Organic Chemistry

4th Edition Paula Yurkanis Bruice

Chapter 9
Reactions of Alkanes
Radicals

Irene Lee Case Western Reserve University Cleveland, OH 2004, Prentice Hall

Petroleum is a complex mixture of alkanes and cycloalkanes that can be separated by distillation

Alkanes are very unreactive compounds because they have only strong s bonds and atoms with no partial charges However, alkanes do react with Cl2 and Br2

Reaction of Alkane with Cl2 or Br2

Factors that determine product distribution

The rate-determining step of the overall reaction is hydrogen abstraction

Consider the relative stabilities of alkyl radicals,

The stable alkyl radical is formed faster, therefore 2-chlorobutane is formed faster

pg 341 middle

In determining the relative amounts of products obtained, both probability and reactivity should be considered

probability: the number of hydrogens that can be abstracted that will lead to the formation of the particular product

reactivity: the relative rate at which a particular hydrogen is abstracted

The ReactivitySelectivity Principle

A bromine radical is less reactive and more selective than a chlorine radical

Why are the relative rates of radical formation so different between the bromine versus the chlorine radical?

The more reactive a species is, the less selective it will be

What about fluorination and iodination? Alkanes undergo chlorination and bromination, but not iodination Fluorination is too violent of a reaction to be useful

Consider the relative stabilities of radicals

Radical Substitution of Benzylic Hydrogens

The more stable radicals form faster

Because of the reactivity of allylic hydrogens,

a milder brominating reagent can be used

Advantage: the low concentration of Br2 and HBr present cannot be added to the double bond

The allylic radical has two resonance contributors

CH3CH2CH + Br

CH2

CH3CHCH

CH2

CH3CH +

CHCH2

HBr Br2 CH3CH2CH CH2 + CH3CH2CH + Br CH2

Stereochemistry of Radical Substitution Reactions

Why are both enantiomers formed? Consider the first propagation step

What happens if the reactant already has an asymmetric carbon and the radical substitution reaction creates a second asymmetric carbon?

Reactions of Cyclic Compounds

I + Cl2 h + HCl

Br2

Br + HBr

Br + HBr Br + NBS peroxide

Reactions of Cyclopropane

Radical Reactions in Biological Systems

Radicals and Stratospheric Ozone

ozone is a major constituent of smog

ozone shields the Earth from harmful radiation

h O2 O + O2 O O3 + O

Chlorofluorocarbons remain very stable in the atmosphere until they reach the stratosphere
Cl F C Cl F h Cl F C F

Cl

The chlorine radicals are ozone-removing agents

Cl ClO + + O3 O3 ClO + O2

Cl + 2 O2