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11.

1 Free Radicals
Free radicals form when bonds break HOMOLYTICALLY.

Note the single-barbed or fishhook arrow used to show


the electron movement.

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Klein, Organic Chemistry 1e

11.1 Free Radicals


Recall the orbital hybridization in carbocations and
carbanions.

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Klein, Organic Chemistry 1e

11.1 Free Radicals


Free radicals can be thought of as sp2 hybridized or
quickly interconverting sp3 hybridized.

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Klein, Organic Chemistry 1e

11.1 Free Radicals Stability


Free radicals do not have a formal charge but are
unstable because of an incomplete octet.
Groups that can push (donate) electrons toward the
free radical will help to stabilize it. WHY? HOW?
Consider hyperconjugation.

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Klein, Organic Chemistry 1e

11.1 Free Radicals Stability


Use arguments that involve hyperconjugation and an
energy diagram to explain the differences in bond
dissociation energy (BDE) below.

Practice with CONCEPTUAL CHECKPOINT 11.1.


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Klein, Organic Chemistry 1e

11.1 Free Radicals Resonance


Drawing resonance for free radicals using fishhook
arrows to show electron movement.
Remember, for resonance, the arrows dont ACTUALLY
show electron movement. WHY?
Draw the resonance hybrid for an allyl radical.

HOW and WHY does resonance affect the stability of


the free radical?
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Klein, Organic Chemistry 1e

11.1 Free Radicals Resonance


The benzylic radical is a hybrid that consists of four
contributors.

Draw the remaining contributors.


Draw the hybrid.

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Klein, Organic Chemistry 1e

11.1 Free Radicals Resonance


Stabilization
How does resonance affect the stability of a radical?
WHY?

What is a bigger factor, hyperconjugation or resonance?


Practice with SKILLBUILDER 11.1.
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Klein, Organic Chemistry 1e

11.1 Free Radicals Resonance


Stabilization
Vinylic free radicals are especially unstable.
No resonance stabilization.

What type of orbital is the vinylic free radical located in,


and how does that affect stability?
Practice with SKILLBUILDER 11.2.
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Klein, Organic Chemistry 1e

11.2 Radical Electron Movement


Free radical electron movement is quite different from
electron movement in ionic reactions.
For example, free radicals dont undergo rearrangement.

There are SIX key arrow-pushing patterns that we will


discuss.
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Klein, Organic Chemistry 1e

11.2 Radical Electron Movement


1. Homolytic cleavage, initiated by light or heat:
2. Addition to a pi bond:
3. Hydrogen abstraction (NOT the same as proton
transfer):
4. Halogen abstraction:
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Klein, Organic Chemistry 1e

11.2 Radical Electron Movement


5. Elimination: the radical from the carbon is pushed
toward the carbon to eliminate a group on the
carbon (reverse of addition to a pi bond):

The X group is NOT a leaving group. WHY?

6. Coupling, the reverse of homolytic cleavage:

Note that radical electron movement generally


involves two or three fishhook arrows.
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Klein, Organic Chemistry 1e

11.2 Radical Electron Movement

Note the reversibility of radical processes:

Practice with SKILLBUILDER 11.3.


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Klein, Organic Chemistry 1e

11.2 Radical Electron Movement

Radical electron movement is generally classified as


either initiation, termination, or propagation.
INITIATION
occurs when
radicals are
created.

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TERMINATION
occurs when
radicals are
destroyed.

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Klein, Organic Chemistry 1e

11.2 Radical Electron Movement


PROPAGATION occurs when radicals are moved from
one location to another.

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Klein, Organic Chemistry 1e

11.3 Radical Reactions Chlorination


of Methane
Lets apply our electron-pushing skills to a reaction.

We must consider each pattern for any free radical that


forms during the reaction.

Is homolytic cleavage also likely for CH4?


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Klein, Organic Chemistry 1e

11.3 Radical Reactions Chlorination


of Methane

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Klein, Organic Chemistry 1e

11.3 Radical Reactions Chlorination


of Methane
Why are termination reactions less common than
propagation reactions?

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Klein, Organic Chemistry 1e

11.3 Radical Reactions Chlorination


of Methane
The propagation steps give the net reaction:

1. Initiation produces a small amount Cl radical.


2. H abstraction consumes the Cl radical.
3. Cl abstraction generates a Cl radical, which can go on to
start another H abstraction.

Propagation steps are self-sustaining.


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Klein, Organic Chemistry 1e

11.3 Radical Reactions Chlorination


of Methane
Reactions that have self-sustaining propagation steps
are called CHAIN REACTIONS.
In a chain reaction, the products from one step are
reactants for a different step in the mechanism.
Polychlorination is difficult to prevent, especially when
an excess of Cl2 is present. WHY?

Practice with SKILLBUILDER 11.4.


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Klein, Organic Chemistry 1e

11.3 Radical Reactions Chlorination


of Methane
Draw a reasonable mechanism that shows how each of
the products might form in the following reaction.

Which of the products above are major, and which are


minor?
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Klein, Organic Chemistry 1e

11.3 Radical Reactions Radical


Initiators
An initiator starts a free radical chain reaction

Which initiator above initiates reactions most readily?


WHY?
The acyl peroxide will be effective at 80 C.
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Klein, Organic Chemistry 1e

11.3 Radical Reactions Radical


Inhibitors
Inhibitors act in a reaction to scavenge free radicals to
stop chain reaction processes.
Oxygen molecules can exist in the form of a diradical,
which reacts readily with other radicals. Use arrows to
show the process.

How can reaction conditions be modified to stop oxygen


from inhibiting a desired chain reaction?
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Klein, Organic Chemistry 1e

11.3 Radical Reactions Radical


Inhibitors
Hydroquinone is also often used as a radical inhibitor.

Draw in necessary arrows in the reactions above.

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Klein, Organic Chemistry 1e

11.4 Halogenation Thermodynamics


If we want to determine whether a process is product
favored, we must determine the sign (+/-) for G.

In a halogenation reaction, will H or -TS have a bigger


effect on the sign of G? WHY?

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Klein, Organic Chemistry 1e

11.4 Halogenation Thermodynamics


Because the -TS term should be close to zero, we can
simplify the free energy equation
Considering the bonds that break and form in the
reaction, estimate Hhalogenation for each of the halogens
in the table below.

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Klein, Organic Chemistry 1e

11.4 Halogenation Thermodynamics

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Klein, Organic Chemistry 1e

11.4 Halogenation Thermodynamics


Fluorination is so exothermic that it is impractical. WHY
does that make it impractical?
Iodination is nonspontaneous, so does not favor
products. The reaction is not PRODUCT-FAVORED.

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Klein, Organic Chemistry 1e

11.4 Halogenation Thermodynamics


Consider chlorination and bromination in more detail.

Chlorination is more product-favored than


bromination.
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Klein, Organic Chemistry 1e

11.4 Halogenation Thermodynamics


Which step in the mechanism is the slow step? Which
reaction has a faster rate? Which is more product
favored?
Both steps are exothermic

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First step is endothermic


Second step is exothermic

Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


With substrates more complex than ethane, multiple
MONOHALOGENATION products are possible.

If the halogen were indiscriminant, predict the product


ratio?

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


For the CHLORINATION process, the actual product
distribution favors 2-chloropropane over 1chloropropane.

Which step in the mechanism determines the


regioselectivity?
Show the arrow pushing for that key mechanistic step.
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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


In one reaction, a 1 free radical forms, and in the other, a
2 radical forms.
Is the chlorination process thermodynamically or
kinetically controlled?
WHY?

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


For the BROMINATION process, the product distribution
vastly favors 2-bromopropane over 1-bromopropane.

Which step in the mechanism determines


regioselectivity?
Show the arrow pushing for that key mechanistic step.

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


Kinetic vs. Thermodynamic

Is the key step in the bromination mechanism kinetically


or thermodynamically controlled? WHY?

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


Focus on the H abstraction step, and consider the
Hammond postulatespecies on the energy diagram
that are similar in energy are similar in structure.

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


When the bromine radical abstracts
the hydrogen, the carbon must be
able to stabilize a large partial
radical.
When the chlorine radical abstracts
the hydrogen, the carbon does not
carry as much of a partial radical.

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


Which process is more regioselective? WHY?

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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity

Bromination at the 3 position happens 1600 times


more often than at the 1 position .
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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


Which process is least regioselective? WHY?

What is the general relationship between reactivity and


selectivity? WHY?
Practice with SKILLBUILDER 11.5.
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Klein, Organic Chemistry 1e

11.5 Halogenation Regioselectivity


For the reaction below, draw the structure for EVERY
possible monobromination product.

Rank the products in order from most major to most


minor.
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Klein, Organic Chemistry 1e

11.6 Halogenation Stereochemistry


The halogenation of butane or more complex alkanes
forms a new chirality center.

2-chlorobutane will form as a racemic mixture.


Which step in the mechanism is responsible for the
stereochemical outcome?
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Klein, Organic Chemistry 1e

11.6 Halogenation Stereochemistry


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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Klein, Organic Chemistry 1e

11.6 Halogenation Stereochemistry


Three monosubstituted products form in the
halogenation of butane.

Draw all of the monosubstituted products that would


form in the halogenation of 2-methylbutane including
all stereoisomers.
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Klein, Organic Chemistry 1e

11.6 Halogenation Stereochemistry


In the halogenation of (S)-3-methylhexane, the chirality
center is the most reactive carbon in the molecule.
WHY?

Name the product and predict the stereochemical


outcome.
Practice with SKILLBUILDER 11.6.
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Klein, Organic Chemistry 1e

11.6 Halogenation Stereochemistry


Draw all of the monosubstituted products that would
form in the halogenation below including all
stereoisomers.

Classify any stereoisomer pairs as either enantiomers or


diastereomers.
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Klein, Organic Chemistry 1e

11.7 Allylic Halogenation


When an C=C double bond is present, it affects the
regioselectivity of the halogenation reaction.
Given the bond dissociation energies below, which
position of cyclohexene will be most reactive toward
halogenation?

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Klein, Organic Chemistry 1e

11.7 Allylic Halogenation


When an allylic hydrogen is abstracted, it leaves behind
an allylic free radical that is stabilized by resonance.

Based on the high selectivity of bromination that we


discussed, you might expect bromination to occur as
shown:
What other set of side-products is likely to
form in this reaction? Hint: addition reaction.
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Klein, Organic Chemistry 1e

11.7 Allylic Halogenation with NBS


To avoid the competing halogen ADDITION reaction,
NBS can be used to supply Br radicals.

Show how resonance stabilizes the succinimide radical.


Heat or light INITIATES the process.
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Klein, Organic Chemistry 1e

11.7 Allylic Halogenation with NBS

Propagation produces new Br radicals to continue the


chain reaction.
Where does the BrBr above come from? The amount
of BrBr in solution is minimal, so the competing
addition reaction is minimized.
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Klein, Organic Chemistry 1e

11.7 Allylic Halogenation with NBS


The succinimide radical that is produced in the initiation
step can also undergo propagation when it collides with
an HBr molecule. Show a mechanism.

H-Br

Give some examples of some termination steps that


might occur.
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Klein, Organic Chemistry 1e

11.7 Allylic Halogenation with NBS


Give a mechanism that explains the following product
distribution. Hint: resonance.

Practice with SKILLBUILDER 11.7.

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Klein, Organic Chemistry 1e

11.8 Applications
Atmospheric Chemistry and O3

Ozone is both created and destroyed in the upper atmosphere.


O3 molecules absorb harmful UV radiation.
O3 molecules are recycled as heat energy is released.

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Klein, Organic Chemistry 1e

11.8 Applications
Atmospheric Chemistry and O3

For this process to be spontaneous, the entropy of the


universe must increase.
Heat is a more disordered form of energy than light. WHY?

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Klein, Organic Chemistry 1e

11.8 Applications
Atmospheric Chemistry and O3
O3 depletion (about 6% each year) remains a serious
health and environmental issue.
Compounds that are most destructive to the ozone layer:
1. Are stable enough to reach the upper atmosphere .
2. Form free radicals that interfere with the O3 recycling process.

CHLOROFLUOROCARBONs (CFCs) fit both criteria.

Atmosphere O3 is vital for protection, but what


effect does O3 have at the earths surface?
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Klein, Organic Chemistry 1e

11.8 Applications
Atmospheric Chemistry and O3
CFC substitutes that generally decompose before
reaching the O3 layer include hydrochlorofluorocarbons.

Hydrofluorocarbons dont even form the chlorine


radicals that interfere with the O3 cycle.

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Klein, Organic Chemistry 1e

11.8 Applications
Combustion and Firefighting
Like most reactions, combustion involves breaking
bonds and forming new bonds:
A fuel is heated with the necessary Eact to break bonds (C-C, CH, and O=O) homolytically.
The resulting free radicals join together to form new OH and
C=O bonds.

Why does the process release energy overall?


What types of chemicals might be used in fire
extinguishers to inhibit the process?

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Klein, Organic Chemistry 1e

11.8 Applications
Combustion and Firefighting
Water deprives the fire of the Eact needed by absorbing
the energy .
CO2 and argon gas deprive the fire of needed oxygen.
Halons are very effective fire-suppression agents.

Halons suppress combustion in three main ways.


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Klein, Organic Chemistry 1e

11.8 Applications
Combustion and Firefighting
Halons suppress combustion in three main ways:
1. As a gas, they can smother the fire and deprive it of O2.
2. They absorb some of the Eact for the fire by undergoing
homolytic cleavage.

3. The free radicals produced can combine with C and H free


radicals to terminate the combustion chain reaction.

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Klein, Organic Chemistry 1e

11.8 Applications
Combustion and Firefighting
How do you think the use of halons to fight fires affects
the ozone layer?
FM-200 is an alternative firefighting agent.

Practice with CONCEPTUAL CHECKPOINT 11.18.


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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Autooxidation
Autooxidation is the process by which compounds react
with molecular oxygen.

The process is generally very slow.

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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Autooxidation Mechanism
The mechanism
illustrates the
need for a
more refined
definition of
initiation and
propagation.
HOW?

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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Autooxidation Mechanism
Propagation can be more precisely defined as the steps
that add together to give the NET chemical equation.

Steps in the mechanism that are not part of the NET


equation must be either initiation or termination.
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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Autooxidation
Some compounds such as ethers are particularly
susceptible to autooxidation.

Because hydroperoxides can be explosive, ethers like


diethyl ether must not be stored for long periods of
time.
They should be dated and used in a timely
fashion.
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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Autooxidation
Light accelerates the autooxidation process.
Dark containers are often used to store many
chemicals such as vitamins.
In the absence of light, autooxidation is
usually a slow process.
Compounds that can form a relatively stable
C radical upon H abstraction are especially
susceptible to autooxidation. WHY?
Consider the autooxidation of compounds
with allylic or benzylic hydrogen.

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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Antioxidants
Triglycerides are important to a healthy diet.

Autooxidation can occur at the allylic positions


causing the food to become rancid and toxic.
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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Antioxidants
Foods with unsaturated fatty acids have a short shelf life
unless preservatives are used.

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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Antioxidants
Preservatives can undergo H abstraction to quench the
C radicals that form in the first step of autooxidation.

One molecule of BHT can prevent thousands of


autooxidation reactions by stopping the chain reaction.
How does BHTs structure make it good at taking on a
free radical? Consider resonance and sterics.
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Klein, Organic Chemistry 1e

11.9 Autooxidation vs. Antioxidation


Natural Antioxidants
Vitamins C is hydrophilic.
Vitamin E is hydrophobic.
What parts of the body do these
vitamins protect?
For each vitamin, show its oxidation mechanism, and
explain how that protects the body from autooxidation.

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Klein, Organic Chemistry 1e

11.10 Addition Anti-Markovnikov


Addition
We learned in Chapter 9 that HX will add across a C=C
double bond with anti-Markovnikov regioselectivity
when peroxides are present.

Now that we have discussed free radicals, we can


explain the mechanism for the
anti-Markovnikov addition.
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Klein, Organic Chemistry 1e

11.10 Addition Anti-Markovnikov


Addition
The OO single bond can break homolytically with a
relatively low Eact.

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Klein, Organic Chemistry 1e

11.10 Addition Anti-Markovnikov


Addition
The Br radical reacts to give the more stable C radical.

A 3 radical forms through a lower transition state than


a 2 radical.
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Klein, Organic Chemistry 1e

11.10 Addition Anti-Markovnikov


Addition
Most of the radicals in solution at any given moment
will be Br radical. WHY?

Give some examples of other termination steps that


might occur but that would be less common.
Go back through each step in the mechanism to explain
the H value for each step.
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Klein, Organic Chemistry 1e

11.10 Addition Thermodynamics


Anti-Markovnikov radical addition of HBr is generally
spontaneous (product favored).
Yet, radical addition of HCl and HI are generally
nonspontaneous (reactant favored).

We will examine the thermodynamics of each


propagation step.
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Klein, Organic Chemistry 1e

11.10 Addition Thermodynamics


Explain the sign (+/) for the entropy term in each
process.

Will the entropy change favor products or reactants?


WHY?
The enthalpy change is affected most by the
relative stability of the two radical species.
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Klein, Organic Chemistry 1e

11.10 Addition Thermodynamics

The HI reaction will never favor products. WHY?


How can the temperature be adjusted to favor products
for the HCl and HBr reaction?
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Klein, Organic Chemistry 1e

11.10 Addition Thermodynamics

For the second propagation step, why is the entropy


term approximately zero?
What small differences in entropy between products
and reactants might account for entropy changes being
slightly + or ?
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Klein, Organic Chemistry 1e

11.10 Addition Thermodynamics


`

`
For HCl and HI, the second propagation step will not be
product-favored. WHY?
HBr is the only reactant that favors product formation for both
propagation steps.

Might the overall propagation involving HCl be productfavored if the G of step 1 outweighs the +G
of step 2 ?
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Klein, Organic Chemistry 1e

11.10 Addition Stereochemistry


Addition reactions often form a new chiral center.

Recall that at least one reagent in the reaction must be


chiral for the reaction to be stereoselective.
Predict the product distribution for the reaction below
and explain the stereochemical outcome.

Practice with SKILLBUILDER 11.8.


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Klein, Organic Chemistry 1e

11.11 Radical Polymerization


In Chapter 9, we learned how some ionic
polymerizations occur.
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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Klein, Organic Chemistry 1e

11.11 Radical Polymerization


Radical polymerizations generally proceed through a
chain reaction mechanism.

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Klein, Organic Chemistry 1e

11.11 Radical Polymerization


Radical polymerizations generally proceed through a
chain reaction mechanism.

Note how the sum of the propagation steps


yields the overall reaction.
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Klein, Organic Chemistry 1e

11.11 Radical Polymerization


Radical polymerizations generally proceed through a
chain reaction mechanism.

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11.11 Radical Polymerization


Radical polymerizations generally produce chains of
monomers with a wide distribution of lengths.
How might experimental conditions be optimized to
control the average length of the chains?
Because the mechanism we just learned proceeds
through 1 carbon free radical intermediates, it is
usually not facile.
In Chapter 27, we will discuss specialized catalysts that
can be used to control such polymerization reactions.
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Klein, Organic Chemistry 1e

11.11 Radical Polymerization


Branching is common in some radical polymerizations.

Branching makes polymer materials


more flexible, such as a polyethylene
used for squeeze bottles.
When catalysts are used to minimize
branching, more rigid materials are produced, such as
the material used for squeeze bottle caps.
Why does branching affect rigidity?
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Klein, Organic Chemistry 1e

11.11 Radical Polymerization


Many derivatives of ethylene are also polymerized.

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11.11 Radical Polymerization

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11.12 Radical Petroleum Processes


Recall the CRACKING and REFORMING processes from
chapters 4 and 8.
Crude oil is CRACKED to produce smaller alkanes and
alkenes.

Reforming increases branching. Propose a mechanism.

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Klein, Organic Chemistry 1e

11.13 Synthetic Utility of


Halogenation
Radical chlorination and bromination are both useful
processes.
Recall that bromination is more selective. WHY?

Temperature can be used to help avoid polysubstitution.


HOW?

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Klein, Organic Chemistry 1e

11.13 Synthetic Utility of


Halogenation
Chlorination can be useful with highly symmetrical
substrates.

It is difficult to avoid polysubstitution. WHY?


The synthetic utility of halogenation is limited:
Chlorination is difficult to control.
Bromination requires a substrate with one site that is
significantly more reactive than all others.

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Klein, Organic Chemistry 1e

11.13 Synthetic Utility of


Halogenation
Synthesizing a target molecule from an alkane is
challenging because of its limited reactivity.
Often halogenation is the best option.

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