Chapter 10 Lecture PDF

Chapter 10: Radical Reactions
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Chapter 10: Radical Reactions
Topics:
I. Radicals
II. Common Patterns in Radical Mechanisms
III. Chlorination of Methane
IV. Thermodynamic Considerations for Halogenation Reactions
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V. Selectivity of Halogenation
VI. Stereochemistry of Halogenation
VII. Allylic Bromination
VIII. Atmospheric Chemistry and the Ozone Layer
IX. Autooxidation and Antioxidants
X. Radical Addition of HBr: Anti-Maokovnikov Addition
XI. Radical Polymerization
XII. Radical Processes in the Petrochemical Industry
XIII. Halogenation as a Synthetic Technique
2
I. Radicals
• Free radicals form when bonds break homolytically
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• Note the single-‐barbed or fishhook arrow used to show the
electron movement
I. Radicals
• Recall the orbital hybridization in carbocations and carbanions
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I. Radicals
• Radicals appear to be trigonal planar (sp2 hybridized) or shallow
trigonal planar (sp3 hybridized)
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sp2 hybridized
I. Radicals
• Radicals are neutral (no formal charge) but still electron deficient
(incomplete octet)
• Radicals follow the same stability trend as carbocations, as they
are both electron Hello
deficient species
I. Radicals
• Bond strength is inversely proportional to carbon radical stability.
• The more stable the resulting radical(s), the weaker the bond
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I. Radicals
• Radicals, like carbocations, are stabilized by resonance

delocalization.
• Fishhook arrows are used to present possible resonance forms

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I. Radicals
• The more resonance delocalized a radical is, the more stable it is
• Benzylic radicals are more stable than allylic radicals because the
radical is delocalized over more carbon atoms
• The entire Hello
molecule is missing just one electron, vs a single
carbon atom missing one electron
I. Radicals
• Resonance stabilized radicals are more stable than 3˚ radicals
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I. Radicals
• Vinylic radicals are especially unstable (as with vinyl cations)
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• A radical in a sp2 orbital is less stable than one in a sp3 orbital
I. Radicals
Hello
I. Radicals
Identify the weakest C-‐H bond in the following compound
a.
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I. Radicals
Answer: The key to this problem is to break each C-‐H bond in your mind, and
think about how stable each resulting radical is. Once you find the most stable
radical, you know that C-‐H bond must be the weakest.
Resonance
Stabilized Hello
a. Weakest C-‐H bond
No C-‐H bond
here
• Like ionic mechanisms, radical mechanisms follow patterns

• But, radical mechanisms are distinctively different.
• For example, radicals do not undergo rearrangement
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• Radical mechanisms follow SIX key arrow-‐pushing patterns

1. Homolytic Cleavage: initiated by light or heat
2. Addition to a pi bond

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3. Hydrogen abstraction: not the same as proton transfer
4. Halogen abstraction
5. Elimination: The reverse of addition

• the radical, on the α carbon is pushed toward the β carbon to
eliminate a radical atom/group
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6. Coupling: the reverse of homolytic cleavage

• Group the relationship(s) among these six patterns and you see
there are only 3 processes, forward and backward
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• The steps in a radical mechanism are classified as either initiation,
termination, or propagation
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• An initiation step is one where
radical species are formed from
a non-‐radical species
• Propagation occurs when radical reacts with a non-‐radical species,

to form a new radical (and a non-‐radical)
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• Termination occurs when two radical species react to form a non-‐
radical species
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• The complete definitions of
initiation, propagation and
termination will be discussed
later
Draw the appropriate fishhook arrows for the following radical
processes:
a. + Br2
Br
+ Br
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b. + Br
Br
c. +
Answers: Don’t forget to use the fishhook arrows.
a. + Br Br
Br
+ Br
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b.
+ Br
Br
c.
+
• Chlorination of methane follows a radical mechanism:

• Radical mechanism consists of three distinct stages:
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1. INITIATION: chlorine radicals are created

2. PROPAGATION: these steps are self-‐sustaining. The first propagation
step consumes a Cl radical, and the second step produces one.
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3. TERMINATION: occurs when radicals collide/couple.
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• The sum of the propagation steps gives the net reaction:
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• Propagation is a chain reaction: the product(s) for a later step

serve as reactant(s) for an earlier step in the mechanism
• Polychlorination is difficult to prevent

• Methyl chloride is more reactive towards radical halogenation
than methane
Hello
• Need excess methane, relative to Cl2, for monochlorination to be
the major product.
• Radical initiator: possesses a weak bond that cleaves

homolytically with heat or light
dihalides
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alkyl
peroxides
acyl
peroxides
• The acyl peroxide is most reactive, and is effective at 80 °C
• Radical inhibitors: react with radicals, and prevent a chain process

from initiating or propagating
• Stabilized radicals and compounds that easily form stabilized

radicals are good inhibitors:
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Oxygen is a diradical, and will react Hydroquinone will also react
with two other radicals with two radicals
• Radical reactions are very slow in the presence of oxygen
• Hydroquinone undergoes H-‐abstraction to form a resonance-‐

stabilized radical
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Draw a mechanism for each of the following reaction:
Chlorination of ethane to produce ethyl chloride
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Answer:
CH3 Cl2
H 3C hv Cl
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H H H H
Cl Cl H C C H Cl H C C Cl
Cl
H H H H
IV. Thermodynamic Considerations for Halogenation
Reactions
• If we want to determine whether a process is product favored, we
must determine the sign (+/-‐) for ΔG
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• In a halogenation reaction, entropy is negligible.

• # of reactants = # of products
Reactions
• Can estimate the value of ΔH based on BDE’s for the bonds broken
versus the bonds made in the reaction:
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Reactions
Hello
Reactions
• Fluorination is so exothermic, it is not practical (too violent)
• too violent = lots of unwanted byproducts.
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• Iodination is endothermic, not thermodynamically favored, and doesn’t occur.
• Only halogenation with Cl2 and Br2 are useful.

Reactions
• Both chlorination and bromination are exothermic (favored).
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• But, ΔH for the first step of bromination is endothermic
Reactions
• So, bromination is much slower than chlorination
• These means bromination is more selective.
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• With substrates more complex than ethane, multiple

monohalogenation products are possible
Hello two monohalogenation

products are possible for
propane
• Chlorine is indiscriminant; significant amount of each product is

formed
• But since 2˚ radicals are more stable than 1˚, the secondary halide
is the major product
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Hydrogen abstraction from

a 2˚ carbon is faster than a
1˚ carbon
• Bromination is much slower, and so it is much more selective for
the the more reactive 2˚ carbon:
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• The fact bromination is more regioselective than chlorination can

be explained by the Hammond Postulate
• Focus on the H abstraction (rate determining) step.

• The transition state will be more like the reactants or more like the
products, whichever is closer in energy
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chlorination TS bromination TS

resembles reactants Resembles products
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• For bromination, the stability of the

transition state largely depends on the
stability of the resulting carbon radical
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• For chlorination, the stability of the

transition state does not depend on the
stability of the resulting carbon radical as
much.
• In short, the difference in TS energies for the formation of a 1 vs. 2˚
vs 3˚ radicals is much bigger for bromination
• Thus, bromination is more selective for the lower energy pathway
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• Bromination at the 3° position happens 1600 times more often
than at the 1° position
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• Fluorination is the fastest process, and thus the least selective
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Predict the major product obtained upon radical bromination of
2,2,4-‐trimethylpentane. Assume only 1 Br is added.
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Answer: There is only one tertiary position so the Br ends up there
since a tertiary radial is the most stable ( just like with carbocations)
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Br
only
ter]ary secondary
posi]on posi]on
quaternary
posi]on
(no C-‐H bond)
• The halogenation of butane or more complex alkanes forms a new
chirality center
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• 2-‐chlorobutane will form as a racemic mixture

• Whether the free radical carbon is sp2 or a rapidly interconverting
sp3, the halogen abstraction will occur on either side of the plane
with equal probability
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sp2 hybridized
• There is actually a total of three monosubstituted products form in
the halogenation of butane
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• In the halogenation of (S)-‐3-‐methylhexane, the chirality center is

the most reactive carbon in the molecule.
Hello A racemic mixture will

be obtained
• The chirality center is a 3˚ carbon, and it has a weaker C-‐H bond
than the 2˚ and 1˚ carbons
Predict the stereochemical outcome of radical bromination of the
following alkanes:
a. Hello
b.
Answers:
Br
a. Br
Hello
a pair of diastereomers
Br
b. Br
a pair of diastereomers
For quesdon b., I suspect that the ﬁrst product(on the lef) is major because there is a giant
t-‐butyl group pardally blocking the top face of the ring.
• Recall the weakest C-‐H bond (lowest BDE) will undergo radical H-‐
abstraction faster than the others.
• Alkenes selectively undergo H-‐abstraction at the allylic carbon
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• H-‐abstraction of an allylic H results in a resonance-‐stabilized allylic

radical:
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• So, bromination of an alkene is selective for the allylic carbon
• But, addition of Br2 to the alkene is a competing reaction…
• To avoid the competing alkene addition, NBS is used as a source of
Br radicals (instead of using Br2)
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• Using NBS keeps the concentration of HBr and Br2 low, so competing
addition reactions to the alkene are minimized
• Propagation produces the allylic radical and HBr
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• The HBr produced reacts with NBS to form Br2 … and this Br2 then
continues propagation and the formation of the product
• With asymmetric alkenes, a mixture of isomeric products is often

obtained
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• The radical is delocalized on two carbon atoms, and so
halogenation occurs at either site
Predict the products that are obtained when each of the following
compounds is treated with NBS and irradiated with UV light.
a. NBS
Hello hv
NBS
b. hv
Answer: First, find the weakest C-‐H bond and break it. Second determine the
possible resonance structures (what carbons are the radical located on). Third,
add in the Br’s. For both (a. and b.), both of the allylic positions are identical
since the molecules are symmetrical.
Br
NBS Br
hv Hello
a.
racemic mixture
Br
NBS
hv Br
b. racemic mixture
Both allylic posi]ons

are the same in this
symmetrical molecule.
• Ozone is both created and destroyed in the upper atmosphere
• No net reaction is had overall, but UV radiation is converted to
heat
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• Heat is a more disordered form of energy, compared to light
• This process is spontaneous because entropy is increased
• O3 depletion is a serious health and environmental problem.

Without it, harmful UV radiation penetrations the atmosphere.
• Chlorofluorocarbons are believed to be the culprit

Hello
• They reach the upper atmosphere, and react with UV light to form
chlorine radicals
• The Cl radicals destroy ozone by the following mechanism
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• Cl radicals are formed during propagation, and continue the

destruction of ozone molecules
• One Cl radical can catalytically destroy thousands of ozone molecules.
• CFC’s have been replaced with hydrofluoroalkanes (HFA’s)

• They are sometimes called hydrofluorocarbons (HFC’s)
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• They are not as harmful as CFC’s because they don’t produce
chlorine radicals, but they still act as greenhouse gases
• Autooxidation is the process by which organic compounds react

with atmospheric oxygen to form a hydroperoxide
Hello
• The process is generally very slow

The initiation step

is actually a
propagation based
on our earlier
Hello definitions…
…so the
definitions need to
be revised
• Propagation steps can be more precisely defined as the steps that
add together to give the net chemical equation
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• So initiation and termination steps are those that are not part of the
net chemical equation
• Ethers are particularly susceptible to autooxidation
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• Hydroperoxides can be explosive, and so ether supplies cannot be
stored for long periods of time.
• Storing sensitive compounds in dark containers prevents light from

accelerating the autooxidation process
• Triglycerides are important to a healthy diet, but also susceptible to
autooxidation (allylic carbons are especially reactive)
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• Autooxidation causes the food to become rancid and toxic

• Foods with unsaturated fatty acids have a short shelf life unless
preservatives are used
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• These preservatives are radical inhibitors.

• One molecule of BHT can prevent thousands of autooxidation

reactions
• BHT can undergo H-‐abstraction to scavenge a radical that would
otherwise initiate an autooxidation radical chain
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• So, inhibitors like BHT are often called antioxidants

• Natural antioxidants prevent the oxidation of cell membranes and

other biologically important compounds
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• Vitamin E is hydrophobic, and finds it’s way

into cell membranes
• Vitamin C is polar, and functions in polar
mediums, such as blood.
Vitamin C
• We learned in chapter 9 that H-‐X will add across a C=C double
bond with anti-‐Markovnikov regioselectivity when peroxides are
present
Hello without
peroxides
with
peroxides
• The peroxides initiate a radical mechanism of addition.

(Different mechanism, different selectivity)
• The reaction is initiated by thermal hemolytic cleavage of the
peroxide, which initiates the formation of a Br radical from HBr.
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• The Br radical then, in theory, could add to either side of the
alkene:
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• But it will add to the side that generates the more stable carbon
radical, as that will be a lower energy intermediate and thus a
lower energy transition state
• The Br radical adds to the less substituted carbon of the alkene,
generating the more stable (more substituted) carbon radical.
Hello

• The carbon radical then abstracts an H to form the product and
propagate the radical chain.
• Most of the radicals in solution at any given moment will be Br•
radical, so combination of them is typically the termination step
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• But, the combination of any two radicals constitutes a termination

step.
• Anti-‐Markovnikov radical addition of HBr is generally spontaneous

(product favored)
• radical addition of HCl and HI are generally nonspontaneous
(reactant favored)
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• Consider the overall thermodynamics of each reaction to

understand why
• Consider the halogen radical adding to the alkene:
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• The iodide radical is so much more stable than a carbon radical
that it’s addition to an alkene is not thermodynamically favored.
• Now consider the product forming step:
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• Abstraction of H from HCl is not thermodynamically favored,

because of the instability of the Cl radical.
• Recall that addition reactions often form a new chirality center
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• If the substrate is not chiral, then a racemic mixture will be
obtained when one new chirality center is formed
• If the starting alkene contains a stereocenter, then a mixture of

diastereomers would be obtained.
Predict the products for the following reactions:
a. HBr
ROOR
Hello
HBr
b. ROOR
c. HBr
ROOR
Answers: You will always form the most stable radical which means that the Br
will end up on the least substituted position. The radical is most stable at the
more substituted position.
a. HBr
ROOR
Hello Br Br
Br Br
HBr
b. ROOR
HBr
c. ROOR
Br Br
• Free radical conditions are also frequently used to form polymers
• Recall that a polymerization process joins together many small

units called monomers in a long chain
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monomer polymer
• Radical polymerizations generally proceed through radical chain

mechanism:
Hello

mechanism:
Hello
• The summation of the propogation steps gives the overall net
reaction

mechanism:
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• Chain Branching is inevitable in this process, and occurs by the
following mechanism
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• Highly branched polyethylene forms

flexible plastic (e.g. squeeze bottle)
• Unbranched polyethylene is brittle and

rigid (like a plastic bottle cap)
• Polymers with varying properties are obtained by polymerizing

substituted ethylene derivatives:
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• Polymers with varying properties are obtained by polymerizing

substituted ethylene derivatives:
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• Cracking of hydrocarbons produces smaller alkanes and alkenes
• Hydrocracking is dHello

one in the presence of H2 gas, forming only
alkane products
• Reforming is also a radical process, producing branched alkanes
diesel type molecule gasoline type molecule

• Gasoline: Contain 4-‐12 carbon atoms per molecule, primarily branched
alkanes.
• Branched alkanes are more stable, have a higher ignition
temperature, and require a spark plug.
• Presences of branded alkanes result in many 2° and 3° radicals,
and will not Hello
burn as hot as diesel. Will also burn more smoothly.
• Diesel: Contains 4-‐20 carbon atoms per molecule. Primarily linear

alkanes.
• Linear alkanes are less stable, compression alone provides hot
enough temperatures for ignition. Diesel burns hotter than
gasoline (more high-‐energy C-‐H bonds).
• Chlorination, to synthesize alkyl chlorides, is only useful when

there is only one possible product
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• Bromination is slower, and more selective, and can be performed
when several monohalogenation products are possible
• Overall, the real advantage of halogenation is functionalizing an

otherwise unreactive alkane, which can then be converted into
other useful functional groups.
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• Radical reactions are synthetically useful, and will be applied to
multistep syntheses throughout this text/course:
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I. Radicals
I. Rank the following radicals in order of stability.
a.
Hello
b.
I. Radicals
I. Answers: Hyperconjugation stabilizes radicals in the exact same way that
hyperconjugation stabilizes carbocations. The stability trend is the same as it
is for carbocations. Tertiary is the most stable, and primary is the least stable
(or most reactive)
Hello
a.
most stable more stable than a primary radical,

least stable
(ter]ary radical) less stable than a ter]ary radical
(primary radical)
(secondary radical)
b.
most stable more stable than a primary radical, least stable

(ter]ary radical) less stable than a ter]ary radical (primary radical)
(secondary radical)
I. Radicals
II. Draw all resonance structures for the following radicals. Make
sure you use the necessary fishhook arrows. Also, rank the stability
of the three radicals in a-‐c.
a.
Hello
b.
c.
I. Radicals
II. Answers: Radical c is the most stable, it has the greatest resonance stabilization.
Radical b is the next most stable since it is resonance stabilized over two secondary
carbons. Radical a is the least stable since it is spread out over two primary carbons.
a.
Hello
least stable
b.
c.
most stable
I. Radicals
IV. Identify the weakest C-‐H bond in the following compounds
a.
Hello
b.
c.
d.
I. Radicals
IV. Answers:
a. H
Resonance
Stabilized
Hello
and its on a ter]ary
carbon Weakest C-‐H bond
b. H
This is the only

Resonance
c. Stabilized Radical
d. Resonance
Stabilized H
and its on a ter]ary Weakest C-‐H bond
carbon
I. Radicals
V. These C-‐H bonds have very similar bond dissociation energies.
Nevertheless, one of these C-‐H bonds is weaker. Explain your choice.
Hello
Hb Ha
I. Radicals
V. Answer: The C-‐Ha bond is the weakest because one of the resonance
structures puts the radical on a tertiary carbocation which has a greater
stabilization due to hyperconjucation. If the C-‐Hb bond is broken, the radical
is only delocalized on primary and secondary carbons.
Hb
Hello Hb Hb
most stable radical (ter]ary)
Ha Ha Ha
Removing Hb will have no resonance forms that result in a ter]ary radical.
I. Radicals
VI. (S)-‐limonene (1) is a natural product and it can be converted to
a compound that displays antimalarial activity (compound 2).
Identify the weakest C-‐H bond is (S)-‐limonene.
O
Hello
O
1 2
I. Radicals
VI. Answer: In this case the weakest C-‐H bond is on a secondary carbon.
That is because the two resonance structures are a secondary radical and
a tertiary radial. If I plucked off the other C-‐H and formed a tertiary
radial, its only other resonance structure is a primary radical.
ter]ary
Hello radical
H
secondary
radical
Weakest C-‐H bond
H
ter]ary
radical primary
radical
VII. Draw the appropriate fishhook arrows for the following radical
processes:
a. + HBr + Br
Hello
b. + CH3
c.
+ Br + HBr
O
O
d. R O
O R
2
R O
O
VII. Answers: Don’t forget to use the fishhook arrows.
a.
+ H Br + Br
Hello
b. + CH3
+ Br + HBr
c.
O
O
O R 2
d. R O
R O
O
VIII. AIBN is used as a catalytic radical initiator to get this radical reaction started.
Tributyltinhydride is utilized since it really likes to grab halogen atoms. Your only job is
to draw the fish hook arrows that convert structure 2 to structure 3. You don't need
to know what AIBN or tributyldtin hydride is for a test, this example simply
demonstrates what radical reactions look like once you start working in a laboratory as
an organic chemist. N
N
C
Hello C
AIBN N N
(Radical Initiator) Bu (likes to grab halogens)
N
C H
N N Sn Sn Bu
2
Bu
C
tributyltin hydride
N
O
I
draw in
OEt
O O fishhook O
arrows
1
O O O Bu
EtO EtO I Sn Bu
4 3 2 OEt
Bu
Bu Bu
H Sn Bu Sn Bu
Bu Bu
Used for more reactions
VIII. Answer:
N C
AIBN C
N N
(Radical Initiator) Bu (likes to grab halogens)
N
C H
N N Sn Sn Bu
Hello 2
Bu
C
tributyltin hydride
N
O
I
draw in
OEt
O O fishhook O
arrows
1
O O O Bu
EtO EtO I Sn Bu
4 3 2 OEt
Bu
Bu Bu
H Sn Bu Sn Bu
Bu Bu
Used for more reactions
IX. Draw a mechanism for each of the following reactions:
a. Chlorination of methylene chloride (CH2Cl2) to produce

chloroform (CHCl3).
Hello
b. Chlorination of chloroform (CHCl3) to produce carbon
tetrachloride (CCl4).
c. Chlorination of 1,1,1-‐trichloroethane to produce 1,1,1,2-‐

tetrachloroethane.
d. Chlorination of 2,2-‐dichloropropane to produce 1,2,2-‐

trichloropropane.
IX. Answers:
H H
a. Cl Cl Cl C H Cl Cl C Cl CHCl3
Cl Cl
Hello
Cl Cl
b. Cl Cl Cl C H Cl Cl C Cl CCl4
Cl Cl
Cl H Cl H
c.
Cl
Cl Cl Cl C C H Cl Cl C C Cl Cl
Cl
Cl H Cl H Cl
Cl H Cl H
d. Cl Cl Cl C C H Cl Cl C C Cl
Cl
Cl
Cl
H 3C H H 3C H
X. Methyl bromide is widely used as a fumigant to prevent the spread
of diseases and pests in agricultural products, and it can be prepared
from methane via radical bromination. More recently, we can actually
use genetically engineered microorganisms to produce large quantities
of methyl bromide.
Hello
a. Draw a mechanism for the radical bromination of methane to
yield bromomethane.
b. In reality, radical bromination of methane produces many by-‐

products such as ethane. Suggest a mechanism for the formation
of ethane.
X. Answers:
H a H
a, b Br Br H C H Br H C Br CH3Br
H H
Hello
b
H H
H C C H H 3C CH3
H H ethane
XI. Predict the major product obtained upon radical bromination of
each of the following compounds. Assume only one Br is added.
Hello
a. b. c.
XI. Answer: In this case they all only have one tertiary position. Therefore, that
is where the bromide ends up. Remember, a tertiary radical is the most stabilized
through hyperconjugation.
Hello
Br
Br Br
a. b. c.
XII. A synthesis of the natural product indomycinone required the
halogenation step shown below. The major product of the reaction
was a monobrominated compound, however a significant amount
of dibrominated product was also formed. Draw both products and
rationalize why the dibrominated product forms so readily.
Hello
O O O
Br2
O hv
O
XII. Answer: The first bromine ends up at the tertiary position as
expected. This position is also resonance stabilized. The second
bromine ends up on the methyl group (the benzylic position). There
are at least 5 different resonance structures so the primary methyl
radical is exceptionally stable. In effect, the radical is spread out over
many different atoms.Hello
Br Br
O O O O O O O O O
Br2
O hv O O
O O O Br
XIII. Predict the stereochemical outcome of radical bromination of
the following alkanes:
a. Hello
b.
XIII. Answers:
Br2
a. Hello hv Br
Br
A pair of enantiomers.
Br Br
b. Br2
hv
A pair of diastereomers.
XIV. Carbohydrates such as the glucose derivative shown below can
be useful as a chiral starting material for biopolymers or the
synthesis of various natural products. Radical bromination will
primarily occur at the specified position. Draw both products and
predict if they will be produced in equal amounts.
Hello
OAc
Br2
O
AcO CO2Me hv
AcO
OAc
XIV. Answer: You form a pair of diastereomers so the products will
not be made in equal amounts. They only form in equal amounts if
you form a pair of enantiomers. By having chiral centers present, one
face of the ring will be more accessible then the other. In terms of
what product is favored, sometimes it is hard to predict. Chemists
often run the reaction and see what happens especially if a model
Hello
doesn't prove to be very useful.
OAc OAc OAc
Br2
O O O
AcO CO2Me hv AcO Br AcO CO2Me
AcO AcO AcO
OAc AcO AcO
CO2Me Br
XV. Predict the products that are obtained when each of the following
compounds is treated with NBS and irradiated with UV light.
a.
Hello
b.
c.
XV. Answer: First, find the weakest C-‐H bond and break it (next to the double
bond). Second determine the possible resonance structures (what carbons
are the radical located on). Third, add in the Br’s.
NBS
hv
Hello
a. Br Br
racemic
mixture
NBS
hv
b. same compound Br
Br Br
NBS
hv
c. racemic
mixture
XVI. When 2-‐methyl-‐2-‐butene is treated with NBS and irradiated with UV
light, five different monobromination products are obtained, one of which
is a racemicmixture of enantiomers. Draw all five monobromination
products and identify the product that is obtained as a racemic mixture.
Hello
XVI. Answer:
Br
Br Br
Br
a b
Hello
Br Br
c
d Br
Br pair of enantiomers
Br
The product from f is
e not drawn since it is
f
the same compund as
the product from d.
d and f are the same compound
XVII. Allylic bromination of the following compound will give a

wide variety of products. Draw all of the products including every
stereoisomer and constitutional isomer.
Hello O
O
XVII. Answer:
CO2Et CO2Et CO2Et Br CO2Et Br CO2Et

Br Br
Hello CO2Et CO2Et
Br Br
CO2Et CO2Et CO2Et CO2Et

Br
Br Br
CO2Et CO2Et
Br Br
XVIII. Most supersonic planes produce exhaust of hot gases

containing many compounds, including nitric oxide (NO). Nitric
oxide is a radical that is believed to play a role in ozone depletion.
First determine the structure of NO, then propose a series of
propagation steps that show how nitric oxide can destroy ozone in
a chain process. Hello
XVIII. Answer: Notice that we converted two ozone molecules into
3 oxygen molecules.
Hello
O O
O N
O O
O2
N
O2
O2
O
O
O hv
O
XIX. Predict the products for the following reactions:
a. HBr
ROOR
b. Hello
HBr
ROOR
HBr
c. ROOR
d. HBr
ROOR
HBr
e. ROOR
XIX. Answers: You will always form the most stable radical which means that the
Br will end up on the least substituted position. The radical is most stable at the
more substituted position.
a. HBr
ROOR
Br Br
Hello
b. HBr
ROOR
Br Br
Br Br
c.
HBr
ROOR
d.
HBr
ROOR
Br Br
Br Br
HBr
e. ROOR

Chapter 10 Lecture PDF

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Chapter 10 Lecture PDF

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Chapter 10: Radical Reactions

• Free radicals form when bonds break homolytically

• Recall the orbital hybridization in carbocations and carbanions

• Bond strength is inversely proportional to carbon radical stability.

• Radicals, like carbocations, are stabilized by resonance

• Fishhook arrows are used to present possible resonance forms

• Resonance stabilized radicals are more stable than 3˚ radicals

• Vinylic radicals are especially unstable (as with vinyl cations)

• Like ionic mechanisms, radical mechanisms follow patterns

• Radical mechanisms follow SIX key arrow-­‐pushing patterns

1. Homolytic Cleavage: initiated by light or heat

2. Addition to a pi bond

3. Hydrogen abstraction: not the same as proton transfer

5. Elimination: The reverse of addition

6. Coupling: the reverse of homolytic cleavage

• Propagation occurs when radical reacts with a non-­‐radical species,

• Chlorination of methane follows a radical mechanism:

1. INITIATION: chlorine radicals are created

• Propagation is a chain reaction: the product(s) for a later step

• Polychlorination is difficult to prevent

• Radical initiator: possesses a weak bond that cleaves

• Radical inhibitors: react with radicals, and prevent a chain process

• Stabilized radicals and compounds that easily form stabilized

• Hydroquinone undergoes H-­‐abstraction to form a resonance-­‐

Chlorination of ethane to produce ethyl chloride

• In a halogenation reaction, entropy is negligible.

• Only halogenation with Cl2 and Br2 are useful.

• Both chlorination and bromination are exothermic (favored).

• With substrates more complex than ethane, multiple

Hello two monohalogenation

• Chlorine is indiscriminant; significant amount of each product is

Hydrogen abstraction from

• The fact bromination is more regioselective than chlorination can

• Focus on the H abstraction (rate determining) step.

chlorination TS bromination TS

• For bromination, the stability of the

• For chlorination, the stability of the

• 2-­‐chlorobutane will form as a racemic mixture

• In the halogenation of (S)-­‐3-­‐methylhexane, the chirality center is

Hello A racemic mixture will

• H-­‐abstraction of an allylic H results in a resonance-­‐stabilized allylic

• Propagation produces the allylic radical and HBr

• With asymmetric alkenes, a mixture of isomeric products is often

Both allylic posi]ons

• O3 depletion is a serious health and environmental problem.

• Chlorofluorocarbons are believed to be the culprit

• The Cl radicals destroy ozone by the following mechanism

• Cl radicals are formed during propagation, and continue the

• CFC’s have been replaced with hydrofluoroalkanes (HFA’s)

• Autooxidation is the process by which organic compounds react

• The process is generally very slow

The initiation step

• Ethers are particularly susceptible to autooxidation

• Storing sensitive compounds in dark containers prevents light from

• Autooxidation causes the food to become rancid and toxic

• These preservatives are radical inhibitors.

• One molecule of BHT can prevent thousands of autooxidation

• So, inhibitors like BHT are often called antioxidants

• Natural antioxidants prevent the oxidation of cell membranes and

• Vitamin E is hydrophobic, and finds it’s way

• The peroxides initiate a radical mechanism of addition.

• But, the combination of any two radicals constitutes a termination

• Anti-­‐Markovnikov radical addition of HBr is generally spontaneous

• Radical mechanisms follow SIX key arrow-‐pushing patterns

• Propagation occurs when radical reacts with a non-‐radical species,

• Hydroquinone undergoes H-‐abstraction to form a resonance-‐

• 2-‐chlorobutane will form as a racemic mixture

• In the halogenation of (S)-‐3-‐methylhexane, the chirality center is

• H-‐abstraction of an allylic H results in a resonance-‐stabilized allylic

• Anti-‐Markovnikov radical addition of HBr is generally spontaneous

• Diesel: Contains 4-‐20 carbon atoms per molecule. Primarily linear

Weakest C-‐H bond

c. Chlorination of 1,1,1-‐trichloroethane to produce 1,1,1,2-‐

d. Chlorination of 2,2-‐dichloropropane to produce 1,2,2-‐

b. In reality, radical bromination of methane produces many by-‐