Chapter 5 – An Overview of Organic Reactions

Goals
 To get a basic understanding of reaction mechanisms
 To understand the differences in bond breaking/making and how to note this with the
arrow notation
 To understand polar reactions and mastering arrow notation in such examples.
 Describing a reaction with an energy diagram

Why?
The understanding of organic reactions will help you to critically analyze any organic substrate
that undergoes a reaction of some sort. That is, the general understanding of reactions will allow
you to problem solve reactions in organic chemistry which cannot be memorized since there are
thousands of reactions and hundreds of reagents typically used in organic chemistry.

Additional Resources
Florida Online Practice Problems

Terms
Homolytic, heterolytic, homogenic, heterogenic.

Review

What is a nucleophile and what is an electrophile? How do we use arrow notation to describe a
reaction between the two? Use the following example to explain these questions.

+ HBr

Food For Thought 1

Which of the following is expected to be the worst nucleophile?
1. NH3
2. H2O
3. BH3
4. Ethylene, C2H4.
5. (CH3) 3P

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Types of Reactions in Organic Chemistry

Additions:

What is added?

Substitutions:

What is substituted?

Eliminations:

What is eliminated?

Rearrangements:

Do the reactant and the product have the same molecular formula?

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Food For Thought 2
What kind of reaction is the transformation shown below?

1. an elimination reaction
2. a rearrangement reaction
3. a substitution reaction
4. an addition reaction
5. none of these

How bonds are broken and made

Bond Breaking:

Homolysis (also called hemolytic bond breaking)

Heterolysis (also called heterolytic bond breaking)

Bond Making: Show (with arrow notation) the following:

Homogenic bond making using Br2.

Heterogenic bond making using Br2.

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An Introduction to Radical Reactions

This is common with the halogens, but not limited to this group of elements. More complex
molecules can undergo homolysis. This is discussed more in chapter 7.

The reaction of alkanes with a halogen via a radical reaction pathway. An example of a
substitution reaction.

As noted, this requires heat or light!

Multiple Substitution Reactions versus Selectivity:

 Radical halogenation can yield a mixture of halogenated compounds because all
hydrogen atoms in an alkane are capable of substitution
 In the reaction above all degrees of methane halogenation will be seen

Monosubstitution can be achieved by using a large excess of the alkane:

A large excess of methane will lead to predominantly monohalogenated product and excess
unreacted methane

Mechanism:
The reaction mechanism has three distinct aspects:
Chain initiation, chain propagation and chain termination

1. Chain initiation

Chlorine radicals form when the reaction is subjected to heat or light

Write this balanced chemical equation.

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 2. Chain propagation
 A chlorine radical reacts with a molecule of methane to generate a methyl radical.
 A methyl radical reacts with a molecule of chlorine to yield chloromethane and
regenerate chlorine radical.
 A chlorine radical reacts with another methane molecule, continuing the chain reaction.

Note: a single chlorine radical can lead to thousands of chain propagation cycles

3. Chain termination
 Occasionally the reactive radical intermediates are quenched by reaction pathways that
do not generate new radicals
 The reaction of chlorine with methane requires constant irradiation to replace radicals
quenched in chain-terminating steps

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 Other possible termination possibilities:

Chlorination of Methane: Energy Changes

The chain propagation steps have overall ΔHo= -101 kJ mol-1 and are highly exothermic

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Ignoring the intermediates and transition states, draw a general energy diagram for this reaction:

Food For Thought 3

In the reaction of Cl2 with 2-methylbutane, how many monochlorinated isomers are produced?
1. 2
2. 3
3. 4
4. 5
5. 6

Energy Diagrams

What is an intermediate? What is a transition state? What is a rate dertermining step? These are
a few things that an energy diagram shows.

Review: What is a rate determining step?

Which line in the diagram demonstrates the slowest reaction and which one the fastest?

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The Hammond-Leffler Postulate
 The transition state for an exergonic reaction looks very much like starting material
 The transition state for an endergonic reaction looks very much like product
 Generally the transition state looks most like the species it is closest to in energy

Now consider a polar reaction, the addition of HBr to ethylene, C2H4.

What can be said about the pathway to TS1?

What can be said about the pathway from TS2 to product?

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Hydrogenation: The Function of the Catalyst
The catalyst provides a new reaction pathway with lower ΔG‡ values

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Clicker questions
Think very carefully about problem 4!
4. Consider the reaction profile shown below. If there is a sufficient amount of thermal
energy available to overcome the highest activation energy and sufficient time for all
molecules to do that multiple times, what is the main structure present under such
conditions?

1. A
2. B
3. C
4. D
5. E

5. Which part of the following energy diagram indicates whether the overall reaction is
exergonic or endergonic?

1. I
2. II
3. III
4. IV
5. V

6. On the reaction energy profile shown below, which of the species is the highest energy
intermediate?

1. I
2. II
3. III
4. IV
5. V

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