Chapter 13

Radicals
Reactions of
Alkanes

Paula Yurkanis Bruice

University of California,
Santa Barbara
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Alkanes Are Saturated Hydrocarbons

Saturated hydrocarbons have no double or triple bonds.

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Alkanes Undergo
Chlorination or Bromination

Alkanes are very unreactive compounds because

they have only strong s bonds and atoms with no partial charges
These halogenation reactions require high temperatures or light.
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Heterolytic and Homolytic

Bond Cleavage

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Mechanism for Chlorination

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Use Excess Alkane

to Get Monochlorination

Using excess alkane minimizes dichlorination, trichloriation, etc.

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Mechanism for Bromination

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Relative Stabilities of Radicals

Tertiary > Secondary > Primary

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Alkyl Groups Stabilize Carbocations Better

Than They Stabilize Radicals

carbocation
both electrons are in
the bonding orbital
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radical
one electron is in
the antibonding oribtal

Chlorination

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It is Easier to Make a Secondary Radical

Than a Primary Radical

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Relative Rates of Radical Formation

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Relative Amounts of Products

to determine the product distribution, consider both probability and reactivity

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Halogenation Converts an Alkane

to a Useful Compound

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Relative Rates of Bromination

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Reactivity-Selectivity Principle

a bromine radical is more selective than a chlorine radical

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The H Values for Removing

a Hydrogen Atom from an Alkane

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Why is a Bromine Radical More Selective

than a Chlorine Radical?

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Because Chlorination is Relatively Nonselective,

It is Useful Only When all the Hydrogens Are the Same

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Why Only Chlorination and Bromination?

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Formation of Explosive Peroxides

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Addition of HBr
in the Presence of Peroxide

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Mechanism for the Addition of HBr

in the Presence of Peroxide

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A Carbocation Intermediate is Not Formed,

So a Carbocation Rearrangement Does Not Occur

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Peroxide Effect Occurs Only with HBr

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Why?

because both propagation steps for HBr addition are exothermic

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The Stereochemistry of
Radical Substitution Reactions

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The Stereochemistry of
Radical Addition Reactions

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Why are Both Enantiomers Formed?

the incoming species has equal access to both sides of the plane

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Racemization

A pair of enantiomers is formed if a hydrogen atom

is removed from an asymmetric center.
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An Allylic Radical Has

Two Resonance Contributors

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A Benzylic Radical Has

Five Resonance Contributors

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Relative Stabilities of Radicals

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Benzylic Substitution

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Allylic Substitution

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N-Bromosuccinimide (NBS) is Used

to Brominate Allylic Carbons

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The Mechanism
The reaction takes place in the presence of a low concentration of Br2 and HBr.

How is the required Br2 generated?

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The Resonance Contributors are Not Identical,

So Two Products are Formed

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Addition versus Hydrogen Removal

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Cyclopropane Undergoes
Ring-Opening Reactions to Relieve Strain

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Designing a Synthesis 1

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The Synthesis

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Designing a Synthesis 2

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The Synthesis

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Designing a Synthesis 3

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The Synthesis

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Designing a Synthesis 4

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Retrosynthetic Analysis and Synthesis

retrosynthetic analysis

synthesis

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A Biological Radical Reaction

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The Mechanism for the Oxidation of Fats and

Oils

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A Radical Inhibitor

A radical inhibitor converts a reactive radical to an unreactive radical

or to a compound with only paired electrons.
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Vitamin C and Vitamin E

Vitamin C traps radicals form in aqueous systems (interior of cells, blood plasma).
Vitamin E traps radicals formed in nonpolar systems (cell membranes).
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Ozone Formation

ozone is a major constituent of smog

ozone shields Earth from harmful radiation
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The Ozone Hole

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Chlorofluorocarbons are the Ozone Depleting

Reagents Because They Form Chlorine Radicals

chlorofluorocarbons remain very stable in the

atmosphere until they reach the stratosphere

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The Ozone Depleting Reaction

the chlorine radicals are ozone-removing agents

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