An Overview of Organic Reactions: Mcmurry Organic Chemistry 6Th E Dition Chapter 5 (C) 2003 1

5.
An Overview of Organic
Reactions
McMurry Organic Chemistry 6th e 1

dition Chapter 5 (c) 2003
Topics to Discuss…
• Kinds of reactions
• How reactions occur
• Radical and polar reactions
• Equilibria, rates and energy changes
• Bond dissociation energy
• Energy diagrams and transition states
• Intermediates

Kinds of Organic Reactions
• Q: What occurs? How does it happen?
• 4 Common patterns:
– Addition reactions
– Elimination reactions
– Substitution
– Rearrangement reactions

Classification of Reactions
• Q: The reaction below is best described
as:
– a. A simple addition reaction
– b. A simple elimination reaction
– c. A simple substitution reaction
– d. A simple rearrangement reaction
CH3 CH3
H 3C O + HBr H3C Br + H2O

H
CH3 CH3

Classification of Reactions
• Q: The reaction below is best described
as:
– a. A simple addition reaction
– b. A simple elimination reaction
– c. A simple substitution reaction
– d. A simple rearrangement reaction
H Br
H
C CH2 + HBr C
CH3
H3C H3C

How Organic Reactions
Occur: Mechanisms
• Q: What is a mechanism?
• Reactions occur in defined steps that…

Steps in Mechanisms
• We classify the types of…
• A step involves either…
• Steps can occur in…
• When several steps occur at the same

time they are…
Types of Steps in Reaction
Mechanisms
• Formation of a covalent bond
• Breaking of a covalent bond
• Oxidation of a functional group
• Reduction of a functional group

Homogenic Formation of a
Bond
• Q: What is homogenic bond formation?

Heterogenic Formation of a
Bond
• Q: What is heterogenic bond formation?

Homolytic Breaking of
Covalent Bonds
• Q: What is homolytic bond breakage?

Heterolytic Breaking of
Covalent Bonds
• Q: What is heterolytic bond breakage?

Indicating Steps in
Mechanisms
• Curved arrows show where…
• Arrow always goes from…
• Arrowheads with a “half” head

(“fish-hook”) indicate…
• Arrowheads with a complete

head indicate…
Radicals
• Alkyl groups are abbreviated “R” for
radical
• A “free radical” is an “R” group on its

own:

Radical Reactions and How
They Occur
• Radicals are highly reactive because…
• Radicals react to complete…
• SUBSTITUTION:
• ADDITION:

3 Steps in Radical
Substitution
• Q: What are the steps involved?
– 1. Initiation
– 2. Propagation
– 3. Termination

Polar Reactions and How
They Occur
• Q: What causes Bond Polarity?
• Q: Why does a Polar Reaction occur?

Electronegativity of Some
Common Elements
• Higher numbers =
• EN __________ as you go ____ and ___ on the periodic table
• Carbon bonded to a more electronegative element has…

Polarizability
• Q: What is Polarizability?
• Polar reactions occur between…
 +C = bound to ______________

 -C = bound to ______________
Generalized Polar Reactions
• Q: What is a typical polar reaction?
– Electrophile
– Nucleophile

Identifying Nucleophilic and
Electrophilic Centers
• Q: Which atom in chloromethane would be
most likely to function as an electrophile?
– a. carbon
– b. chlorine H
– c. hydrogen Cl
C
H
H

Identifying Nucleophilic and
Electrophilic Centers
• Q: Which of the following would you
expect to be the most reactive nucleophile?
– a. Br-
– b. Br+
– c. HBr
– d. Br2

An Example of a Polar
Reaction: Addition of HBr to
Ethylene
• Q: Why does it work?

Br
H

Mechanism
• Q: How does it work?
• Q: Why do we care?

Using Curved Arrows in Polar
Reaction Mechanisms
• Q: What are curved arrows for?
• Q: What do the curved arrows do?
• Q: What do I need to know about

curved arrows?
Rules for Using Curved
Arrows
• Q: What are the rules?

Polar Reaction Mechanisms
• Q: How would you use a curved arrow to
indicate the spontaneous loss of bromide
anion and formation of intermediate
carbocation?
CH3
H3C C Br
CH3

Describing a Reaction:
Equilibria, Rates, and Energy
Changes
• Q: What is equilibrium?
• Q: What is an equilibrium constant?

Equilibria, Rates, and Energy
Changes
• Reactions can go either ___________ or
_____________ to reach equilibrium.
• Q: What can Keq tell us?

Magnitudes of Keq
• Keq > 1 =
• Keq < 1 =
• Keq = 10
• Keq = 0.10
• Overall, the Keq is a…

Free Energy and Equilibrium
• Q: What is Gibbs Free Energy?
• -G =
• +G =

Relationship of Keq and G
• The standard free energy change at 1 atm
pressure and 298 K is Gº
• The relationship between free energy change

and an equilibrium constant is:
 Gº = - RT ln Keq

Changes in Energy at
Equilibrium
• Free energy changes (Gº) can be divided
into:
– ENTROPY: (Sº)
– ENTHLAPY: (Hº)
• Overall relationship: Gº = Hº - TSº

Calculating G and Keq
• Q: What is the value of G at 298K?
– HO- + CH3Cl  CH3OH + Cl-
– Ho = -75 kJ/mol
– So = +54 J/K mol

Calculating G and Keq
• Q: Using the G at 298K, determine the
Keq.
– Keq = e –G/RT
– R = 8.315 X 10-3 kJ/mol K (gas constant)

Bond Dissociation Energies
• Q: What is bond dissociation energy?
• Q: What determines the bond

dissociation energy?
• Changes in bonds can be used to…

Calculating Ho for Reactions

Energy Diagrams and Transition
States
• Energy Diagram:
• Transition state:
• Activation Energy:

Intermediates
• If a reaction occurs in more than one step, it
must…
• These are called…
• Each step has its own…
• The complete diagram for the reaction

shows…
Keq and Reaction Energy
Diagrams

Keq and Reaction Energy
Diagrams
• Q: Draw the reaction energy diagram for
a reaction with Keq = 1. What is the value
of Go in this reaction?
– G = -RT ln Keq, where Keq = 1
– R = 8.315 J/mol K, T = 298K

Formation of a Carbocation
Intermediate
• HBr, a Lewis acid, adds
to the  bond
• This produces an
intermediate with a
positive charge on
carbon - a carbocation
• This is ready to react
with bromide

Carbocation Intermediate
Reactions with Anion
• Bromide ion adds an
electron pair to the
carbocation
• An alkyl halide
produced
• The carbocation is a
reactive intermediate
Reaction Diagram for Addition
of HBr to Ethylene
• Two separate steps,
each with a own
transition state
• Energy minimum
between the steps
belongs to the
carbocation reaction
intermediate.

Biological Reactions
• Reactions in living organisms follow
reaction diagrams too.
• They take place in very controlled
conditions
• They are promoted by catalysts that…
• The catalysts are usually…
• Enzymes provide an alternative
mechanism that is compatible with the
conditions of life
Summary
• Kinds of reactions
• How reactions occur
• Radical and polar reactions
• Equilibria, rates and energy changes
• Bond dissociation energy
• Energy diagrams and transition states
• Intermediates


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5.

McMurry Organic Chemistry 6th e 1

McMurry Organic Chemistry 6th e 2

McMurry Organic Chemistry 6th e 3

H 3C O + HBr H3C Br + H2O

McMurry Organic Chemistry 6th e 4

McMurry Organic Chemistry 6th e 5

• Reactions occur in defined steps that…

McMurry Organic Chemistry 6th e 6

• A step involves either…

• Steps can occur in…

• When several steps occur at the same

• Breaking of a covalent bond

• Oxidation of a functional group

• Reduction of a functional group

McMurry Organic Chemistry 6th e 8

McMurry Organic Chemistry 6th e 9

McMurry Organic Chemistry 6th e 10

McMurry Organic Chemistry 6th e 11

McMurry Organic Chemistry 6th e 12

• Arrow always goes from…

• Arrowheads with a “half” head

• Arrowheads with a complete

• A “free radical” is an “R” group on its

McMurry Organic Chemistry 6th e 14

• Radicals react to complete…

McMurry Organic Chemistry 6th e 15

McMurry Organic Chemistry 6th e 16

• Q: Why does a Polar Reaction occur?

McMurry Organic Chemistry 6th e 17

McMurry Organic Chemistry 6th e 18

• Polar reactions occur between…

 +C = bound to ______________

McMurry Organic Chemistry 6th e 20

McMurry Organic Chemistry 6th e 21

McMurry Organic Chemistry 6th e 22

McMurry Organic Chemistry 6th e 23

McMurry Organic Chemistry 6th e 24

• Q: What do the curved arrows do?

• Q: What do I need to know about

McMurry Organic Chemistry 6th e 26

McMurry Organic Chemistry 6th e 27

• Q: What is an equilibrium constant?

McMurry Organic Chemistry 6th e 28

• Q: What can Keq tell us?

McMurry Organic Chemistry 6th e 29

• Overall, the Keq is a…

McMurry Organic Chemistry 6th e 30

McMurry Organic Chemistry 6th e 31

• The relationship between free energy change

McMurry Organic Chemistry 6th e 32

• Overall relationship: Gº = Hº - TSº

McMurry Organic Chemistry 6th e 34

McMurry Organic Chemistry 6th e 35

• Q: What determines the bond

• Changes in bonds can be used to…

McMurry Organic Chemistry 6th e 36

McMurry Organic Chemistry 6th e 37

McMurry Organic Chemistry 6th e 38