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Organic Reactions
Organic Reactions
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• When two sequential reactions are carried out without
drawing any intermediate compound, the steps are usually
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, not at the same
time.
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Kinds of Organic Reactions
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• Substitution reactions involve bonds: one bond breaks
and another forms at the same carbon atom.
• The most common examples of substitution occur when Z is
a hydrogen or a heteroatom that is more electronegative than
carbon.
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• Elimination is a reaction in which elements of the
starting material are “lost” and a bond is formed.
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• 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.
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• Addition is a reaction in which elements are added to the
starting material.
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• 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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• 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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Classify each of the following as either substitution,
elimination or addition reactions.
a) OH
Br
substitution
b)
addition
c) elimination
OH
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Bond Making and Bond Breaking
• 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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• 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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• Homolysis and heterolysis require energy.
• Homolysis generates uncharged reactive intermediates with
unpaired electrons.
• Heterolysis generates charged intermediates. 14
• To illustrate the movement of a single electron, use a half-
headed curved arrow, sometimes called a fishhook.
• A full headed curved arrow shows the movement of an
electron pair.
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• 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 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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Figure 6.2
Three reactive intermediates
resulting from homolysis and
heterolysis of a C – Z bond
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• Radicals and carbocations are electrophiles because they
contain an electron deficient carbon.
• Carbanions are nucleophiles because they contain a carbon
with a lone pair.
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Heterolytically cleave each of the carbon-hetratom
bonds and label the organic intermediate as a
carbocation or carbanion
a)
OH + OH
carbocation
carbanion
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• Bond formation occurs in two different ways.
• Two radicals can each donate one electron to form a two-
electron 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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• A number of types of arrows are used in describing organic
reactions.
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Use arrows to show the movement of electrons in the
following reactions.
a)
+ N N
N N
b) 2 OH
HO OH
c)
+ Br Br
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Bond Dissociation Energy
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• 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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Which has the higher bond dissociation energy?
a) H-Cl or H-Br
b) H3C SH
H3C OH
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• 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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Bond dissociation energies have some important limitations.
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Calculate H for each of the following reactions, knowing
H of O2 and O-H = 119 kcal/mol, H of C-H = 104 kcal/ml
and H of one C=O = 128 kcal/mol.
a)
CH4 + 2O2 CO2 + 2H2O
Bonds Broken Bonds Formed
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• 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.
• When Keq < 1, equilibrium favors the starting materials (A and B)
and the equilibrium lies to the left as the equation is written.
• For a reaction to be useful, the equilibrium must favor the
products, and Keq > 1.
• The position of the equilibrium is determined by the relative
energies of the reactants and products.
• G° is the overall energy difference between reactants and
products.
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Figure 6.3
Summary of the relationship
between ∆G° and Keq
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• G° is related to the equilibrium constant Keq by the following
equation:
• When Keq > 1, log Keq is positive, making G° negative, and
energy is released. Thus, equilibrium favors the products when
the energy of the products is lower than the energy of the
reactants.
• When Keq < 1, log Keq is negative, making G° positive, and
energy is absorbed. Thus, equilibrium favors the reactants when
the energy of the products is higher than the energy of the
reactants. 34
• 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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• These equations can be used for any process with two states in
equilibrium. As an example, monosubstituted cyclohexanes exist
as two different chair conformations that rapidly interconvert at
room temperature, with the conformation having the substituent
in the roomier equatorial position favored.
• Knowing the energy difference between two conformations
permits the calculation of the amount of each at equilibrium.
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Enthalpy and Entropy
• G° depends on H° and the entropy change, S°.
• Entropy change, S°, is a measure of the change in the
randomness of a system. The more disorder present, the higher
the entropy. Gas molecules move more freely than liquid
molecules and are higher in entropy. Cyclic molecules have
more restricted bond rotation than similar acyclic molecules and
are lower in entropy.
• S° is (+) when the products are more disordered than the
reactants. S° is (-) when the products are less disordered than
the reactants.
• Reactions resulting in increased entropy are favored.
• G° is related to H° and S° by the following equation:
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• This equation indicates that the total energy change is due
to two factors: the change in bonding energy and the
change in disorder.
• 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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• 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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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 energy difference between reactants and products is H°. If
the products are lower in energy than the reactants, the reaction
is exothermic and energy is released. If the products are higher
in energy than the reactants, the reaction is endothermic and
energy is consumed.
• 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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• For the general reaction:
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• 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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Figure 6.4
Some representative
energy diagrams
Example 1
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Figure 6.4
Some representative
energy diagrams
Example 2
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Figure 6.4
Some representative
energy diagrams
Example 3
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Figure 6.4
Some representative
energy diagrams
Example 4
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Figure 6.5
Comparing ∆H° and Ea in two
energy diagrams
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• Consider the following two step reaction:
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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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Kinetics
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• 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.
• A rate equation 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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• A two-step reaction has a slow rate-determining step, and a fast
step.
• In a multi-step mechanism, the reaction can occur no faster than
its rate-determining step.
• Only the concentration of the reactants in the rate-determining
step appears in the rate equation.
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Catalysts
Figure 6.7
The effect of a catalyst
on a reaction
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