is
resonance stabilized, making it very unreactive.)
Cl
H
C
Cl C
Cl Cl O
Cl H
Cl
carbon cyclohexane hexane dichloromethane diethyl ether
benzene tetrachloride
suitable solvents NOT suitable solvents

Consider the partial resonance representation of a benzyl radical species.

a) Use curved half-arrows to generate the other three resonance structures.

b) On the incomplete composite structure of this benzyl radical (shown below),
mark each carbon that has partial radical character with a delta radical.

 = "delta radical"

c) Explain why a benzyl radical is much lower in potential energy than the
radical drawn below. (Hint:are there important resonance structures for the
species below that show the spreading out of the radical over several atoms?)
 ChemActivity 20 Radical Halogenation of Alkanes 6

2. Based on the analogy to carbocations, circle the species below that is lower in
potential energy.

a) Construct an explanation for your choice. (Hint: use curved arrows to draw
any other resonance structures for each of the radical species above.)
b) Which one of these radicals is an allyl radical? Explain why.
c) Draw an allyl carbocation and explain the similarity between an allyl radical
and an allyl carbocation.

3. Give an example of each of the following and label each example with one of the
following words: primary radical, secondary radical, tertiary radical, methyl radical,
benzyl radical, allyl radical.