Radical Reactions

Richard F. Daley and Sally J.
Daley
www.ochem4free.com
Organic
Chemistry
Chapter 21
Radical Reactions
21.1 Radical Structure and Stability 1093
21.2 Halogenation of Alkanes 1095
Sidebar - Atmospheric Ozone Depletion 1099
21.3 Allylic Bromination 1102
21.4 Benzylic Bromination 1105
Synthesis of 1-Bromo-1-phenylethane 1106
21.5 Radical Addition to Alkenes 1107
21.6 Radical Oxidations 1112
21.7 Radical Reductions 1115
Synthesis of 1-Methoxy-1,4-cyclohexadiene 1121
Special Topic - Electron Spin Resonance Spectroscopy 1122
Key Ideas from Chapter 21 1125
Organic Chemistry - Ch 21 1092 Daley & Daley
Copyright 1996-2005 by Richard F. Daley & Sally J. Daley

All Rights Reserved.
No part of this publication may be reproduced, stored in a retrieval system, or

transmitted in any form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of the copyright
holder.
www.ochem4free.com 5 July 2005

Chapter 21
Radical Reactions
Chapter Outline
21.1 Radical Structure and Stability
A chemical species with an unpaired
electron in the valence shell
21.2 Halogenation of Alkanes
The reaction of alkanes and halogens with
energy provided by light or heat to form
alkyl halides
21.3 Allylic Bromination
The reaction of bromine radicals with
alkenes in the allylic position
21.4 Benzylic Bromination
The reaction of bromine radicals with alkyl
benzenes in the benzylic position
21.5 Radical Addition to Alkenes
Anti-Markovnikov additions to double bonds
21.6 Radical Oxidations
A brief survey of autooxidation processes in
organic chemistry
21.7 Radical Reductions
A brief survey of radical reduction reactions
Objectives
9Understand the structure of a radical

9Know the distribution of the halogens in a radical halogenation of
an alkane
9Recognize that radicals at the allylic and benzylic positions are
more stable than alkyl radicals
9Know why a radical addition to an alkene leads to an “anti-
Markovnikov” product
9Understand the autooxidation processes
9Be able to use radical reductions in synthesis

Whoever in discussion adduces authority uses not

intellect but rather memory.
—Leonardo da Vinci
A ny atom, or group of atoms, that bears an unpaired

electron is a radical. Although a radical may be
charged or uncharged, most organic radicals are uncharged. This
chapter covers only the uncharged species. Because electrons tend to
exist in pairs and because radicals have an unpaired electron, radicals
are usually highly reactive. Unlike the reactions discussed to this
point, radical reactions involve the movements of single electrons
instead of pairs of electrons.
This chapter is an introduction to some of the many laboratory,
industrial, and biological processes that involve radicals. For example,
many polymers of commercial importance are synthesized via radical
Radical polymerization reaction processes. Additionally, the oxygen carrying capability of
is discussed in several hemoglobin depends on the diradical nature of oxygen. Biochemical
sections in Chapter 22. degradation processes often involve radicals, too.
21.1 Radical Structure and Stability

During the latter part of the nineteenth century, most chemists
thought that radicals were sufficiently unstable to preclude their
observation. Many also thought that radicals were so unstable that
they could not even exist. However, in 1900, Moses Gomberg at the
University of Michigan generated the first laboratory example of a
radical, although it was another 30 years before anyone realized what
it was that he had made. Gomberg had successfully synthesized
tetraphenylmethane in 1897 and wished to synthesize
hexaphenylethane to study its properties. Gomberg's plan was to
produce hexaphenylethane by reacting triphenylmethyl chloride with
silver ion.
Ag
Ph3CCl Ph3CCPh3
When Gomberg ran the reaction, he obtained a yellow solution

that contained a very reactive material. This material reacted rapidly
with oxygen from the air to form Ph3COOCPh3, or with iodine to form
Ph3CI. When Gomberg reported this reaction, he suggested that the
intermediate was a trivalent carbon. However, he proposed that it was
a carbocation instead of a radical. Although chemists have come to

understand the part radicals had in Gomberg's experiment, no one has

yet accomplished Gomberg's goal of synthesizing hexaphenylethane.
The structure of radicals is very similar to the structure of
carbocations because both are sp2 hybridized. However, carbocations
have an empty p orbital, whereas radicals have an unpaired electron
in the p orbital.
C C
Carbocation Radical
The structure of a radical varies somewhat depending on the

substituents bonded to the carbon atom. When the substituents are
hydrocarbons, the radicals have a mostly planar structure. When one
of the substituents is a heteroatom with nonbonding electron pairs,
however, the radical tends towards an sp3 arrangement due to the
repulsive influence that the nonbonding electrons exert on the single
electron of the radical. Note that nonbonding electrons, particularly if
close to the radical site as with an oxygen or nitrogen, can also
stabilize the radical.
Repulsion
Less repulsion
• •• •
••
C X C
X
Radical stability is also similar to carbocation stability. Thus,

the order of stability for radicals is 3o > 2o > 1o > methyl. A vinyl or
phenyl group bonded adjacent to the site of the radical makes the
radical more stable than a tertiary radical. This is because allylic and
benzylic radicals are resonance stabilized.
• •
C C C C C C
Allylic radical
•
CH2• CH2 CH2 CH2
• •
Benzylic radical

With uncharged radicals, the polarity of the solvent does not

usually affect the rate of radical reaction. However, the presence of an
inhibitor does affect the rate. Oxygen is a common inhibitor. It
An inhibitor is some
chemical species, either
normally exists as a diradical with two unpaired electrons in two
a molecule or radical, different degenerate orbitals.
which is particularly
reactive with a radical.
21.2 Halogenation of Alkanes
Alkanes react with chlorine in the presence of ultraviolet light
(represented as hQ) or heat (usually 200-300oC) to produce alkyl
chlorides. Generally, the reaction gives a mixture of products, as does
the reaction of methane with chlorine.
Cl2
CH4 CH3Cl + CH2Cl2 + CHCl3 + CCl4
h
The composition of this mixture of alkyl chlorides varies with the
concentrations of the chlorine and the alkane. However, even if you
use a large excess of the alkane, the reaction still forms a mixture.
Radicals and Atoms
The reaction of chlorine with an alkane is a radical reaction. Chemists refer to the
species that forms when the chlorine molecule dissociates as chlorine atoms. They are
called chlorine atoms because chlorine has seven valence electrons, giving the chlorine
atom an unpaired electron. The reaction is a radical reaction because the chlorine
When a bond breaks in atom reacts with an alkane forming an alkyl radical.
a homolytic bond
dissociation, each atom
takes one electron.
The bond dissociation energy of the chlorine molecule is only
58 kcal/mol, so chlorine readily undergoes a homolytic bond
When a bond breaks in dissociation. All the reactions that you have studied in the previous
a heterolytic bond chapters underwent heterolytic bond dissociations.
dissociation, one atom
takes both electrons.
h or
Cl Cl 2 Cl• H = 58 kcal/mol
The single barbed
mechanism arrows in The chlorine atoms that form in a homolytic bond dissociation reaction
this reaction indicate
the movement of single
are very reactive because each has an unpaired electron. They are
electrons. electrophilic, thus each seeks an electron to complete its unfilled shell
of electrons. In a reaction with methane, a chlorine atom readily
removes a hydrogen from the methane.
Cl •
CH3 H CH3• + HCl

The resulting methyl radical, which also is very electrophilic, then

removes a chlorine atom from a chlorine molecule.
CH3•
Cl Cl Cl • + CH3Cl
Notice that the last step in the mechanism produced another

chlorine atom. This chlorine atom can then remove a hydrogen atom
from another methane molecule to produce another methyl radical.
Each step in a chain The methyl radical can then react with another chlorine molecule to
reaction produces a
produce another chlorine atom to start the cycle again. This type of
chemical species that
initiates another step reaction is known as a chain reaction.
in the reaction. A chain reaction mechanism consists of three categories of
Initiation forms the steps: 1) the initiation step, 2) the propagation steps, and 3) the
initial radicals to begin termination steps. The initiation step produces the reactive species,
a chain reaction. or radicals. In the radical chlorination reaction above, the initiation
step is the formation of chlorine atoms. The propagation steps produce
Propagation continues
the chain reaction.
the major portion of the reaction product and are repeated many
times. With each propagation series a new reactive species forms,
Termination stops the keeping the reaction going. The next two steps of the radical
chain reaction. chlorination above, consuming a chlorine atom then producing
another, are the propagation steps. The termination steps are the
steps that stop the chain reaction. For the radical chlorination, the
possible termination steps are as follows:
CH3•
Cl • CH3Cl
CH3•
CH3• CH3CH3
Cl•
Cl• Cl2
The initiation step is generally the slowest step in the radical

halogenation reaction because it requires 58 kcal/mol to produce the
reactive halogen atom. The propagation steps carry the reaction
forward. The propagation steps in an alkane halogenation reaction
produce one molecule of the product and a new halogen atom. For
radical halogenation, about 10,000 propagation steps occur for each
initiation step. Moreover, termination happens infrequently because
the concentrations of the radicals are low compared to the
concentrations of the other reagents.

When 2-methylbutane reacts at 300oC with one mole of

chlorine, the result is a mixture of four monochlorinated products in
the following relative amounts.
CH3 CH3 CH3

Cl2
CH3CHCH2CH3 ClCH2CHCH2CH3 + CH3CCH2CH3 +
300oC
2-Methylbutane Cl
33.3% 22%
CH3 CH3
CH3CHCHCH3 + CH3CHCH2CH2Cl
Cl
28% 16.7%
Using the above percentages of the reaction's products, you can

determine the relative reactivity of each of the hydrogens in the
substrate, 2-methylbutane. Nine of the 12 hydrogens are primary
hydrogens. Reactions involving these nine hydrogens form only 50%
(the 33.3% and 16.7% products) of the total amount of product. In
comparison, the two secondary hydrogens forms 28% of the product
and the single tertiary hydrogen forms 22%.
50% of the product
CH3
CH3CHCH2CH3
22% of the product

28% of the product
Based on statistical predictions, if these three classes of

hydrogens all had the same reaction rate, you would expect 75% (9/12)
of the product to form from the primary hydrogens, 16.7% (2/12) from
the secondary hydrogens and 8.3% (1/12) from the tertiary hydrogen.
However, the primary hydrogens have less than the statistical amount
of product and the secondary and tertiary hydrogens have more, so
there is a difference in their reactivity.
To calculate the relative rates for the reaction that occurs at
each of the hydrogens, assume that the rate of reaction for primary
hydrogens is 1. Then perform the following calculations.

Secondary 28/2
Primary = 50/9 = 2.5
Tertiary 22/1
Primary = 50/9 = 4
These calculations show you that the secondary hydrogens react 2.5
times faster than the primary hydrogens, and the tertiary hydrogens
react four times faster than the primary hydrogens.
This difference in reactivity in the various types of hydrogens is
the result of how readily the various radicals form. The tertiary
radical is the most stable and the easiest to form. The primary radical
is the least stable radical and the hardest to form.
The differences in radical reactivity are less important in
reactions that involve fluorine radicals and alkanes than in reactions
that involve chlorine radicals and alkanes. The fluorine atom is more
reactive than the chlorine atom. Thus, the fluorine atom is much less
selective than the chlorine atom. In contrast, the iodine atom is so
unreactive that it does not even react with alkanes.
Although bromine radicals are much more selective than
chlorine atoms, they are sufficiently reactive to allow some reaction to
occur. For example, the radical bromination of 2-methylbutane gives
more than 90% 2-bromo-2-methylbutane. The reaction requires both
heat and light to proceed.
CH3 CH3 CH3

Br2
CH3CHCH2CH3 CH3CCH2CH3 + CH3CHCH2CH2Br +
h , 127oC
Br
90.3% 0.2%
CH3 CH3
CH3CHCHCH3 + BrCH2CHCH2CH3
Br
9.1% 0.4%
If you perform the same calculations for bromine as with chlorine, the
relative reactivities are 1 : 83 : 1640. Thus, radical bromination is
much more selective for the tertiary position than is chlorination. This
increased selectivity makes the reaction synthetically useful for the
preparation of tertiary alkyl bromides.
Exercise 21.1

The regioselectivity of chlorine is dependent on the temperature of the

reaction. The relative rates for chlorination of 2-methylbutane at
600oC are 1 : 2.1 : 2.5 rather than the 1 : 2.5 : 4 at 300oC. Explain this
observation.
Exercise 21.2
Even at relatively high temperatures and in the presence of light,

neopentane (2,2-dimethylpropane) reacts much faster with chlorine
than it does with bromine. Explain this observation.
[SIDEBAR]
Atmospheric Ozone Depletion

Seventy-five years ago, refrigerators used toxic and noxious
gases such as ammonia and sulfur dioxide as refrigerants. If a leak
Roy Plunkett is the developed in a refrigerator, dangerous amounts of these gases escaped
inventor of Teflon. See into the air of the home or workplace. In the 1920s, Roy Plunkett and
Section 0.3, page 000.
his assistant, Jack Rebok, experimented to find an odorless, tasteless,
and nontoxic substitute for these substances.
After a careful survey of the chemical literature, they decided
that the best possible candidates were the organic compounds that
contained both chlorine and fluorine. They synthesized a sample of a
gaseous compound of chlorine and fluorine and placed some of the
substance, along with a guinea pig, under a bell jar. The guinea pig
was unharmed. Although this test seems crude by today's
experimental standards, it was a standard practice then.
Encouraged by the low toxicity demonstrated by this test, they
synthesized a variety of these chlorofluorocarbons (CFCs). Further
tests indicated that these compounds were indeed nontoxic to animals
and, by inference, nontoxic to humans as well. Du Pont introduced
these CFCs under the trade name of Freon.
For a number of years, industry used the CFC chemicals
widely. Not only were they used as refrigerants, but they were also
used for such things as propellants in aerosol products and foaming
agents for foam plastics. As a result of their extensive use, thousands
of tons of CFCs were introduced into the atmosphere. In the mid-
1970s, environmental chemists proposed that these otherwise inert
materials could destroy the stratospheric ozone layer.
To understand the problem, review the process of ozone
formation in the upper atmosphere. Incoming ultraviolet radiation
causes a homolytic bond dissociation in molecular oxygen.

h
O2 2 O•
More incoming ultraviolet radiation provides the energy needed by

each of these oxygen atoms to either react with another oxygen atom
to reform a molecule of oxygen or to react with a molecule of oxygen to
produce ozone.
h
O2 + O • O3
As well as dissociating the molecular oxygen, ultraviolet radiation also

dissociates molecules of ozone to produce an electronically excited
oxygen atom and an oxygen molecule.
h
O3 O2 + O •
These reactions make up a chain reaction that will continue as long as

oxygen and ultraviolet radiation are available. The net result of these
three reactions is the absorption of most of the incoming ultraviolet
radiation that would otherwise reach earth's surface damaging the
plant and animal life there.
Oxygen and ozone are not the only compounds that absorb
ultraviolet radiation. Two widely used CFCs, CFCl3 and CF2Cl2,
absorb radiation at the same wavelengths as molecular oxygen and
ozone. When these CFCs absorb ultraviolet radiation, a C—Cl bond
homolytically cleaves to form a chlorine atom.
h
CFCl3 CFCl2 • + Cl •
h
CF2Cl2 CF2Cl • + Cl •
Once formed, the chlorine atom can react with ozone to produce
ClO and molecular oxygen. The ClO, in turn, reacts with atomic
oxygen to form a chlorine atom and a molecule of oxygen.
Cl • + O3 ClO + O2
ClO + O • Cl • + O2
Net: O3 + O • 2 O2
These reactions take place more readily than do reactions involving

just oxygen and ozone. Moreover, the reactions with chlorine take

place without the presence of ultraviolet radiation. The net result is a

catalytic cycle that destroys a molecule of ozone while regenerating
the chlorine atom. Notice that the oxygen atom reacts with the ClO
instead of with another oxygen atom to form an oxygen molecule, or
with an oxygen molecule to form ozone.
Both chain reactions take place between 25 and 40 km above
the earth's surface. The low reactivity that makes CFCs so attractive
for their industrial uses also gives them a long lifetime in the
atmosphere. Environmental chemists estimate that it will take from
40 to 150 years for the CFCs to diffuse into the upper atmosphere and
react there. This means that even if CFCs were immediately removed
from the marketplace, their concentration in the upper atmosphere
would continue to increase for a number of years.
Not all scientists accept that CFCs are responsible for the
decline of the ozone layer. Some feel that there is not enough data to
even conclude that there is a genuine loss of the ozone layer. From
their viewpoint, because the baseline of data covers only a few years,
there is insufficient data to justify the conclusion that human
activities are damaging the ozone layer. Perhaps what is happening
with the ozone is a part of some, as yet unknown, natural cycle. All do
agree, however, that the loss of the ozone is a potentially serious
problem and must be closely monitored.
The chlorine in the CFCs is not the only potential culprit in the
destruction of the ozone layer in the upper atmosphere.
Environmental chemists know of other chemical substances that react
with ozone in similar ways to the CFCs. Two of these are nitrogen
oxides and hydroxyl radicals. The nitrogen oxides originate in
automobile exhaust gases and other high temperature processes. The
hydroxyl radicals form in nature as a result of the homolytic cleavage
of an H—OH bond of water.
If human activity is responsible for the decline of the ozone
layer, it is urgent to understand the extent of the problem and to
correct it. If the decline of the ozone is a natural process, measures
must be taken to minimize the damages from the resulting increase in
UV levels at the earth's surface. Perhaps you could be instrumental in
solving these problems.
21.3 Allylic Bromination

In general, when chemists want to substitute a halogen onto an
allylic carbon of an alkene, they use a radical halogenation reaction.
An excellent source of bromine atoms for this reaction is N-
bromosuccinimide (NBS). Simply dissolve NBS in a nonpolar
substance, such as CCl4, in the presence of light and heat:

O O
h or
N Br N • + Br •
CCl4
O O
After the bromine atom forms, it abstracts a hydrogen atom from the
allylic position of an alkene. This abstraction produces a resonance-
stabilized allyl radical and HBr.
+ HBr
Br •
H
Allyl radical
The HBr then reacts with another molecule of NBS to form Br2 and
succinimide. Succinimide is a by-product of the reaction.
•• •• ••
H H
O•• O •
• O
•• ••
• •
•• H Br
••
•
• ••
• Br
••
•
N Br N Br N ••
O ••
••
O••
•• ••
O••
NBS
Tautomerize
••
O••
••
N H
O••
••
Succinimide
At this point in the reaction, the reaction mixture contains a low

concentration of bromine molecules. These bromine molecules react

with the allylic radicals to produce the allyl bromide and a bromine
atom. The new bromine atom can then react with the alkene to form
another allylic radical.
Br Br Br
•
+ Br•
Because the allylic radical reacts with Br2 instead of NBS to

form the final product of the reaction, you may be wondering why Br2
wasn’t used to begin with instead of NBS? The problem is, the
bromine would add to the double bond instead of substituting onto the
The addition of
allylic carbon. With NBS as the reagent, the addition reaction does not
bromine to a double occur.
bond was discussed in The addition reaction does not occur with NBS as the reagent
Section 14.6, page 000. because the concentration of bromine is too low to have much
probability of occurring. Recall from Chapter 14 that the first step in
the addition of bromine to the double bond is the reversible formation
The bromonium ion is of a bromonium ion. The next step is an attack of a bromide ion on this
introduced in Section intermediate. If no bromide ion is nearby, the bromonium ion
14.2, page 000. dissociates. Another reason that the addition reaction does not occur is
that NBS competes with the bromonium ion for bromide ions. Because
there is a far higher concentration of NBS, most bromide ions in
solution will find a molecule of NBS before they will find a bromonium
ion.
Monitoring the NBS Reaction
Chemists can easily monitor the progress of an allylic halogenation reaction being run
in CCl4 because both the NBS and the by-product, succinimide, are nearly insoluble
whereas the product is soluble. Furthermore, the NBS is denser than the solvent, so it
sinks below the solvent whereas succinimide is lighter than the solvent so it floats on
top of the reaction mixture. The reaction is complete when the NBS on the bottom of
the reaction mixture disappears.
The reaction also proceeds well in the presence of a radical

initiator. Two good radical initiators are benzoyl peroxide and
azobisisobutyronitrile (AIBN). Both molecules readily form radicals
that initiate the chain reaction of NBS with an alkene.

O
O
O O•
O
Benzoyl peroxide
N N + N2
CN CN CN
Azobisisobutyronitrile
Chemists have extensively studied the mechanism for this

reaction, but do not yet clearly understand it. For simple cases, the
mechanism proposed in this section explains the outcome of the
reaction; but in more complicated cases, it doesn't. Chemists are still
working to answer the questions that arise, so they can clearly
understand the mechanism.
Solved Exercise 21.1
How many isomeric bromoalkenes are formed from the reaction of 2-pentene
with NBS?
Solution
There are two allylic positions in 2-pentene: one primary at C1 and one
secondary at C4. The secondary radical is more stable than the primary
radical, so the secondary radical forms almost exclusively. The resulting
radical is symmetrical and only one bromoalkene is formed.
NBS • •
CH3CH2CH CHCH3 CH3CHCH CHCH3 CH3CH CHCHCH3
CCl4,
CH3CHCH CHCH3
Br
Exercise 21.3
When 3-phenyl-1-propene is heated with NBS in CCl4, it forms two

products in a 5:1 ratio. The two products are 3-bromo-1-phenyl-1-
propene and 3-bromo-3-phenyl-1-propene. Which of the two products
forms in the higher yield? Why?

21.4 Benzylic Bromination

The hydrogens attached to the carbon in the benzylic position
of an alkyl benzene react similarly to the hydrogens attached to the
carbon in the allylic position of an alkene. Both sites readily react in a
radical halogen substitution reaction. The reaction of NBS with
toluene produces an excellent yield of benzyl bromide.
CH3 CH2Br
NBS
CCl4,
(88%)
The reaction proceeds via a resonance-stabilized benzylic

radical in which the electron deficiency spreads over four carbon
atoms. This resonance stabilization makes the benzylic radical a
relatively stable species.
CH2 • CH2 CH2 •

CH2
• •
Following a mechanistic pathway similar to the allylic radical, the

benzylic radical reacts in a radical chain mechanism resulting in a
substitution on the benzylic carbon.
The following additional examples of benzylic substitutions
react similarly to toluene. Thus, the reaction mechanism is quite
general for all benzylic substitutions and usually produces a good yield
of the product.
NBS
CH2 CH
CCl4,
Br
(84%)
CH3 CH2Br
NBS
CCl4,
(90%)

Synthesis of 1-Bromo-1-phenylethane
Br
NBS, CCl4
O
(PhCO)2
Ethylbenzene 1-Bromo-1-phenylethane
(82%)
In a 25 mL round bottom flask place 5.5 mL of dry carbon tetrachloride and a

magnetic stir bar. Add 1.17 g (1.1 mmol) of ethylbenzene, 1.78 g (1.0 mmol) of NBS,
and 0.03 g of benzoyl peroxide. Stir to dissolve the reactants and flush the flask with
nitrogen. Reflux the solution for 30 minutes. Cool the reaction mixture and filter out
the insoluble succinimide. Wash the succinimide with two portions of 2 mL of carbon
tetrachloride. Remove the carbon tetrachloride on a rotary evaporator. Distill the
residue under reduced pressure. The yield of product is 1.52 g (82%), b.p. 94oC/16 mm.
Discussion Questions
1. Why is this reaction run in a nitrogen atmosphere? What effect might the presence
of oxygen have on the outcome of the reaction?
Exercise 21.4
In Section 21.1, you studied the triphenylmethyl radical. The

triphenylmethyl radical is stable enough to be isolated and studied.
Propose an explanation for its stability.
21.5 Radical Addition to Alkenes

See Section 14.3, page In the hydrohalogenation reaction, which was discussed in
000, for more on Chapter 14, hydrogen adds to the least substituted carbon of a double
hydrohalogenation
reactions.
bond, and a halogen adds to the most substituted carbon. This pattern
of addition follows Markovnikov's rule. However, in the 1920s and
1930s, as chemists studied the hydrohalogenation reaction, they saw
that when they reacted HBr with an alkene the reaction did not
always form a product that followed Markovnikov's rule. In fact, the
reaction gave variable results. On one occasion, it produced mostly the
expected Markovnikov product; on another occasion, it produced
significant amounts of anti-Markovnikov product.

HBr
CH3CH CH2 CH3CH2CH2Br + CH3CHCH3
Br
Anti-Markovnikov Markovnikov
product product
Morris S. Karasch of the University of Chicago was able to

trace the unpredictability of the reaction to the presence of oxygen in
the reaction mixture. When he excluded oxygen from the reaction
mixture by using carefully purified reagents, he received an excellent
yield of the expected Markovnikov product. But when he deliberately
added oxygen, his product was predominately the anti-Markovnikov
product.
CH3CHCH3 Markovnikov
HBr product
Br
(91%)
CH3CH CH2
HBr
O2
CH3CH2CH2Br Anti-Markovnikov
(78%) product
The formation of the anti-Markovnikov product in the presence

of oxygen, a diradical, suggests that the reaction follows a radical
mechanism. Furthermore, adding a radical initiator, such as benzoyl
peroxide, to the reaction mixture increases the yield of the anti-
Markovnikov product in comparison to the yield without the initiator.
A mixture of propene, HBr, and benzoyl peroxide at –78oC rapidly
reacts to produce 1-bromopropane in a 97% yield. The yield without
the radical initiator is 78%.
HBr
CH3CH CH2 CH3CH2CH2Br
O
(97%)
(PhCO)2
o
–78 C
The reaction mechanism for this process begins with a

homolytic cleavage of the benzoyl peroxide to form the benzoyl radical.
The hydrogen from the HBr then reacts with the benzoyl radical to
form benzoic acid and a bromine atom. This sequence makes up the
initiation step of the reaction.

O O
O O• H Br
2
Benzoyl peroxide Benzoyl radical O
OH
+ Br •
Benzoic acid
The propagation step follows the sequence shown below:
Br• • H Br
CH3CH CH2 CH3CHCH2Br CH3CH2CH2Br + Br•
The bromine atom reacts with the double bond of propene to form a 1-
bromo-2-propyl radical. The 1-bromo-2-propyl radical reacts with a
molecule of HBr to give 1-bromopropane and a bromine atom. The
bromine atom is then available to propagate the chain reaction by
reacting with the double bond of another propene molecule. Of the
hydrogen halides, only HBr can form radicals reactive enough to
undergo anti-Markovnikov addition to the double bond of an alkene.
Exercise 21.5
Write the termination steps for the radical addition of HBr to an

alkene.
Radical addition reactions to alkenes are regioselective due to

the stability of the alkyl radical and steric factors. Alkyl radical
stability follows the same sequence as carbocation stability: allyl,
benzyl > 3o > 2o > 1o > methyl. However, the difference in stability is
smaller for radicals than for carbocations, so radical reactions are
often less selective than reactions with carbocations. Additionally,
incoming radicals are very sensitive to steric factors, so they attack
the least hindered carbon of the double bond.
Although HBr is the only hydrogen halide that forms the anti-
Markovnikov product in a radical addition reaction to an alkene, there
are other reagents that also do so. Examples include thiols,
bromotrichloromethane, chlorosilanes, and even other alkenes. With
each reagent you must adjust the reaction conditions appropriately to

generate the radical. These reaction conditions vary from adding a

radical initiator, such as oxygen or a peroxide, to heating the reaction
mixture to a high temperature and using ultraviolet radiation.
CH3CH2SH
SCH2CH3
1-Ethylthio-2-methylcyclohexane
(91%)
Br
Cl3CBr
CH3CH2C CH2 CH3CH2CCH2CCl3
O
CH3 CH3
(CH3CO)2
h
3-Bromo-1,1,1-trichloro-3-methylpentane
(85%)
CH3SiCl2H
CH3(CH2)4CH CH2 CH3(CH2)5CH2SiCl2CH3
O
Dichloroheptylmethyl silane
(CH3CO)2
(98%)
An important industrial process is the radical formation of long

chains of carbon—carbon bonds. These long chains of carbon—carbon
bonds form when alkenes react in the presence of a radical initiator.
The compound that forms is called a polymer. The plastics and fibers
that you use in your daily life are polymers. Chapter 22 discusses
polymers in greater depth.
(PhCO)2
n
Polystyrene
Solved Exercise 21.2

Predict the major product of the following reaction and write a mechanism to
explain its formation.
HBr
O
(PhCO)2
Solution
The product of this reaction is 1-bromo-2-phenylethane.
Br
HBr
O
(PhCO)2
The first step in the mechanism forms a bromine atom. This step initiates the
radical chain reaction.
O O O O
H Br
PhCO OCPh PhCO • PhCOH + Br •
In the propagation steps, the bromine atom reacts with the double bond to
form a benzylic radical. The benzylic radical then reacts with HBr to form the
product and a bromine atom ready to begin another propagation sequence.
•
Br
• Br H Br
H
Br
+ Br •
Exercise 21.6
Predict the major products of each of the following reactions.
a)

Cl3CBr
(CH3)3CCH CH2
O
(PhCO)2
h
b)
CH3SH
h
c)
HBr
H2O2, warm
d)
Cl3SiH
(CH3)3CCH CH2
O
(CH3CO)2
e)
CH3SH
h
C(CH3)3
Sample Solution
b)
SCH3
CH3SH
h
21.6 Radical Oxidations

When an organic compound oxidizes, a new carbon—oxygen
bond forms, or the oxidizing agent removes hydrogen from two
adjacent carbons to form a new S bond. Many organic molecules
oxidize spontaneously in the presence of oxygen in a process called
autooxidation. Light can also catalyze the autooxidation reaction of
some molecules, so those organic compounds must be stored in dark
In the process of
colored bottles and cans. The more stable the radical, the more readily
autooxidation, a
molecule spontaneously autooxidation occurs to form that radical. Compounds especially
reacts with oxygen.

susceptible to autooxidation are benzylic and allylic compounds, as

well as ethers, amines, and similar compounds containing
heteroatoms. All these compounds readily form radicals.
Autooxidation occurs so readily with ethers that ether solvents
that are stored for a long time oxidize to form some amount of
hydroperoxide products. Hydroperoxide products are unstable and
decompose violently when heated. Therefore, when chemists want to
use diethyl ether from old bottles in the lab, they must first remove
the hydroperoxide to prevent possible explosions.
O2
CH3CH2OCH2CH3 CH3CH2OCHCH3
OOH
Diethyl ether Hydroperoxide of diethyl ether
The mechanism for the autooxidation of organic molecules is

not known for sure. An oxygen molecule is believed to abstract a
hydrogen from the carbon bearing the ether oxygen, which produces a
radical and a hydroperoxide radical. These two radicals then react
with each other to form the ether hydroperoxide.
H •• ••
• O
••
O•
•• •• •
CH3CH2OCHCH3 CH3CH2••
O CHCH3
•• ••
HO
••
O•
••
OOH
CH3CH2OCHCH3
Autooxidation is a process that has practical value. For

example, autooxidation accounts for the drying of many oil based
paints. The most commonly used oil in these oil based paints is linseed
oil, which contains a mixture of esters of various long chain carboxylic
Fatty acids are long acids, called fatty acids. Approximately 90% of the fatty acids in
chain carboxylic acids. linseed oil contain one or more double bonds. The allylic position of
Generally, fatty acids these double bonds readily forms a radical. These radicals dimerize,
contain at least 12 then trimerize, then tetramerize, etc., ultimately producing high
carbon atoms. molecular weight polymers. Linoleic acid, a fatty acid, is a major
constituent of linseed oil. As the linoleic acid reacts in an
autooxidation reaction and forms a polymer, the paint dries.

H H H H
O
C C C C
CH3(CH2)4 C (CH2)7COH
H H H H H H
•• ••
•O O• O
•• •• C C C C
Linoleic acid CH3(CH2)4 C (CH2)7COH
•
H
H H
C C
R R
From another
linoleic acid
H H H H
O
C C C C
Repeat reaction
Polymer CH3(CH2)4 H C (CH2)7COH
with double bond H C H
•
C R
R
Autooxidation is a process that has practical consequences, too.

For example, the main causes of food spoilage are microbial (mold, and
bacteria) and autooxidation. Since autooxidation takes place in so
Antioxidants are many foods, food processors add antioxidants to the food or
compounds that react packaging materials. Using an antioxidant gives the food a longer
more readily with shelf life by preserving the taste and nutrient levels. The antioxidants
molecular oxygen than that food processors commonly use are BHA and BHT. BHA is an
the molecules in food or
acronym for Butylated Hydroxy Anisole and is a mixture of 2- and 3-
other sensitive products
react with oxygen. tert-butyl-4-methoxyphenol. BHT is an acronym for Butylated
Hydroxy Toluene and is 2,6-di-tert-butyl-4-methylphenol.
OH CH3 OH CH3 OH CH3

C CH3 CH3 C C CH3
CH3 CH3 CH3
CH3
C
CH3
OCH3 OCH3 CH3 CH3
2-tert-Butyl-4- 3-tert-Butyl-4- 2,6-di-tert-Butyl-4-methylphenol

methoxyphenol methoxyphenol
"Butylated Hydroxy Anisole" "Butylated Hydroxy Toluene"
BHA BHT

Both BHA and BHT form resonance-stabilized phenoxy radicals with

oxygen or other radicals. These phenoxy radicals then react with a
hydroperoxide radical to form a dienone. The structures below are
generalized for both BHA and BHT, as the mechanisms for both are
identical.
O H O • O
R R •
• •• R R R R
O
•
••
O•
••
•
R R R
O O
O
R R R R
•• •• R • R
H O
••
O•
••
HOO R
R
R
Oxidations with molecular oxygen are seldom used in

laboratory syntheses, but they are used extensively in industry. For
example, acetic acid is made industrially via the oxidation of butane
with oxygen in the presence of an initiator.
O
O2
CH3CH2CH2CH3 CH3COH
initiator
Exercise 21.7
The commercial synthesis of BHA involves p-methoxyphenol and 2-

methylpropene. Describe the laboratory method used to synthesize
BHA. BHT is prepared in a similar fashion, but the reaction is much
more regioselective than the synthesis of BHA. Why?
Exercise 21.8

Would you expect the autooxidation of ethyl ether to occur more

readily than the autooxidation of isopropyl ether? Explain your
answer.
21.7 Radical Reductions

Radical reductions are A radical reduction reaction generally involves the addition
reduction reactions of hydrogen to a S bond. The reduction reaction types that you studied
that proceed via a
radical mechanism. previously were catalytic reductions, some ionic reductions, and one
radical reduction. The radical reduction was the trans addition of
See Section 14.7, page hydrogen to an alkyne.
000, for the trans
addition of hydrogen to
an alkyne. H R'
Na
R C C R' C C
NH3, -33oC
R H
To proceed, a radical reduction reaction requires a source of

electrons. Some of the older methods for reducing organic molecules
used metals (especially alkali metals) as an electron source. To make
the electrons from the alkali metal available, the reaction needs some
solvent that dissolves the metal. The solvents most commonly used
In a dissolving metal are alcohols and liquid ammonia. Because the reaction proceeds by
reaction, the reaction
proceeds by using a
dissolving the metal in the solvent, chemists call this reaction a
metal as an electron dissolving metal reaction. However, since the introduction of metal
source to effect the hydrides, dissolving metal reactions are not used very often anymore.
reaction. The substrates for a large number of dissolving metal reactions
are carbonyl groups.
See Section 7.7, page
000, and Section 8.5,
•• ••
page 000, for more •
• •
O •
O•• Na OH
about metal hydrides. Na • •
••
H OCH(CH3)2 •
••
Na •
•• ••
•
• OH •
• OH
(CH3)2CHO H •
•
The reaction begins when an electron from the metal transfers to the
carbonyl group forming a radical anion. A hydrogen from the alcohol
solvent protonates the radical anion producing a neutral radical

intermediate. Then an electron from another metal atom transfers to

the neutral radical intermediate to form a strongly basic carbanion. A
second protonation of the carbanion produces the alcohol.
The dissolving metal reduction reaction readily reduces
aldehydes, ketones, and esters. The reaction does not work with
isolated double bonds, but it does reduce triple bonds, conjugated
double bonds, and conjugated carbonyl systems. An alkyne forms a
trans alkene. A conjugated diene, by a radical 1,4-addition reaction,
forms an alkene. The double bond is reduced in a conjugated carbonyl.
Na, EtOH OH
O
H
Cycloheptanol
(83%)
O
Na, EtOH
CH3(CH2)5COCH2CH3 CH3(CH2)5CH2OH + CH3CH2OH
1-Heptanol Ethanol
(77%)
CH3 CH3
Li, EtOH H3O

NH3, -33oC
O O
H
trans-6-Methylbicyclo[4.4.0]decane-3-one
(95%)
Exercise 21.9
In the last reaction above, the carbonyl group was not reduced, but in
the first example above, the carbonyl group was reduced. Provide an
explanation for this difference. (Hint: Temperature is not the
important difference.)
All the reduction reactions that you have looked at to this point
included a proton source. If the reaction mixture provides no source of
protons, or if the radical anion is stabilized, dimerization of the
substrate occurs. To get the best yield of the desired dimer, chemists
choose a metal that has two or more electrons to donate, such as
magnesium, zinc, or aluminum. These metals react most effectively

when they are used in the form of a mercury alloy called an amalgam.
The synthesis of pinacol is an example of a radical dimerization
reaction:
O CH3 CH3
CH3 CH3
Mg(Hg) • •• •• •
CH3 C C CH3
CH3CCH3 C O
••
•
• •
• O
••
C
C6H6,
CH3 Mg2 CH3 •
• O •
• •
• O •
•
•• ••
Mg2
H2O
••
H H OH2
••
CH3 CH3
CH3 C C CH3
•
• OH
••
•
• OH
••
2,3-Dimethylbutane-2,3-diol
(Pinacol)
(55%)
The reaction starts with acetone and forms a radical anion. The
radical anion then dimerizes to form a vicinal diol. This reaction is
The pinacol reaction is sometimes called the pinacol reaction after the common name of the
a dimerization of a product, 2,3-dimethylbutane-2,3-diol.
ketone using a Esters undergo a dimerization reduction reaction that is called
magnesium amalgam. an acyloin condensation. This name comes from the common name
An acyloin of the simplest reaction product, acyloin, which is an D-hydroxy
condensation is the ketone. The initial product of the reaction is the disodium salt of an
dimerization of an
ester using sodium.
enediol. To form the acyloin product, the disodium salt hydrolyzes in
aqueous acid.

O
O O CH3COMe O O
Na CH3COMe
CH3COMe CH3C CCH3
OMe OMe
Na Na
O O O O O O
CH3C CCH3 CH3C CCH3 CH3C CCH3
H2O
H H
O O O
Tautomerize
CH3C CCH3 CH3CHCCH3
OH
Acyloin
The acyloin condensation is one of the best methods to use

when synthesizing medium to large sized rings. The synthesis begins
with the metal and solvent. Then the diester substrate is added very
slowly. This procedure allows the two ends of the substrate to find
each other in an intramolecular reaction, while it suppresses any
intermolecular reactions.
O
COOMe Na
COOMe Xylene,
OH
2-Hydroxytetradecanone
(48%)
Using sodium or lithium metal with a benzene ring forms a

The Birch reduction is cyclohexadiene. This reaction is called the Birch reduction. When
the reaction of an running the Birch reduction in liquid ammonia with two equivalents
aromatic ring with
sodium metal forming of an alcohol, the reaction produces a 1,4-cyclohexadiene ring.
a cyclohexadiene.

Na, EtOH
NH3, -35oC
1,4-Cyclohexadiene
(88%)
The mechanism for the Birch reduction reaction is as follows:
H
H H H
••
Na • H OEt
• •
H H
H
Na •
H H H H
EtO H
••
H H H
The mechanism begins with an electron transfer from the alkali metal
to the aromatic ring, which forms a radical anion. A hydrogen from the
alcohol then protonates the radical anion, followed by another electron
transfer to the radical from the metal. The final step in the reaction
sequence is another protonation of the anion by another molecule of
alcohol.
When a Birch reduction occurs on a benzene ring with an
electron-donating substituent, the substituent destabilizes the radical
anion intermediate. As a result of this destabilization, the substituent
usually ends up on a carbon of the double bond in the product.
CH3 CH3
Na, EtOH
NH3, -33oC
1-Methyl-1,4-cyclohexadiene
(84%)

If the substituent is an electron-withdrawing group, the substituent

stabilizes the radical anion intermediate. In this case, the substituent
ends up on one of the sp3 carbons in the product.
COOH COOH
Na, EtOH
NH3, -33oC
1,4-Cyclohexadiene-3-carboxylic acid
(96%)
Synthesis of 1-Methoxy-1,4-cyclohexadiene
OCH3 OCH3
Li, NH3
(CH3)3COH
Anisole 1-Methoxy-1,4-cyclohexadiene
(75%)
Fit a 500 mL round bottom flask with an inlet tube, mechanical stirrer, and a dry ice
condenser. Place 15 mL of dry tetrahydrofuran, 25 mL of tert-butyl alcohol, and 5 g
(0.047 mol) of anisole into the flask. Fill the trap of the condenser with dry ice and
acetone. Dry the ammonia by transferring 160 mL into a flask cooled in a dry
ice/acetone bath. Add about 0.5 g of sodium to the ammonia and stir about 15-20
minutes. Warm the flask and distill about 150 mL of the dried liquid ammonia into
the round bottom flask. Cautiously, add 1.15 g (0.38 mol) of lithium with stirring. As
the lithium dissolves, the solution will become deep blue. Reflux for 1 hour.
Cautiously add methanol dropwise to discharge the blue color. About 10 mL of
methanol is required. Then add 75 mL of water. Remove the dry ice condenser and let
the reaction mixture stand in the hood overnight to evaporate the excess ammonia. If
any lithium salts are not dissolved, add enough water to dissolve them. Extract the
reaction mixture with three 10 mL portions of petroleum ether (b.p. 30-40oC).
Combine the petroleum ether extracts and wash them four times with 10 mL portions
of water to remove the excess tert-butyl alcohol and methanol. Dry the petroleum
ether layer over anhydrous magnesium sulfate. Fractionally distill the solution under
reduced pressure to remove the solvent, then distill the residue. The yield of product
is 3.9 g (75%), b.p. 40oC/20 mm.
Discussion Questions
1. Commercial anisole is purified by washing with sodium hydroxide, then washing

with water, followed by distillation. This process removes the phenol from which
anisole is synthesized. What product is produced by the Birch reduction of phenol?
2. Using a rotary evaporator to remove the solvent results in a considerably lower
yield of product. Why?
Exercise 21.10

Predict the major products of each of the following reactions.
a)
O
Na, EtOH
b)
O
1) Mg(Hg), C6H6
2) H3O
c)
OCH3
Li, EtOH
NH3, –33oC
d)
O O
Li, EtOH
CH3OC(CH2)8COCH3
e)
O
Li, EtOH
NH3, –33oC
CH2CH3
Sample Solution
a)
O OH
Na, EtOH
[Special Topic]
Electron Spin Resonance Spectroscopy

Electron spin The development of the electron spin resonance (ESR)

resonance looks at technique has enabled chemists to spectroscopically detect radicals.
unpaired electrons in
ways similar to how
ESR is similar to NMR in that ESR is also a type of magnetic
NMR looks at nuclei. spectroscopy. Electrons possess a magnetic moment similar to the
magnetic moments associated with nuclei. Because paired electrons
have opposite spins, their magnet moments cancel one another. Thus,
ESR does not detect them. However, when they are unpaired, the
magnetic moment takes on one of two possible alignments as specified
by its spin. ESR detects this spin.
The two possible alignments for the spin of unpaired electrons
are either in a parallel or an antiparallel direction to the applied
magnetic field. These alignments are similar to the alignments of the
nuclei in the magnetic field of an NMR instrument. ESR generally
requires radio frequencies in the microwave region. For a given
magnetic field, the frequency for ESR spectroscopy is approximately
1000 times higher than the frequency for an NMR.
Similar to an NMR spectrometer, an ESR spectrometer records
the spectrum with the magnetic field increasing from left to right on
the graph. Unlike NMR, however, the ESR spectrum records the first
derivative of the absorption signal rather than the typical absorption
peak. Recording the first derivative of the absorption provides a
cleaner spectrum than does an absorption spectrum.
Absorption curve First derivative curve
Any nuclei possessing a magnetic moment—1H is the most

common—that are located adjacent to the radical site give rise to
Hyperfine splitting is hyperfine splitting of the peak. If a single hydrogen atom is on the
analogous to the spin- carbon that bears an unpaired electron, the signal for that electron
spin splitting in NMR.
splits into a doublet. The methyl radical contains a four line spectrum
as a result of the interaction of the three equivalent hydrogens with
the unpaired electron. Similar to a methyl signal in NMR, these four
peaks have a 1:3:3:1 integration ratio.

23 Gauss
ESR spectrum of CH3•
The benzene radical anion has a total of seven peaks in its spectrum.
Benzene's resonance distributes the unpaired electron over the six
carbon atoms.
3.7 Gauss
ESR spectrum of
Exercise 21.11
The hyperfine coupling constant for a hydrogen attached to carbon

bearing an unpaired electron is about 20-25 gauss.
a) The hyperfine coupling constant for a hydrogen atom is 500

gauss. Why is this value so much larger than for the methyl
radical?
b) Why is the hyperfine coupling constant for the benzene
radical anion so much smaller than for the methyl radical?
c) Sketch the appearance of the ESR spectrum for the 2,2-
dimethylpropyl radical.

Key Ideas from Chapter 21

❑ A radical is a chemical species that has a single unpaired
electron in one of its orbitals.
❑ Structurally, radicals and carbocations are similar because

both have a planar trigonal sp2 geometry. However, radicals
contain a single electron in the unhybridized p orbital, whereas
the unhybridized p orbital of carbocations is empty.
❑ A nonbonding pair of electrons on an atom adjacent to the

radical site causes some electron repulsion and tends to give
the radical a more tetrahedral (sp3) geometry.
❑ An alkane reacts with chlorine or bromine in the presence of

either heat or light to form alkyl chlorides or alkyl bromides.
❑ The halogenation of an alkane is a radical chain reaction. The

initiation step is the homolytic cleavage of the halogen. In the
chain propagation steps that follow, each time the reaction uses
a halogen, it produces a new one. The reaction terminates
when two radicals react together.
❑ For chlorination, the reactivity of various sites in an alkane is

tertiary > secondary > primary. The relative rates of reaction
are 4 : 2.5 : 1.
❑ A radical bromination is a slower reaction than a radical

chlorination. Because of this slowness, a radical bromination is
much more selective than a radical chlorination. The reactivity
of the various sites in an alkane is tertiary > secondary >
primary. The relative rates of reaction are 1640 : 83 : 1.
❑ N-Bromosuccinimide is an excellent source of bromine in low

concentrations. The low concentrations of bromine react at the
allylic position of an alkene.
❑ Benzylic and allylic radicals readily form because both are

resonance-stabilized.
❑ The anti-Markovnikov addition of HBr proceeds via a radical

intermediate. The amount of the anti-Markovnikov product
increases as the amount of radical initiator such (e.g. peroxide)
increases.

❑ Autooxidation is the reaction of some substrate with oxygen.

Autooxidation occurs when a substrate can form some
particularly stable radical. Light usually accelerates the
reaction.
❑ A dissolving metal reduction uses a reactive metal as a source

of electrons. The most common metals are sodium, lithium,
magnesium, and zinc.
❑ Dissolving metal reductions reduce aldehydes, ketones, and

esters to alcohols.
❑ When no source of protons is available, a dissolving metal

reduction causes dimerization. Examples of this dimerization
are the pinacol reaction and the acyloin condensation.
❑ The Birch reduction adds two hydrogens to positions 1 and 4 on

the benzene ring. The product of a Birch reduction is a 1,4-
cyclohexadiene.
❑ In the Birch reduction, electron-donating substituents

destabilize the radical anion intermediate. This destabilization
directs the substituent to the sp2 carbon of the product. An
electron-withdrawing substituent stabilizes the intermediate,
so the substituent ends up on the sp3 carbon.

Radical Reactions

Uploaded by

Document Information

Original Description:

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Radical Reactions

Uploaded by

Copyright:

Available Formats

Richard F. Daley and Sally J.

Copyright 1996-2005 by Richard F. Daley & Sally J. Daley

No part of this publication may be reproduced, stored in a retrieval system, or

www.ochem4free.com 5 July 2005

9Understand the structure of a radical

www.ochem4free.com 5 July 2005

Whoever in discussion adduces authority uses not

A ny atom, or group of atoms, that bears an unpaired

21.1 Radical Structure and Stability

When Gomberg ran the reaction, he obtained a yellow solution

www.ochem4free.com 5 July 2005

understand the part radicals had in Gomberg's experiment, no one has

The structure of a radical varies somewhat depending on the

Radical stability is also similar to carbocation stability. Thus,

www.ochem4free.com 5 July 2005

With uncharged radicals, the polarity of the solvent does not

Radicals and Atoms

www.ochem4free.com 5 July 2005

The resulting methyl radical, which also is very electrophilic, then

Notice that the last step in the mechanism produced another

The initiation step is generally the slowest step in the radical

www.ochem4free.com 5 July 2005

When 2-methylbutane reacts at 300oC with one mole of

CH3 CH3 CH3

Using the above percentages of the reaction's products, you can

50% of the product

22% of the product

Based on statistical predictions, if these three classes of

www.ochem4free.com 5 July 2005

CH3 CH3 CH3

www.ochem4free.com 5 July 2005

The regioselectivity of chlorine is dependent on the temperature of the

Even at relatively high temperatures and in the presence of light,

Atmospheric Ozone Depletion

www.ochem4free.com 5 July 2005

More incoming ultraviolet radiation provides the energy needed by

As well as dissociating the molecular oxygen, ultraviolet radiation also

These reactions make up a chain reaction that will continue as long as

These reactions take place more readily than do reactions involving

www.ochem4free.com 5 July 2005

place without the presence of ultraviolet radiation. The net result is a

21.3 Allylic Bromination

www.ochem4free.com 5 July 2005

At this point in the reaction, the reaction mixture contains a low

www.ochem4free.com 5 July 2005

Because the allylic radical reacts with Br2 instead of NBS to

Monitoring the NBS Reaction

The reaction also proceeds well in the presence of a radical

www.ochem4free.com 5 July 2005

Chemists have extensively studied the mechanism for this

Solved Exercise 21.1

When 3-phenyl-1-propene is heated with NBS in CCl4, it forms two

www.ochem4free.com 5 July 2005

21.4 Benzylic Bromination

The reaction proceeds via a resonance-stabilized benzylic

CH2 • CH2 CH2 •

Following a mechanistic pathway similar to the allylic radical, the

www.ochem4free.com 5 July 2005

In a 25 mL round bottom flask place 5.5 mL of dry carbon tetrachloride and a

In Section 21.1, you studied the triphenylmethyl radical. The

21.5 Radical Addition to Alkenes

www.ochem4free.com 5 July 2005

Morris S. Karasch of the University of Chicago was able to