RADICAL REACTIONS

0.1 INTRODUCTION:
Ionic reactions are those in which covalent bonds break heterolytically, and in which ions are
1. Ionic reactions are those in which covalent bonds break heterolytically, and in
involved as reactants, intermediates, or product
which ions are involved as reactants, intermediates, or products.
Heterolytic bond dissociation (heterolysis): electronically unsymmetrical bond breaking ⇒
1) Heterolytic
produces ions. bond dissociation (heterolysis): electronically unsymmetrical bond
breaking produces ions.
Heterogenic bond formation: electronically unsymmetrical bond making.
2) Heterogenic bond formation: electronically unsymmetrical bond making.
Homolytic bond dissociation
3) Homolytic (homolysis):
bond dissociation electronically
(homolysis symmetrical bond
): electronically breaking ⇒
symmetrical bond
produces radicals (free radicals).
breaking produces radicals (free radicals).
Hemogenic bond formation: electronically symmetrical bond making.
4) Hemogenic bond formation: electronically symmetrical bond making.

homolysis
A B A + B
Radicals

i) Single-barbed arrows are used for the movement of a single electron.

 i) Single-barbed arrows are used for the movement of a single electron.
PRODUCTION OF RADICALS

10.1A PRODUCTION OF RADICALS

1. Energy must be supplied by heating or by irradiation with light to cause

homolysis of covalent bonds.
1) Homolysis of peroxides:

heat
R O O R 2 R O
Dialkyl peroxide Alkxoyl radicals

2) Homolysis of halogen molecules: heating or irradiation with light of a wave

length that can be absorbed by the halogen molecules.

homolysis
X X 2 X
heat or light

1. Almost all small radicals are short-lived, highly reactive species.

10.1B
2. RThey
EACTIONS
tend toOF RADICALS
react in a way:that leads to pairing of their unpaired electron.
1) Abstraction of an atom from
~ 3 ~ another molecule:
 2. They tend to react in a way that leads to pairing of their unpaired electron.
2. They tend to react in a way that leads to pairing of their unpaired electron.
1) Abstraction of an atom from another molecule:
1) Abstraction of an atom from another molecule:
i) Hydrogen abstraction:
i) Hydrogen abstraction:
General Reaction
General Reaction
X + H R XH + R
X + H R XH + R
Alkane Alkyl radical
Alkane Alkyl radical

Specific Example
Specific Example
Cl + H CH3
H CH3
Cl H + CH3
Cl + Cl H + CH3
Methane
Methane Methyl radical
Methyl radical

2) Addition
2) Addition to a compound
to a compound containing
containing a multiple
a multiple bond bond to produce
to produce a new,alarger
new, larger
radical:
radical:
R R R
R
C CC C C CC C

Alkene
Alkene New radical
New radical
1. Radical reactions are of vital importance in biology and medicine.
1) Radical reactions are ubiquitous (everywhere) in living things, because radicals
are produced in the normal course of metabolism.

2) Radical are all around us because molecular oxygen ( O O ) is itself a

diradical.

3) Nitric oxide ( N O ) plays a remarkable number of important roles in living

systems.

~4~

i) Although in its free form nitric oxide is a relatively unstable and potentially
toxic gas, in biological system it is involved in blood pressure regulation and
blood clotting, neurotransmission, and the immune response against tumor
cells.
ii) The 1998 Nobel Prize in Medicine was awarded to the scientists (R. F.
Furchgott, L. J. Ignarro, and F. Murad) who discovered that NO is an important
 signaling
signalingmolecule
molecule(chemical
(chemical messenger).
messenger).

2.2. Radical
Radical are
are capable
capable of
of randomly
randomly damaging
damaging all
all components
components of
of the
the body because
body because
they
theyare
arehighly
highlyreactive.
reactive.
1)1) Radical
Radical are
are believed
believed to
to be
be important
important in
in the
the “aging
“aging process”
process” in
in the
the sense that
sense that
radicals
radicals are
are involved
involved in
in the
the development
development of
of the
the chronic
chronic diseases
diseases that are life
that are life
limiting.
limiting.
2)2) Radical
Radicalare
areimportant
important in
in the
the development
development of
of cancers
cancers and in the development of
atherosclerosis
atherosclerosis(( ).).

Superoxide((OO22 ))isis aa naturally

3.3. Superoxide naturally occurring
occurring radical
radical and
and is associated with both the
immune
immune response
response against
against pathogens
pathogens and
and at
at the
the same
same time the development of
certain
certaindiseases.
diseases.
1)1) An
Anenzyme
enzymecalled
called superoxide
superoxide dismutase
dismutase regulates
regulates the
the level of superoxide in the
body.
body.

4.4. Radicals
Radicalsinincigarette
cigarettesmoke
smokehave
have been
been implicated
implicated in
in inactivation
inactivation of an antiprotease
ininthe
thelungs
lungswhich
whichleads
leadsto
tothe
the development
development of
of emphysema
emphysema ( ).
 certain diseases.
1) An enzyme called superoxide dismutase regulates the level of superoxide in the
body.

4. Radicals in cigarette smoke have been implicated in inactivation of an antiprotease

in the lungs which leads to the development of emphysema ( ).

5. Radical reactions are important in many industrial processes.

1) Polymerization: polyethylene (PE), Teflon (polytetrafluoroethylene, PTFE),
polystyrene (PS), and etc.
2) Radical reactions are central to the “cracking” process by which gasoline and
other fuels are made from petroleum.
3) Combustion process involves radical reactions.

~5~
 Table 10.1 Single-Bond Homolytic Dissociation Energies H° at 25°C
A B A + B
Bond Broken Bond Broken
kJ mol–1 kJ mol–1
(shown in red) (shown in red)
H–H 435 (CH3)2CH–Br 285
D–D 444 (CH3)2CH–I 222
F–F 159 (CH3)2CH–OH 385
Cl–Cl 243 (CH3)2CH–OCH3 337
Br–Br 192 (CH3)2CHCH2–H 410
I–I 151 (CH3)3C–H 381
H–F 569 (CH3)3C–Cl 328
H–Cl 431 (CH3)3C–Br 264
H–Br 366 (CH3)3C–I 207
H–I 297 (CH3)3C–OH 379
CH3–H 435 (CH3)3C–OCH3 326
CH3–F 452 C6H5CH2–H 356
CH3–Cl 349 CH2=CHCH2–H 356
CH3–Br 293 CH2=CH–H 452
CH3–I 234 C6H5–H 460
CH3–OH 383 HC C H 523
CH3–OCH3 335 CH3–CH3 368
CH3CH2–H 410 CH3CH2–CH3 356
CH3CH2–F 444 CH3CH2CH2–H 356
CH3CH2–Cl 341 CH3CH2–CH2CH3 343
CH3CH2–Br 289 (CH3)2CH–CH3 351
CH3CH2–I 224 (CH3)3C–CH3 335
CH3CH2–OH 383 HO–H 498
CH3CH2–OCH3 335 HOO–H 377
CH3CH2CH2–H 410 HO–OH 213
CH3CH2CH2–F 444 (CH3)3CO–OC(CH3)3 157
CH3CH2CH2–Cl 341 O O
CH3CH2CH2–Br 289 139
C6H5CO OCC6H5
CH3CH2CH2–I 224
CH3CH2CH2–OH 383 CH3CH2O–OCH3 184
CH3CH2CH2–OCH3 335 CH3CH2O–H 431
(CH3)2CH–H 395 O
(CH3)2CH–F 439 364
CH3C H
(CH3)2CH–Cl 339
 HOMOLYTIC BOND DISSOCIATION ENERGIES

10.2 HOMOLYTIC BOND DISSOCIATION ENERGIES

1. Bond formation is an exothermic process:

H• + H• H–H H° = – 435 kJ mol–1
Cl• + Cl• Cl–Cl H° = – 243 kJ mol–1

2. Bond breaking is an endothermic process:

H–H H• + H• H° = + 435 kJ mol–1
Cl–Cl Cl• + Cl• H° = + 243 kJ mol–1

3. The hemolytic bond dissociation energies, H°, of hydrogen and chlorine:

H–H Cl–Cl
( H° = 435 kJ mol–1) ( H° = 243 kJ mol–1)

10.2A HOMOLYTIC BOND DISSOCIATION ENERGIES AND HEATS OF

REACTION:

1. Bond dissociation energies can be used to calculate the enthylpy change ( H°)
 H° = 435 kJ mol–1 H° = 243 kJ mol–1 ( H° = 431 kJ mol–1) × 2
–1 –1
H H is required
+678 kJ mol + Cl Cl – 862 kJ 2mol
H Cl is evolved
for bond cleavage.
–1
in bond formation.
H° = 435 kJ mol H° = 243 kJ mol–1 –1
( H° = 431 kJ mol ) × 2
–1
H• + 2isCl•
+678 kJ2 mol required 2 H–Cl – 862 kJ mol–1 is evolved
i) The overall for
reaction2 H•
bond is + 2 Cl•
exothermic:
cleavage. 2 H–Cl in bond formation.
10.2B 10.2B
HOMOLYTIC BOND
HOMOLYTIC B DISSOCIATION
OND D ISSOCIATION
–1 ENERGIES
ENERGIES
–1 AND
AND THE
THE RRELATIVE
–1 ELATIVE
° =OF
(– 862
Hoverall
STABILITIES
i) STABILITIES
The R kJ mol
reaction
ADICALS : + :678 kJ mol ) = – 184 kJ mol
is exothermic:
OF RADICALS
–1 –1 –1
1. Bond dissociation
ii)1. The following
Bond ° = (–
Henergies
pathway
dissociation 862can
iskJassumed
energies mol
be be
can +used
used 678 kJ
intothe mol
toeatimate ) =the
calculation:
eatimate –the184 kJ molstabilities
relative
relative stabilitiesofof
radicals.
radicals.
ii) The following pathwayH–His assumed in the 2 H•
calculation:
1) H1) ° for H1°° for
and1°2°and
C–H2° C–H bonds
bonds of propane:
of propane:
CH3CH2CH2–H
Cl–Cl
H–H 2 Cl•
2 H•
(CH )2CH–H
CH3CH2CH2–H (CH3)32CH–H
( H° = 410 kJ–1mol–1) Cl–Cl ( H° =2395 –1
Cl•kJ mol–1 )
( H° = 410 kJ mol ) ~ 7 (~ H° = 395 kJ mol )
2) H° for the reactions: ~7~
2) H° for the reactions:
CH3CH2CH2–H CH3CH2CH2• + H• H° = + 410 kJ mol–1
CH3CH2CH2–H CHPropyl
3CH2CH2• + H•
radical
H° = + 410 kJ mol–1
(a 1°
Propyl radical)
radical
(CH3)2CH–H (a(CH
1° 3radical)
)2CH• + H• H° = + 395 kJ mol–1
(CH3)2CH–H (CH 3)2CH•radical
Isopropyl + H• H° = + 395 kJ mol–1
(a 2° radical)
 CH3 CH3
H 3C C CH2 H CH3CCH3 + H H° = + 381 kJ mol–1
H tert-Butyl radical (a 3o radical)

CH3 CH3
H3C C CH2 H CH3CCH2 + H
H° = + 410 kJ mol–1
H H
Isobutyl radical (a 1o radical)

1o radical CH3
1o radical
2o radical 3o radical CH3CHCH2 + H
CH3CH2CH2 + H

CH3CHCH3 + H CH3 29 kJ mol 1

 H° = + 410 kJ mol–1
H H
Isobutyl radical (a 1o radical)

1o radical CH3
1o radical
2o radical 3o radical CH3CHCH2 + H
CH3CH2CH2 + H

CH3CHCH3 + H CH3 29 kJ mol 1

1 CH3CCH3 + H
15 kJ mol
Ho = +410 kJ mol 1

PE Ho = +410 kJ mol 1
PE
Ho = +381 kJ mol 1

Ho = +395 kJ mol 1

CH3
CH3CH2CH2 CH3CHCH3

Figure 10.1 (a) Comparison of the potential energies of the propyl radical (+H•)
and the isopropyl radical (+H•) relative to propane. The isopropyl
radical –– a 2° radical –– is more stable than the 1° radical by 15 kJ
mole–1. (b) Comparison of the potential energies of the tert-butyl
 is electron deficient.
Tertiary > alkyl
ii) Electron-releasing Secondary >
groups attached Primary > provide
to this carbon Methyla stabilizing
C C H H
effect, and more alkyl groups that are attached to this carbon, the more stable
C C > C C > C C > H C
the radical is.
C H H H

1) The order of stability of alkyl radicals is the same as for carbocations.

i) Although alkyl radicals are uncharged, the carbon that bears the odd electrons
10.3 THETHE REACTIONS
REACTIONS OF
OF A ALKANES
LKANES WITH
WITH
is electron deficient.
HALOGENS
HALOGENS
ii) Electron-releasing
1. Methane, alkyl
ethane, and other groups
alkanes attached
react to this carbon
with fluorine, provide
chlorine, a stabilizing
and bromine.
effect, and more alkyl groups that are attached to this carbon, the more stable
1) Alkanes do not react appreciably with iodine.
the radical is.
2) With methane the reaction produces a mixture of halomethanes and a HX.

H H X X X
heat
H 10.3
C HT + HE
X2 REACTIONSH C OF X +AH C X WITH
LKANES X+ X C X + H X
+ H CHALOGENS
or
H light H H X X
1. Methane,
Methane Halogen ethane, and other alkanes
Halo- react with
Dihalo- fluorine, chlorine,
Trihalo- and bromine.
Tetrahalo- Hydrogen
1) Alkanes do notmethane methane
react appreciably methane
with iodine. methane halide
2) With methane(The sum of the
the reaction numbera mixture
produces of molesofofhalomethanes
each halogenated methane
and a HX.
produced equals the number of moles of methane that reacted.)
H H
 products as well asofmore
3. Chlorination mosthighly halogenated
of higher compounds.
alkanes gives a mixture of isomeric monochloro
1) Chlorine is relatively
products as well as unselective it does not
more highly halogenated discriminate greatly among the
compounds.
different types is
1) Chlorine ofrelatively
hydrogenunselective
atoms (1°, 2°,itand 3°)not
does in discriminate
an alkane. greatly among the
different types of hydrogen atoms (1°, 2°, and 3°) in an alkane.
CH3 CH3 CH3
Cl2
CH3CHCHCH 3 3 Cl CH3CHCH CH3Cl + CH CHCH
2 3
CH3 + polychlorinated + H Cl
3
light 2 products
CH3CHCH3 CH3CHCH2Cl + CH3CHCH3 + polychlorinated + H Cl
light Cl products
Isobutane Isobutyl chloride tert-Buty chloride
Cl (23%)
Isobutane Isobutyl -Buty chloride
(48%) chloride tert(29%) (23%)
(48%) (29%)
4. Alkane chlorinations usually give a complex mixture of products they are not
4. Alkane chlorinations usually give a complex mixture of products they are not
1)generally useful synthetic
Halogenation methods
of an alkane (orfor the preparation
cycloalkane) of aequivalent
with specific alkyl chloride.
hydrogens:
generally useful synthetic methods for the preparation of a specific alkyl chloride.
~ 11 ~
~ 11 ~
CH3 CH3
heat
H3C C CH3 + Cl2 H3C C CH2Cl + H Cl
or light
CH3 CH3
Neopentane Neopentyl chloride
(excess)

5. Bromine is generally less reactive toward alkanes than chlorine bromination is

 or light
5. A Mechanism
Reaction:
Bromine for less
is generally the reactive
Reaction toward alkanes than chlorine bromination is
A Mechanism for theCH
Mechanism: Reaction
+ Cl
heat
CH3Cl + HCl
more regio-selective. 4 2
1 (chain-initiating
StepChlorination
Radical of Methane or light are created)
step –– radicals
Radical Chlorination of Methane
Reaction:
Mechanism: heat
Reaction: Cl Cl heat Cl + Cl
CH4 + Cl2 or light CH 3Cl + HCl
Step 1 (chain-initiating
10.4 CHLORINATION OFCH Mstep
ETHANE –– radicals
or: M
heat
light are created) OF REACTION
ECHANISM
4 + Cl 2 CH3Cl + HCl
Under the influence of heat ororlight light a This step produces two highly
heat
Several molecule
1. Mechanism:important of chlorine
Cl Cl dissociates;
experimental observations each reactive
about halogenation chlorine
+
Cl reactions: atoms.
Cl
atom takes one of the bonding electrons. or light
Mechanism:
Step 1 (chain-initiating step –– radicals are created)
CHUnder
+ Cl the influence
CH of +
Cl heat
HCl or light
(+ CH a Cl , CHCl
This step, andproduces
CCl ) two highly
Step
Step 1 ( chain-initiating
2 (chain-propagating step –– radicals
step –– one are created )
radical generates
reactiveanother)
4 2 3 2 2 3 4
molecule of chlorine dissociates; each
heat chlorine atoms.
atom takes oneClof Cl the bonding
H electrons. Cl + Cl
heat
or light H
1) The reaction is promoted Cl Cl by heat or light. Cl + Cl
Under + H
Clthe influence C heat
of H or light Cl H produces+ CtwoHhighly
i) At Step
room2 (chain-propagating
temperature methane andor
step –– light
chlorine ado notThis
one radical reactstep
generates another)
at a perceptible rate as
molecule of chlorine dissociates;
Under the influenceHof heat or light a each reactive chlorine
H atoms.
This step produces two highly
long as
atom the mixture
takes of is kept
onechlorine Haway
of the bonding from light.
electrons. H
molecule dissociates; each This step reactive chlorine atoms.of
produces a molecule
Aatom
chlorine atom abstracts a hydrogen
H at electrons.
ii) MethanetakesCl one
+ H of the
and chlorine doCbonding
react room hydrogen
temperature Cl ifHthe +gaseous
chloride and a C
H
reaction
methyl radical.
atom from a methane molucule.
Step 2 (chain-propagating step –– one radical generates another)
mixture is irradiated with H UV light. H
Step 23 (chain-propagating
Step (chain-propagating H step step –––– one
one radical
radical generates
generates another)
another)
A chlorine
iii) Methane andatom abstracts
chlorine in the dark ifThis
a hydrogen
do Hreact the step produces
gaseous aHmolecule
reaction mixture isof
atomCl fromH +a methane
H H
C molucule. hydrogen Cl chloride
H H and + aHmethyl
C H radical.
heated to temperatures greater than 100°C.
H ClC + +H Cl C H H ClC HCl + + H Cl C H
Step 3 (chain-propagating Cl
H step –– one radical generates another)
2) The light-promoted
A chlorine reaction
H abstracts
atom H aishydrogen
highly efficient. This stepHproduces aHmolecule of
H H
hydrogen chloride and a methyl radical.
 1) The chain reaction accounts for the observation that the light-promoted react
is highly efficient.

4. Chain-terminating steps: used up one or both radical intermediates.

H H
H C + Cl H C Cl
H H
H H H H
H C + C H H C C H
H H H H

Cl + Cl Cl Cl

1) Chloromethan and ethane, formed in the terminating steps, can dissipate th

excess energy through vibrations of their C–H bonds.
2) The simple diatomic chlorine that is formed must dissipate its excess ener
10.5 CHLORINATION OF METHANE: ENERGY CHANGES

1. The heat of reaction for each individual step of the chlorination:

Chain Initiation ~ 14 ~

Step 1 Cl–Cl 2 Cl• H° = + 243 kJ mol–1

( H° = 243)

Chain Propagation
Step 2 CH3–H + •Cl CH3• + H–Cl H° = + 4 kJ mol–1
( H° = 435) ( H° = 431)

Step 3 CH3• + Cl–Cl CH3–Cl + •Cl H° = – 106 kJ mol–1

( H° = 243) ( H° = 349)

Chain Termination
CH3• + •Cl CH3–Cl H° = – 349 kJ mol–1
( H° = 349)
CH3• + CH3• CH3–CH3 H° = – 368 kJ mol–1
( H° = 368)
•Cl + •Cl Cl–Cl H° = – 243 kJ mol–1
( H° = 243)

2. In the chain-initiating step only the bond between two chlorine atoms is broken,
 4) Iodine is so unreactive that the reaction between it and methane does not take
place for all practical purposes.
place for all practical
10.5C REACTION purposes.
OF METHANE WITH OTHER HALOGENS:
2. The reactivity of halogens can be explained by their H° and Eact for each step:
1) F2. 1.: Theofreactivity
The reactivity
LUORINATION halogens of one
cansubstance toward another
be explained by theiris measured
H° andbyEactthefor at which
rateeach step:
the two substances react.
1) FLUORINATION : H° (kJ mol–1) Eact (kJ mol–1)
1) Fluorine is most reactive –– so reactive that without special precautions mixtures
Chain Initiation ~ 19 ~
F2 2 F• + 159 (kJ mol–1) Eact (kJ mol–1)
+ °159
H
Chain Initiation
Chain Propagation
F
2
F• + CH3–H
2 F•
H–F + CH3• – 134
+ 159
+ 5.0
+ 159
CH3• + F–F CH3–F + F• – 293 Small
Chain Propagation Overall H° = – 427
F• + CH3–H
i) The chain-initiating H–F
step in fluorination + CHendothermic
is highly 3• – 134
and thus has a + 5.0
high energy
CHof3•activation.
+ F–F CH3–F + F• – 293 Small
ii) One initiating step is able to produce thousandsOverall
of fluorination
H° reactions
= – 427 the
high activation energy for this step is not an obstacle to the reaction.
i) The chain-initiating
iii) Chain-propagating stepto have
steps cannot afford in fluorination isactivation.
high energies of highly endothermic and thus has a
high
iv) Both of the energy of activation.
chain-propagating steps in fluorination have very small energies of
activation.
ii) One initiating step is able to produce thousands of fluorination reactions the
v) The overall heat of reaction, H°, is very large large quantity of heat is
high activation energy for this step is not an obstacle to the reaction.
evolved as the reaction occurs the heat may accumulate in the mixture faster
thaniii) Chain-propagating
it dissipates steps causing
to the surroundings cannotthe
afford totemperature
reaction have hightoenergies
rise of activation.
 vii) Fluorination reactions can be controlled by diluting both the hydrocarbon and
in a reactor packed with copper shot to absorb the heat produced.
the fluorine with an inert gas such as helium or the reaction can be carried out
2) CHLORINATION:
in a reactor packed with copper shot to absorb the heat produced.
H° (kJ mol–1) Eact (kJ mol–1)
2) CHLORINATION:
Chain Initiation
Cl2 2 Cl• + 243 + 243
H° (kJ mol–1) Eact (kJ mol–1)
Chain Propagation
Chain Initiation
Cl• + CH3–H H–Cl + CH3• +4 + 16
Cl
2
CH3• + Cl–Cl
2 Cl•
CH3–Cl + Cl• – 106 Small
+ 243 + 243
Overall H° = – 102
Chain Propagation
i) The higher energy of activation of the first chain-propagating step in
Cl•(16
chlorination + CH 3–H
kJ mol–1 H–Cl
), versus the lower + CH
energy •
of 3activation + 4kJ mol–1)
(5.0 + 16
CH3•partly
in fluorination, + Cl–Cl
explains the lowerCH 3–Cl of
reactivity + chlorine.
Cl• – 106 Small
ii) The greater energy required to break the Cl–ClOverall
bond in theH ° = – 102
initiating step (243
kJ mol–1 for Cl2 versus 159 kJ mol–1 for F2) has some effect, too.
iii) The i)muchThe higher
greater overall energy of activation
heat of reaction of probably
in fluorination the first
playschain-propagating
the step in
chlorination
greatest role in accounting(16
for kJ much–1greater
the mol ), versus the lower
reactivity energy
of fluorine. of activation (5.0 kJ mol–1)
in fluorination, partly explains the lower reactivity of chlorine.
3) BROMINATION:
ii) The greater energy required to break the Cl–Cl bond in the initiating step (243
–1
H° (kJ mol–1–1) Eact (kJ mol–1)
kJ mol for Cl2 versus 159 kJ mol for F2) has some effect, too.
Chain Initiation
 –1 –1
greatest rolekJinmol for for
accounting Cl2theversus 159 kJ
much greater mol offor
reactivity F2) has
fluorine. some effect, too.
iii) The much greater overall heat of reaction in fluorination probably plays the
3) BROMINATION:
greatest role in accounting for the much greater reactivity of fluorine.
H° (kJ mol–1) Eact (kJ mol–1)
Chain Initiation
3) BROMINATION:
Br2 2 Br• + 192 + 192

Chain Propagation H° (kJ mol–1) Eact (kJ mol–1)

Br• Chain
+ CH3–HInitiation
H–Br + CH3• + 69 + 78
CH3• + Br–Br CH3–Br + Br• – 100 Small
Br2 2 Br• + 192 + 192
~ 21 ~

Chain Propagation
Br• + CH3–H H–Br + CH3• + 69 + 78
CH3• + Br–Br CH3–Br + Br• – 100 Small
~ 21 ~
Overall H° = – 31

i) The chain-initiating step in bromination has a very high energy of activation

(Eact = 78 kJ mol–1) only a very tiny fraction of all of the collisions between
bromine and methane molecules will be energetically effective even at a
 temperature of 300 °C.
ii) Bromine
4) IODINATION : is much less reactive toward methane than chlorine even though the
net reaction is slightly exothermic.
H° (kJ mol ) Eact (kJ mol–1)
–1

Chain Initiation
I2
4) IODINATION
2 I•
: + 151 + 151

Chain Propagation H° (kJ mol–1) Eact (kJ mol–1)

Chain
I• + CH3–H Initiation
H–I + CH3• + 138 + 140
CH3• + I–I CH3–I + I• – 84 Small
I2 2 I• + 151 + 151
Overall H° = + 54

i) The I–I bond Propagation

Chain is weaker than the F–F bond the chain-initiating step is not
responsible for the observed reactivities: F2 > Cl2 > Br2 > I2.
I• + CH3–H H–I + CH3• + 138 + 140
ii) The H-abstraction step (the first chain-propagating step) determines the order
CH3• + I–I CH3–I + I• – 84 Small
of reactivity.
Overall H° = + 54
iii) The energy of activation for the first chain-propagating step in iodination
reaction (140 kJ mol–1) is so large that only two collisions out of every 1012
i) The I–I bond is weaker than the F–F bond the chain-initiating step is not
have sufficient energy to produce reactions at 300 °C.
responsible for the observed reactivities: F2 > Cl2 > Br2 > I2.
5) The halogenation
ii) The reactions are quitestep
H-abstraction similar
(theand thuschain-propagating
first have similar entropystep) determines the order
changes the relative reactivities of the halogens toward methane can be
of reactivity.
compared on energies only.
iii) The energy of activation for the first chain-propagating step in iodination
 formed in each reaction.

Cl2
CH3CH2CH3 o CH3CH2CH2Cl + CH3CHCH3
light, 25 C
Cl
Propane Propyl chloride Isopropyl chloride
(45%) (55%)

CH3 CH3 CH3

Cl2
CH3CHCH 3 o
CH3CHCH 2Cl + CH3CCH3
light, 25 C
Cl
Isobutane Isobutyl chloride tert-butyl chloride
(63%) (37%)

CH3 CH3 CH3

Cl2
CH3CCH2CH3 o
ClCH2CCH2CH3 + CH3CCH2CH3
300 C
H Cl
2-Methylbutane 1-Chloro-2methyllbutane 2-Chloro-2-methylbutane
(30%) (22%)
CH3 CH3
+ CH3CCHCH 3 + CH3CCH2CH2Cl
Cl
2-Chloro-3-meyhylbutane 1-Chloro-3-methylbutane
(33%) (15%)
 more selective in the site of attack when it does react.
2. The reaction of isobutene and bromine gives almost exclusive replacement of the
3° hydrogen atom.

CH3 CH3 CH3

Br2
CH3CCH2H CH3CCH3 + CH3CHCH 2Br
light, 127 oC
H Br
(>99%) (trace)

i) The ratio for chlorination of isobutene:

CH3 CH3 CH3
Cl2
CH3CCH2H CH3CCH3 + CH3CHCH 2Cl
h , 25 oC
H Cl
(37%) (63%)

3. Fluorine is much more reactive than chlorine fluorine is even less selective
than chlorine.

10.7 THE GEOMETRY OF ALKYL RADICALS

 10.7 THE GEOMETRY OF ALKYL RADICALS

1. The geometrical structure of most alkyl radicals is trigonal planar at the

having the unpaired electron.
1) In an alkyl radical, the p orbital contains the unpaired electron.

~ 25 ~

(a) (b)
ure 10.6 (a) Drawing of a methyl radical showing the sp2-hybridized
atom at the center, the unpaired electron in the half-filled p
and the three pairs of electrons involved in covalent bonding
unpaired electron could be shown in either lobe. (b) Cal
10.8 REACTIONS
10.8 REACTIONS
THAT GENERATE
THAT TETRAHEDRAL
GENERATE TETRAHEDRAL
STEREOCENTERS
STEREOCENTERS

1. 1. When
When achiral
achiral molecules
molecules react
react to produce
to produce a compound
a compound with
with a single
a single tetrahedral
tetrahedral
stereocenter,
stereocenter, the the product
product willwill be obtained
be obtained as aasracemic
a racemic form.
form.
1) 1)
TheThe radical
radical chlorination
chlorination of pentane:
of pentane:

Cl2 Cl2 *CH*CH

CH CH CH CH CH
CH3CH32CH22CH22CH23 3 CHCH
3CH3CH
2CH2CH
2CH
2CH
2CH2CH
2Cl2Cl
+ +
CH CH
3CH3CH
2CH
2CH
2 2 ClCHClCH
3 3
(achiral)
(achiral)
Pentane
Pentane 1-Chloropentane
1-Chloropentane (±)-2-Chloropentane
(±)-2-Chloropentane
(achiral)
(achiral) (achiral)
(achiral) (a racemic
(a racemic form)
form)

+ +CHCH
3CH3CH 2CHClCH
2CHClCH 2CH2CH
3 3
3-Chloropentane
3-Chloropentane (achiral)
(achiral)

1) 1) Neither
Neither 1-chloropentane
1-chloropentane nor nor 3-chloropentane
3-chloropentane containsa stereocenter,
contains a stereocenter,butbut
2-chloropentane
2-chloropentane does,
does, andand is obtained
it isitobtained as aasracemic
a racemic form
form . .

~ 26~~26 ~
A Mechanism for the Reaction
A Mechanism for the Reaction
The Stereochemistry of Chlorination at C2 of Pentane

The Stereochemistry of Chlorination at C2 of Pentane

C2
CH3CH2CH2CH2CH3
C2
Cl
CH3CH2CH2CH2CH3
CH3
CH3 Cl2 Cl2 Cl H3C
Cl + Cl C C C Cl + Cl
H H
CH2CH2CH3 H CH2CH2CH3 CH
H3CH2CH2C
3
(S)-2-Chloropentane
CH3Trigonal
Clplanar
2 radical Cl2
(R)-2-Chloropentane
H3C
Cl +(50%)
Cl C C C Cl + Cl
H (achiral) (50%) H
CH2CH2Enantiomers
CH3 H CH2CH2CH3 H3CH2CH2C
(S)-2-Chloropentane Trigonal planar radical (R)-2-Chloropentane
Abstraction of a hydrogen atom from C2 produces a trigonal planar radical that is
(50%) then reacts with chlorine
achiral. This radical is achiral at either face [by path (50%)
(achiral) (a)
or path (b)]. Because the radical is achiral the probability of reaction by either
path is the same; therefore, the two enantiomersEnantiomers
are produced in equal amounts,
and a racemic form of 2-chloropentane results.
Abstraction of a hydrogen atom from C2 produces a trigonal planar radical that is
achiral. This radical is achiral then reacts with chlorine at either face [by path (a)
or path (b)]. Because the radical is achiral the probability of reaction by either
10.8A path
GENERATION OF A
is the same; SECOND Sthe
therefore, TEREOCENTER IN A Rare
two enantiomers ADICAL
produced in equal amounts,
 and are separable by conventional means (by GC, LC, or by careful fractional
distillation). OF A SECOND STEREOCENTER IN A RADICAL
10.8A GENERATION
HALOGENATION:
A Mechanism for the Reaction
1. When a chiral molecule reacts to yield a product with a second stereocenter:
The Stereochemistry of Chlorination at C3 of (S)-2-Chloropentane
1) The products of the reactions are diastereomeric (2S,3S)-2,3-dichloropentane
and (2S,3R)-2,3-dichloropentane.
3 CH
i) The two diastereomers are not produced
H in equal amounts.
Cl
C
ii) The intermediate radical itself is chiral reactions at the two faces are not
CH2
equally likely.
CH2
iii) The presence of a stereocenter in the radical (at C2) influences the reaction that
CH3
introduces the new stereocenter (at C3).
Cl
~ 27 ~

CH3 CH3 CH3

H Cl H Cl H Cl
C C C
Cl2 Cl2
Cl + C C C + Cl
Cl H H Cl
CH2 H CH2 CH2
CH3 CH3 CH3
(2S,3S)-2,3-Dichloropentane Trigonal planar radical (2S,3R)-2,3-Dichloropentane
(chiral) (chiral) (chiral)

Diastereomers
10.9
10.9 R
R10.9 AADDITION
REDICAL
EDICAL
EDICAL ADDITION
DDITION TOTO A
TOAA LKENES
LKENES
LKENES : THE
::THE
THE ANTI
ANTI ANTI
-M -MARKOVNIKOV
-MARKOVNIKOV
ARKOVNIKOV
A ADDITION
ADDITION
DDITION OFH
OF HH YDROGENB
OFYDROGEN
YDROGEN BROMIDE
B
ROMIDE
ROMIDE
1. Kharasch and Mayo (of the University of Chicago) found that when alkenes that
1.1. Kharasch
Kharasch and
and Mayo
contained Mayo (of the
(ofor
peroxides
University
the University
hydroperoxides
of of
Chicago) found
reactedChicago)
that when
with HBr found
alkenes
that when
anti-Markovnikov
that th
alkenes
contained
contained peroxides
peroxides
addition ororhydroperoxides reacted
hydroperoxides
of HBr occurred. reacted HBrHBr anti-Markovnikov
withwith anti-Markovniko
addition of HBr occurred.
addition of HBrRoccurred.
O O R R O O H

R AnOorganic R
O peroxide R hydroperoxide
An organic O O H
R O O R R O O H
1) An
In the presenceperoxide
organic of peroxides, propene yields An
1-bromopropane.
organic hydroperoxide
An organic peroxide An organic hydroperoxide
1) In the ROORpropene yields 1-bromopropane.
CHpresence
3CH=CH2 of peroxides,
+ HB r CH3CH2CH2BrAnti-Markovnikov addition
1) In the presence of peroxides, propene yields 1-bromopropane.
2) In the absence of peroxides, or in the presence of compounds that would “trap”
ROOR
CH3CH=CH + HB
radicals,
2 r
normal Markovnikov CH 3CHoccurs.
addition 2CH2Br Anti-Markovnikov addition
ROOR
CH3CH=CH2 + HBr CH3CH2CH2BrAnti-Markovnikov addition
2) In the
CHabsence of peroxides,
no or in the presence of compounds that would “trap”
3CH=CH2 + HBr CH3CHBrCH2–H Markovnikov addition
peroxides
2) In the absence
radicals, normal of peroxides, addition
Markovnikov or in theoccurs.
presence of compounds that would “trap
2. HF, HCl, and HI do not give anti-Markovnikov addition even in the presence of
radicals, normal Markovnikov addition occurs.
peroxides. no
CH3CH=CH 2 + HBr CH3CHBrCH2–H Markovnikov addition
peroxides
no orientation of Br in the product because a more stable
3. Step 3 determines the final
 CH3CH=CH2 ++ HB
CH HBr ROOR CH3CH
CH2CH
CH2Br
BrAnti-Markovnikov
Anti-Markovnikov addition
addition
CH33CH=CH
CH=CH22 + HBrr CH
CH33CH22CH22Br Anti-Markovnikov addition

2) In theradicals,
absence normal
of Markovnikov
peroxides, or in the addition
presence of occurs.
compounds that
that would
would “trap”
“trap”
2)
2) In
In the
the absence
absence of
of peroxides, or in
peroxides, or in the
the presence
presence of
of compounds
compounds that would “trap”
radicals, normal Markovnikov
radicals, Markovnikov addition
addition occurs.
occurs.
radicals, normal
normal Markovnikov addition
no occurs.
CH3CH=CH2 + HBr CH3CHBrCH2–H Markovnikov ad
no peroxides
CH CH=CH2 ++ HBr
HBr no CH3CHBrCH
CHBrCH2–H–H Markovnikov
Markovnikov addition
addition
CH333CH=CH
CH CH=CH22 + peroxides CH 3
3 CHBrCH22–H Markovnikov addition
peroxides
2. HF, HCl, and HI do not give anti-Markovnikov addition even in the
2. HF, HCl,
2. HCl, and
and HI
HI do
do not give anti-Markovnikov
not give anti-Markovnikov addition
addition even
even in
in the
the presence
presence of
of
2. HF,
HF, HCl, and
peroxides. anti-Markovnikov addition even in the presence of
peroxides.
peroxides.
peroxides.
3. Step 3 determines the final orientation of Br in the product because a
3. Step
3. Step 333 determines
3. Step
determines the final orientation of Br
Br in
determines the final orientation of Br
in the
in the product
the productbecause
product becauseaaamore
because morestable
more stable
stable
2° 2° radical
radical is is produced
produced and and attack
because becauseat attack
the 1° at theis1°
carbon carbon
less is.less hind
hindered
2° radical is
2° radical is produced
produced and because attack at
at the
the 1°1° carbon
carbon isis less hindered. .
lesshindered

xx x
Br x CH CH2x CH
Br ++ H
H
Br2C +CH
2C
CH CH3 CH
H 2C
CH 3 x CH
3 22 CH
CH CH
CH
CH3332 CH CH3
CH
CH
Br
Br Br
Br

1) Attack
1) Attack at
at the
the 2° carbon atom would
would have
have been
beenmore
morehindered.
hindered.
1) Attack at the 2° carbon atom been more hindered.
1) Attack at the 2° carbon atom would have been more hindered.
Anti-Markovnikov Addition
Chain Initiation

heat
Step 1 R O O R 2R O H° + 150 kJ mol–1

Heat brings about homolytic cleavage of the weak oxygen-oxygen bond.

Step 2 R O + H Br R O H + Br H° – 96 kJ mol–1

Eact is low
The alkoxyl radical abstracts a H-atom from HBr, producing a Br-atom.

Step 3 Br + H2C CH CH3 Br CH2 CH CH3

2° radical
A Br-atom adds to the double bond to produce the more stable 2° radical.

Step 4 Br CH2 CH CH3 + H Br Br CH2 CH CH3 + Br

H
1-Bromopropane
The 2° radical abstracts a H-atom from HBr. This leads to the product and
 1) Proton is small steric effects are unimportant.
2) Proton attaches itself to a carbon atom by an ionic mechanism to form the more
stable carbocation Markovnikov addition.
H Br + Br
H2C addition
Ionic CHCH3 H CH2CHCH3 H CH2CHCH3
~ 30 ~ Br
H More
Br stable carbocation
+ BrMarkovnikov product
H2C CHCH3 H CH2CHCH3 H CH2CHCH3
2. In the presence of peroxides, the reagent that attacks the double bond first is the
Br
larger bromine atom. More stable carbocation Markovnikov product
1)2. Bromine attaches of
In the presence itself to the less
peroxides, thehindered carbon
reagent that atomthe
attacks by double
a radicalbond
mechanism
first is the
tolarger
form bromine stable radical intermediate anti-Markovnikov addition.
the more atom.
Radical addition
1) Bromine attaches itself to the less hindered carbon atom by a radical mechanism
to form the
Brmore stable radical intermediate anti-Markovnikov addition.
H Br
H2C CHCH3 Br CH2CHCH3 Br CH2CHCH3 + Br
Radical addition
H
Br More stable radical H Br anti-Markovnikov product
H2C CHCH3
4-23-02 Br CH2CHCH3 Br CH2CHCH3 + Br
H
10.10 RADICAL POLYMERIZATION OF ALKENES
More stable radical :
anti-Markovnikov product
CHAIN-GROWTH POLYMERS
4-23-02

10.10
1. RADICAL
Polymers, calledPmacromolecules,
OLYMERIZATION OF Aup
are made LKENES : repeating subunits
of many
Chain Initiation
Radical Polymerization
O of Ethene
O O
Chain Initiation
Chain Initiation O O O
Step 1 R O C O O O C R 2R C O O 2 CO2 + 2 R
Step 1 R O C O O O C R 2R C O O O 2 CO + 2 R
Step 1 R DiacylC Operoxide
O C R 2R C 2 CO22 + 2 R
Step 1 R DiacylC Operoxide
O C R 2R C O 2 CO2 + 2 R
Diacyl peroxide
Step 2 R + H2C CH2 R CH2 CH2
Diacyl peroxide
Step 2 R + H2C CH2 R CH2 CH2
Step
The 2 Rperoxide
diacyl + H2C dissociates
CH2 to CH2 CH
Rproduce radicals,
2 which in turn initiate chains.
Step
The 2 Rperoxide
diacyl + H2C dissociates
CH2 to
Rproduce
CH2 CH radicals,
2 which in turn initiate chains.
The diacyl
Chain peroxide
Propagation dissociates to produce radicals, which in turn initiate chains.
The diacyl
Chain peroxide dissociates to produce radicals, which in turn initiate chains.
Propagation
Step
Chain 3 R CH 2 CH 2 + n H2C CH 2
Propagation R ( CH 2CH 2 )n CH 2CH 2
Step
Chain 3 R CH
Propagation CH 2 + n H C CH R ( CH 2CH 2 )n CH 2CH 2
Step
Chain 3 R CH 22 by
propagation CH adding H22C CHethylene
2 + nsuccessive
2
2 ( CHuntil
Runits, )n CHgrowth
2CH 2their 2CH 2 is stopped
Step
Chain 3 R CH 2 by
propagation CH by
2 +combination
adding n successive
H 2 C or
CH 2disproportionation.
ethylene R CH 2CH 2 n CH 2CH 2 is stopped
units,
( until their
) growth
Chain propagation by adding successive ethylene units, until their growth is stopped
by combination or disproportionation.
Chain
Chain Termination by combination
propagation by adding successiveorethylene
disproportionation.
units, until their growth is stopped
Chain Termination by combination or disproportionation.
Step
Chain 4
Termination
Step
Chain 4
Termination combination
Step 4 R ( CH2CH2 )n CH2CH2 2
combination
Step combination R ( CH CH ) CH CH
2 R 4( CH2CH2 )n CH2CH2 R ( CH22CH22 )nn CH22CH22 22
disproportionation
combination R ( CH CH ) CH CH +
2 R ( CH2CH2 )n CH2CH2 R ( CH22CH22 )nn CH2CH22 2
2 R ( CH2CH2 )n CH2CH2 disproportionation RR ((( CH
CH
CH22CH CH22 )))nnCH
CH CH CH
CH2CH +
CH23 +
disproportionation R n
2R ( CH 2 CH )
2 n CH 2 CH 2
2 2
R (( CH2CH2 ))n CH2CH3
2
The radical at the end of the growing disproportionation
polymer chain R can CH
R also22CHCH 22 )nnCHa2hydrogen
abstract CH23 +
atomradical
The from itself
at thebyend
what is called
of the growing“back biting.”
polymer chainThis
can(leads
R also
CH CH to chain
abstract
2 )n CHabranching.
hydrogen
CH3
The radical at the end of the growing polymer chain can also2 abstract a2hydrogen
atom from itself by what is called “back biting.” This leads to chain branching.
Chain
The Branching
atomradical
from itself
at thebyend
what is called
of the growing“back biting.”
polymer chainThis
canleads to chain abranching.
also abstract hydrogen
Chain
atomBranching
from itself by what is called “back biting.” This leads to chain branching.
Chain Branching H CH2
Chain Branching H CH2 RCH2CH ( CH2CH2 )n CH2CH2 H
R CH2CH H CH2
R CH2CH RCH2CH ( CH2CH H22C))n CH CH
CH 2CH H
H ( CH2CH2 )CH n 22 RCH2CH ( CH2CH 2CH2 22 H
R CH2CH 2 n
( CH CH )CH n 2
H C CHCH
CH (( CH H2222C))nn CH
RCH 2
R CH2CH( CH22CH22 )CH n 2 RCH22CH CH22CH
CH CH
CH 22CH H
2 22 H
( CH2CH2 )n RCH2CH ( CH2CH H C) CH CHCH 2 2 H
RCH2CH CH2( CH2CH222 )nn CH22CH 2 H
CH ( etc.
RCH2CH CH22 CH2CH 2 )n CH2CH2 H
etc.
CH22 etc.
CH
 1) The PE is of higher density, has a higher melting point, and has greater strength.

Table 10.2 Other Common Chain-Growth Polymers

Monomer Polymer Names
( CH2 CH )n
CH2=CHCH3 Polypropylene
CH3
( CH2 CH )n
CH2=CHCl Poly(vinyl chloride), PVC
Cl
( CH2 CH )n
CH2=CHCN Polyacrylonitrile, Orlon
CN
CF2=CF2 ( CF2 CF2 )n Polytetrafluoroethene, Teflon
CH3
CH3 Poly(methyl methacrylate),
( CH2 C )n
H2C CCO2CH3 Lucite, Plexiglas, Perspex
CO2CH3

10.11 OTHER IMPORTANT RADICAL CHAIN REACTIONS

10.1110.11
OTHER IMPORTANT
OTHER RADICAL
IMPORTANT CHAIN
RADICAL CHAINRREACTIONS
EACTIONS
10.11 OTHER IMPORTANT RADICAL CHAIN REACTIONS
10.11A MOLECULAR
10.11A OXYGEN
MOLECULAR OXYGEN
AND SUPEROXIDE
AND SUPEROXIDE
10.11A MOLECULAR OXYGEN AND SUPEROXIDE
1. Molecular
1. Molecular oxygen
oxygen in ground
in the the ground state
state is aisdiradical
a diradicalwith
withone
oneunpaired
unpaired electron
electronon
on
1. each
Molecular oxygen in the ground state is a diradical with one unpaired electron on
oxygen.
each oxygen.
1) each
As aoxygen.
radical, oxygen can abstract hydrogen atoms just like other radicals.
1) As a radical, oxygen can abstract hydrogen atoms just like other radicals.
1) As asystems,
2. In biological radical, oxygen
oxygencan abstract
is an hydrogen
electron atoms just like other radicals.
acceptor.
~ 33 ~
~ 33 ~
1) Molecular oxygen accepts one electron and
~ 33 ~ becomes a radical anion called

superoxide ( O2 ).

2) Superoxide is involved in both positive and negative physiological roles:

i) The immune system uses superoxide in its defense against pathogens.
ii) Superoxide is suspected of being involved in degenerative disease processes
associated with aging and oxidative damage to healthy cells.

3) The enzyme superoxide dismutase regulates the level of superoxide by

catalyzing conversion of superoxide to hydrogen peroxide and molecular
oxygen.
 associated with aging and oxidative damage to healthy cells.

3) The enzyme superoxide dismutase regulates the level of superoxide by

catalyzing conversion of superoxide to hydrogen peroxide and molecular
oxygen.
i) Hydrogen peroxide is also harmful because it can produce hydroxyl (HO•)
radicals.
ii) The enzyme catalase helps to prevent release of hydroxyl radicals by
converting hydrogen peroxide to water and oxygen.

superoxide dismutase
2 O2 + 2 H+ H2O2 + O2
catalase
2 H2O2 2 H2O + O2

10.11B COMBUSTION OF ALKANES

1. When alkanes react with oxygen a complex series of reactions takes place,
ultimately converting the alkane to CO2 and H2O.

R H + O2 R + OOH Initiating
 10.11C AUTOXIDATION

1. Linoleic acid is a polyunsaturated fatty acid (compound containing two or more

Step 1 Chain initiation
H HH double H in polyunsaturated
H bonds) occurs as an ester HH H fats.
ROH

CH3(CH2)4 C (CH2)7CO
H 2R' H CH
H 3(CH2H
)4 C (CH2)7CO2R'
H H
H HH H H Linoleic acid (as an ester)
RO CH3(CH2)4 (CH2)7CO2R'
C
H H
CH3(CH2)4 C (CH2)7CO2R'
2. Polyunsaturated H fats occur widely in the fats and oils that are components of our
diet and are widespread in the tissues of the body where they perform numerous
Step 2 Chain Propagation
vital functions.
O O
H H3.H The hydrogen
H atoms of theO–CH
O2– group
H Hlocated Hbetween the two double bonds of
linoleic ester (Lin–H) are especially susceptible to abstraction by radicals.
H
CH3(CH2)4 (CH
C1) Abstraction) CO R' CH (CH
2 7 of 2one of these
3 2)4
hydrogen (CH2)7CO
Catoms produces R' radical (Lin•) that
a 2new
H H
can react with oxygen in autoxidation.
2) The result of autoxidation is the formation of a hydroperoxide.
Step 3 Chain Propagation
Another radical
O O H4.H Autoxidation
H HOthatOoccurs
is a process H in
H many substances:
H
Lin H 1) Autoxidation is responsible for the development + of Lin
the rancidity that occurs
H H
CH3(CH2)4 C when (CH 2)7and
fats CO2R' oilsCH 3(CH
spoil 2)4 for the
and (CH2)7combustion
C spontaneous CO2R' of oily rags left
H open to the air. H
Hydrogen abstraction from another A hydroperoxide
2) Autoxidation occurs in the body which may cause irreversible damage.