Organic Chemistry, Second Edition

Janice Gorzynski Smith

University of Hawaii

Chapter 6
Organic Reactions
Prepared by Rabi Ann Musah
State University of New York at Albany

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Understanding Organic Reactions

Chapter 6 Topics:
Writing organic reaction equations and use of arrows.
Types of reactions: substitution, elimination, addition.
Bond breaking:

homolytic and heterolytic

Reactive species: radicals, carbocations and carbanions.

Calculation of H of reaction (enthalpy) from bond
dissociation energies.
Thermodynamics: free energy (G), enthalpy (H), entropy
(S) and the equilibrium constant Keq.
Energy diagrams: single step concerted and multistep.
Kinetics: 1st & 2nd order rates, activation energy, catalysis.
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Understanding Organic Reactions

Writing Equations for Organic Reactions:
Equations for organic reactions are usually drawn with
reagents to the left of a reaction arrow () and products
to the right.
A reagent, the chemical substance with which an organic
compound reacts, may be placed to the left of the arrow
or on the arrow itself.
The solvent and temperature are often omitted but at
times is also placed above or below the arrow.
The symbols h and are placed above or below the
arrow for reactions that require light and heat,
respectively.
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Understanding Organic Reactions

Writing Equations for Organic Reactions:
Figure 6.1 Different ways of writing organic reactions

Here, all are needed together.

Understanding Organic Reactions

Writing Equations for Organic Reactions:
When two sequential reactions are carried out without
drawing any intermediate compound, the steps are
numbered above or below the reaction arrow. This
convention signifies that the first step occurs before the
second step, and the reagents are added in sequence.
Omitting the numbers means they are present together.

Kinds of Organic Reactions

Substitution Reactions:
A substitution is a reaction in which an atom or a group
of atoms is replaced by another atom or group of atoms.
Below, Y replaces Z on a carbon atom.

Kinds of Organic Reactions

Substitution Reactions:
Substitution reactions involve breaking one bond and
forming another at the same carbon atom.
In a nucleophilic attack, the group that departs needs to
have some stability to exist by itself (a weak base).

Kinds of Organic Reactions

Elimination Reactions:
Elimination is a reaction in which elements of the
starting material are lost and a bond is formed.
Water is frequently an eliminated component.

Kinds of Organic Reactions

Elimination Reactions:
In an elimination reaction, two groups X and Y are removed
from a starting material.
Two bonds are broken, and a bond is formed between
adjacent atoms.
The most common examples of elimination occur when X = H
and Y is a heteroatom more electronegative than carbon.

Kinds of Organic Reactions

Addition Reactions:
Addition is a reaction in which elements are added to
the starting material. (Opposite of elimination.)

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Kinds of Organic Reactions

Addition Reactions:
In an addition reaction, new groups X and Y are added
to the starting material. A bond is broken and two
bonds are formed.

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Kinds of Organic Reactions

Addition and Elimination Reactions:
Addition and elimination reactions are exactly
opposite. A bond is formed in elimination reactions,
whereas a bond is broken in addition reactions.

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Understanding Organic Reactions

Bond Making and Bond Breaking are the essence of
chemical reactions:
A reaction mechanism is a detailed description of how
bonds are broken and formed as starting material is
converted into product.
A reaction can occur either in one step or a series of steps.

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Understanding Organic Reactions

Homolytic Bond Breaking:
Regardless of how many steps there are in a reaction, there
are only two ways to break (cleave) a bond: the electrons in
the bond can be divided equally or unequally between the
two atoms of the bond.

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Understanding Organic Reactions

Heterolytic Bond Breaking:

Homolysis and heterolysis require energy.

Homolysis generates uncharged reactive intermediates
with unpaired electrons (radicals).
Heterolysis generates charged intermediates.

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Understanding Organic Reactions

Bond Making and Bond Breaking:
To illustrate the movement of a single electron, use a halfheaded curved arrow, sometimes called a fishhook.
A full headed curved arrow shows the movement of an
electron pair.

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Understanding Organic Reactions

Homolysis:
Homolysis generates two uncharged species with
unpaired electrons.
A reactive intermediate with a single unpaired electron is
called a radical.
Radicals are highly unstable because they contain an atom
that does not have an octet of electrons.

Heterolysis:
Heterolysis generates a carbocation or a carbanion.
Both carbocations and carbanions are unstable
intermediates. A carbocation contains a carbon surrounded
by only six electrons, and a carbanion has a negative charge
on carbon, which is not a very electronegative atom.
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Understanding Organic Reactions

Radicals, Carbocations and Carbanions
Figure 6.2 Three reactive intermediates resulting
from homolysis and heterolysis of a C Z bond

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Understanding Organic Reactions

Radicals, Carbocations and Carbanions
Radicals and carbocations are electrophiles because they
contain an electron deficient carbon (sp2 carbon atoms).
Carbanions are nucleophiles because they contain a
carbon with a lone pair (sp3 carbon atoms).

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Understanding Organic Reactions

Bond Making:
Bond formation occurs in two different ways.
Two radicals can each donate one electron to form a twoelectron bond.
Alternatively, two ions with unlike charges can come
together, with the negatively charged ion donating both
electrons to form the resulting two-electron bond.
Bond formation always releases energy.

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Understanding Organic Reactions

Use of Arrows:
A number of types of arrows are used in describing organic
reactions.

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Understanding Organic Reactions

Bond Dissociation Energy:

The energy absorbed or released in any reaction, symbolized

by H0, is called the enthalpy change or heat of reaction.

Bond dissociation energy is the H0 for a specific kind of

reaction, the homolysis of a covalent bond to form two
radicals.
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Understanding Organic Reactions

Bond Dissociation Energy:
Because bond breaking requires energy, bond dissociation
energies are always positive numbers, and homolysis is
always endothermic.
Conversely, bond formation always releases energy, and thus
is always exothermic. For example, the HH bond requires
+104 kcal/mol to cleave and releases 104 kcal/mol when
formed.

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Understanding Organic Reactions

Bond Dissociation Energy:
Comparing bond dissociation energies is equivalent to
comparing bond strength.
The stronger the bond, the higher its bond dissociation
energy.
Bond dissociation energies decrease down a column of the
periodic table.
Generally, shorter bonds are stronger bonds.

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Understanding Organic Reactions

Bond Dissociation Energy:
Bond dissociation energies are used to calculate the
enthalpy change (H0) in a reaction in which several bonds
are broken and formed.

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Understanding Organic Reactions

Bond Dissociation Energy:

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Understanding Organic Reactions

Bond Dissociation Energy:
Bond dissociation energies have some important limitations.
Bond dissociation energies present overall energy changes
only. They reveal nothing about the reaction mechanism or
how fast a reaction proceeds.
Bond dissociation energies are determined for reactions in
the gas phase, whereas most organic reactions occur in a
liquid solvent where solvation energy contributes to the
overall enthalpy of a reaction.
Bond dissociation energies are imperfect indicators of
energy changes in a reaction. However, using bond
dissociation energies to calculate H gives a useful
approximation of the energy changes that occur when
bonds are broken and formed in a reaction.
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Understanding Organic Reactions

Thermodynamics and Kinetics:
For a reaction to be practical, the equilibrium must favor
products and the reaction rate must be fast enough to form
them in a reasonable time. These two conditions depend
on thermodynamics and kinetics respectively.
Thermodynamics describes how the energies of reactants
and products compare, and what the relative amounts of
reactants and products are at equilibrium.
Kinetics describes reaction rates.
The equilibrium constant, Keq, is a mathematical expression
that relates the amount of starting material and product at
equilibrium.

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Understanding Organic Reactions

Thermodynamic Terms:
G is the term for standard state free energy and represents
the overall energy difference between reactants (R) and
products (P).
H is the term for enthalpy in the standard state.
S is the term for entropy in the standard state.
Standard state conditions have reactants and products at
1 M concentrations or 1 atmosphere pressure.
The overall free energy at any concentrations of R and P is:
G = G + RT ln [P]/[R]
Where R is the constant 8.314 joules /mol-oK and T = oK
(R also = 1.987 cal /mol-oK)
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Understanding Organic Reactions

Thermodynamics:
At equilibrium the overall free energy of reaction is zero.
G = 0
so the equation: G = G + RT ln [P]/[R]
Becomes:

G = - RT ln Keq

This provides a relationship between the standard state free

energy and the equilibrium constant.
For the reaction:
R P
G = -(8.314)(298) ln 1000
G = -17118 cal/mol

Keq = 1000 at 25oC

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Understanding Organic Reactions

Thermodynamics:
The size of Keq expresses whether the starting materials or
products predominate once equilibrium is reached.
When Keq > 1, equilibrium favors the products (C and D) and
the equilibrium lies to the right as the equation is written. This
is a useful reaction.
When Keq < 1, equilibrium favors the starting materials (A and
B) and the equilibrium lies to the left as the equation is
written.
The position of the equilibrium is determined by the relative
energies of the reactants and products.

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Understanding Organic Reactions

Thermodynamics:
Figure 6.3 Summary of the relationship between G and Keq.
Note the use of base a 10 log vs a natural log in these equations.

G = - 2.3 RT log Keq = - RT ln Keq

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Understanding Organic Reactions

Thermodynamics:
Compounds that are lower in energy have increased
stability.
The equilibrium favors the products when they are
more stable (lower in energy) than the starting
materials of a reaction.
Because G depends on the logarithm of Keq, a small
change in energy corresponds to a large difference in
the relative amount of starting material and product at
equilibrium.

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Understanding Organic Reactions

Thermodynamics:

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Understanding Organic Reactions

Thermodynamics:
These equations can be used for any process with two states
in equilibrium. E.g., monosubstituted cyclohexanes exist as
two different chair conformations that rapidly interconvert at
room temperature and equatorial position favored.
Knowing the energy difference between two conformations
permits the calculation of the amount of each at equilibrium.

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Understanding Organic Reactions

Enthalpy and Entropy:
G depends both on H and S.
Entropy change, S, is a measure of the change in the
randomness of a system. The more disorder present, the
higher the entropy.
The value of S is (+) when the products are more
disordered than the reactants and (-) when the products
are less disordered than the reactants.
Reactions resulting in increased entropy contribute to a
negative G.
G is related to H and S by the following equation:

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Understanding Organic Reactions

Enthalpy (H) and Entropy (S) :
The previous equation indicates that the total free
energy change is due to two factors: the change in
bonding energy (H) and the change in disorder (S).
The change in bonding energy can be calculated from
bond dissociation energies.
Entropy changes are important when
The number of molecules of starting material differs
from the number of molecules of product in the
balanced chemical equation.
An acyclic molecule is cyclized to a cyclic one, or a
cyclic molecule is converted to an acyclic one.
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Understanding Organic Reactions

Enthalpy and Entropy:

In most other reactions that are not carried out at high

temperature, the entropy term (TS) is small compared to
the enthalpy term (H0), and therefore it is usually
neglected.

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Understanding Organic Reactions

Energy Diagrams:
An energy diagram is a schematic representation of the
energy changes that take place as reactants are
converted to products.
An energy diagram plots the energy on the y axis versus
the progress of reaction, often labeled as the reaction
coordinate, on the x axis.
The bond energy difference between reactants and
products is H. If the products have lower bond energy
than the reactants, the reaction is exothermic and energy
is released. If the products have higher bond energy
than the reactants, the reaction is endothermic and
energy is consumed.
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Understanding Organic Reactions

Energy Diagrams:
A diagram can also be made by plotting free energy.
Then energy difference between reactants and products
is G. If the products are lower in energy than the
reactants, the reaction is exergonic and energy is
released. If the products are higher in energy than the
reactants, the reaction is endergonic and energy is
required.
The unstable energy maximum as a chemical reaction
proceeds from reactants to products is called the
transition state. The transition state species can never
be isolated.
The energy difference between the transition state and
the starting material is called the energy of activation,
Ea.

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Understanding Organic Reactions

Energy Diagrams:
For the general reaction:

The energy diagram would be shown as:

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Understanding Organic Reactions

Energy Diagrams:
The energy of activation is the minimum amount of energy
needed to break the bonds in the reactants.
The larger the Ea, the greater the amount of energy that is
needed to break bonds, and the slower the reaction rate.
The structure of the transition state is somewhere between
the structures of the starting material and product. Any
bond that is partially formed or broken is drawn with a
dashed line. Any atom that gains or loses a charge contains
a partial charge in the transition state.
Transition states are drawn in brackets, with a superscript
double dagger ().

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Understanding Organic Reactions

Energy Diagrams:
Example 1

Figure 6.4 Some

Representative
energy diagrams

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Understanding Organic Reactions

Energy Diagrams:
Example 2

Figure 6.4 Some

Representative
energy diagrams

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Understanding Organic Reactions

Energy Diagrams:
Example 3

Figure 6.4 Some

Representative
energy diagrams

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Understanding Organic Reactions

Energy Diagrams:
Example 4

Figure 6.4 Some

Representative
energy diagrams

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Understanding Organic Reactions

Energy Diagrams:
Figure 6.5 Comparing H and Ea in two energy diagrams

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Understanding Organic Reactions

Energy Diagrams:
Consider the following two step reaction:

An energy diagram must be drawn for each step.

The two energy diagrams must then be combined to form
an energy diagram for the overall two-step reaction.
Each step has its own energy barrier, with a transition state
at the energy maximum.
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Understanding Organic Reactions

Energy Diagrams:

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Understanding Organic Reactions

Energy Diagrams:

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Understanding Organic Reactions

Energy Diagrams:

Figure 6.6 Complete energy diagram for

the two-step conversion of

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Understanding Organic Reactions

Kinetics:
Kinetics is the study of reaction rates.
Recall that Ea is the energy barrier that must be exceeded
for reactants to be converted to products.

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Understanding Organic Reactions

Kinetics:
The higher the concentration, the faster the rate.
The higher the temperature, the faster the rate.
G, H, and Keq do not determine the rate of a reaction.
These quantities indicate the direction of the equilibrium
and the relative energy of reactants and products.
A rate law or rate equation shows the relationship between
the reaction rate and the concentration of the reactants. It is
experimentally determined.

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Understanding Organic Reactions

Kinetics:
Fast reactions have large rate constants.
Slow reactions have small rate constants.
The rate constant k and the energy of activation Ea are
inversely related. A high Ea corresponds to a small k.
A rate equation contains concentration terms for all
reactants in a one-step mechanism but contains
concentration terms for only the reactants involved in the
rate-determining step in a multi-step reaction.
The order of a rate equation equals the sum of the
exponents of the concentration terms in the rate equation.

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Understanding Organic Reactions

Kinetics:
A two-step reaction has a slow rate-determining step,
and a fast step.
The reaction can occur no faster than its slow step.
Only the concentration of the reactants in the ratedetermining step appears in the rate equation.

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Understanding Organic Reactions

Catalysts:
Some reactions do not proceed at a reasonable rate unless
a catalyst is added.
A catalyst is a substance that speeds up the rate of a
reaction. It is recovered unchanged in a reaction, and it
does not appear in the product.
Figure 6.7 The effect of a catalyst on a reaction

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Organic Chemistry, Second Edition

Janice Gorzynski Smith
University of Hawaii

End Chapter 6
Prepared by Rabi Ann Musah
State University of New York at Albany

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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