CHAPTER 5
Organic Reactions
Reaction Pathways and mechanisms
Most organic reactions proceed by a defined
sequence or set of steps. The detailed pathway
which an organic reaction follows is called a
mechanism.
Knowing a reaction mechanism is very valuable
information. It allows the chemist to predict what
products will be formed when a chemical reaction
occurs.
The organic chemist can use this information to
modify compounds and to synthesize new
compounds with certain desired characteristics.
Diagram of common organic
reactions
.
Diagram of common organic
reactions
categories of organic reactions
There are so many types of organic
reactions. Were going to focus on just a
few.
Addition Reactions
Substitution Reactions
Elimination Reactions
Oxidation Reduction Reaction
Steps in Mechanisms
We classify the types of steps in a sequence
A step involves either the formation or
breaking of a covalent bond
Steps can occur in individually or in
combination with other steps
When several steps occur at the same time
they are said to be concerted
Types of Steps in Reaction Mechanisms
Bond formation or breakage can be symmetrical
or unsymetrical
Symmetrical- homolytic
Unsymmetrical- heterolytic
Indicating Steps in Mechanisms
Curved arrows indicate
breaking and forming of bonds
Arrowheads with a half head
(fish-hook) indicate
homolytic and homogenic
steps (called radical
processes)
Arrowheads with a complete
head indicate heterolytic and
heterogenic steps (called
polar processes)
8
I- Addition Reactions
In alkenes and alkynes
In addition reactions,
reactants are added to
the carbon atoms in
the double or triple
bond.
The double or triple
bond is easily broken,
since it is highly
reactive.
1- Hydrogenation
(addition of Hydrogen)
In hydrogenation,
Hydrogen atoms add to the carbon atoms of a double bond or
triple bond.
converts unsaturated molecule to saturated
alkene or alkyne + H2 alkane
A catalyst such as Pt or Ni is used to speed up the reaction.
Unsaturated vegetable oils reduced to produce saturated fats used
in margarine and cooking products
H2C CH2 + H2
HC CH + 2H2
Pt
Ni
H H
H2C CH2
H H
HC CH
H H
2- Hydration
(addition of water H2O)
an acid H+ catalyst is required.
water (HOH) adds to a double bond.
an H atom bonds to one C in the double bond.
an OH bonds to the other C.
H OH
H+
CH3CH=CHCH3 + HOH
CH3CHCHCH3
Hydration
When hydration occurs with a double bond that has
an
unequal number of H atoms,
the H atom bonds to the C in the double bond
with the more H.
the OH bonds to the C in the double bond with
the fewer H atoms.
OH H
H+
CH3CH=CH2 + HOH
CH3CHCH2
3- Halogenation
In Halogenation,
halogen atoms add to the carbon atoms
of double bond or triple bond.
Addition of Br2 and Cl2 to alkenes to yield
1,2-dihalides
A colour test for c=c Bond
Br
C C
+ Br2
C C
Br
Halogenation
4- Hydrohalogenation
In hydrohalogenation,
the atoms of a hydrogen halide add
to the carbon atoms of a double bond
or triple bond.
Br H
CH3 CH=CH2
Propene
+ HBr
H Br
CH3 CH-CH2 + CH3 CH-CH2
2-Bromopropane 1-Bromopropane
(not observed)
Markovnikovs Rule
In the addition of HX, H2O, or ROH to an alkene, H
adds to the carbon of the double bond having the
greater number of hydrogens.
Substitution Reactions
In a substitution reaction, one atom or
group of atoms, takes the place of another
in a molecule
Examples
CH3CH2Br + KCN CH3CH2CN + KBr
(CH3)3CCl + NaOH (CH3)3 COH + NaCl
18
Nucleophilic Substitution
A nucleophile is a molecule or ion that has a high
electron density.
It is attracted to atoms in molecules with a lower
electron density.
It may replace another group in an organic
molecule.
The molecule to which the nucleophile is
attracted is called the substrate
The group that the nucleophile replaces is called
the leaving group
These reactions are known as nucleophilic
substitutions.
19
Nucleophilic Substitution
One covalent bond is broken as a new
covalent bond is formed
The general form for the reaction is
Nu:- + R-X R-Nu +
X:
Nucleophile
Substrate
Product
Leaving group
20
Nucleophilic Substitution
Nu:- + R-X R-Nu +
X:
The bond to the leaving group is broken
The leaving group takes both electrons that
formed the bond with it
The nucleophile provides the electrons to form
the new bond
Nucleophile
Substrate
Product
Leaving group
21
Nucleophilic Substitution
Alkyl halides commonly undergo nucleolophilic
substitution reactions. The nucleophile displaces
the halide leaving group from the alkyl halide.
There are two common ways for nucleophilic
substitutions to occur. They are known as S N1
and SN2.
Nucleophile
Substrate
Product
Leaving group
22
Examples of Nucleophilic
Substitutions
Nucleophilic substitutions may be SN1 or SN2
23
Nucleophilic Substitution
Bimolecular or SN2
A reaction is bimolecular when the rate depends on both
the concentration of the substrate and the nucleophile.
SN2 mechanisms occur most readily with methyl
compounds and primary haloalkanes SN2 reaction
Substitution, Nucleophilic, Bimolecular.
Essential features of the SN2 Reaction
Takes place in a single step without intermediates
Incoming nucleophile reacts with the alkyl halide or (the
substrate) from a direction opposite the group that is displaced
(the leaving group)
24
The SN2 Reaction
The mechanism of the SN2 reaction
when (S)-2-bromobutane reacts with
OH to give (R)-butan-2-ol
The reaction takes place in a single
step
Incoming nucleophile approaches
from a direction 180 away from the
leaving halide ion, thereby inverting
the stereochemistry at carbon
Substitution, Nucleophilic, Bimolecular
SN2
Nuc :
C X
Nuc
transition state
Nuc C
+X
An Example of a SN2
Mechanism
The nucleophilic substitution of ethyl bromide is shown
above. This reaction occurs as a bimolecular reaction.
The rate of the reaction depends on both the
concentration
of both the hydroxide ion and ethyl bromide
This is a one step process since both
the nucleophile and the substrate
must be in a rate determining step.
27
Carbocations
Carbocation: a species
in which a carbon atom
has only six electrons in its
valence shell and bears
positive charge
Carbocations are
classified as 1, 2, or
3 depending on the
number
of
carbons
bonded to the carbon
bearing the positive
charge.
electrophiles; that is,
they
are
electronloving.
Lewis acids.
Order of stability:
Nucleophilic
Substitution
Unimolecular or SN1
A unimolecular reaction occurs when
the rate of reaction depends on the
concentration of the substrate but not
the nucleophile.
A unimolecular reaction is a two step
process since the subtrate and the
nucleophile cannot both appear in the
rate determining step
SN1 mechanisms occur most readily
with tertiary haloalkanes and some
secondary haloalkanes.
29
The SN1 Reaction
Unimolecular nucleophilic substitution reaction
Mechanism of
the SN1
reaction of 2bromo-2methylpropane
with H2O
involves three
steps
The first step
spontaneous,
unimolecular
dissociation
of the alkyl
bromide to
yield a
carbocation
SN1 mechanism
1st step is rate determining
SN1 and SN2 Reactions
SN1
SN2
=k[RX]
=k[RX][Nuc:-]
Carbocation
intermediate?
Yes
No
Stereochemistr
y
mix
Inversion of
configuration
Rearrangemen
t
~H, ~ CH3
possible
No
rearrangement
s
Rate
32
Radical Reactions
Radicals react to complete electron octet of
valence shell
A radical can break a bond in another
molecule and abstract a partner with an
electron, giving substitution in the original
molecule
A radical can add to an alkene to give a new
radical, causing an addition reaction
33
Steps in Radical Substitution
Three types of steps
Initiation homolytic formation of two reactive
species with unpaired electrons
Example formation of Cl atoms form Cl2 and
light
Propagation reaction with molecule to generate
radical
Example - reaction of chlorine atom with
methane to give HCl and CH3.
34
Free Radical Substitutions
Many organic molecules undergo
substitution reactions.
In a substitution reaction one atom or group
of atoms is removed from a molecule and
replaced with a different atom or group.
Example:
Cl2 + CH4 CH3Cl + HCl
35
Three Basic Steps in a
Free Radical Mechanism
Chain initiation
The chain is initiated (started) by UV light
breaking a chlorine molecule into free radicals.
Cl2 2Cl.
Chain propagation reactions
These are the reactions which keep the chain
going.
CH4 + Cl. CH3. + HCl
CH3. + Cl2 CH3Cl + Cl
Chain termination reactions
These are reactions which remove free radicals
from the system without replacing them by
new ones.
36
.
Free Radical Mechanism-The
Initiation Step
The ultraviolet light is a source of energy that causes
the chlorine molecule to break apart into 2 chlorine
atoms, each of which has an unpaired electron
The energies in UV are exactly right to break the
bonds in chlorine molecules to produce chlorine
atoms.
37
Homolytic Fission
Free radicals are formed if a bond
splits evenly - each atom getting
one of the two electrons. The name
given to this is homolytic fission.
38
Free Radical Propagation
The productive collision happens if a chlorine radical
hits a methane molecule.
The chlorine radical removes a hydrogen atom from the
methane. That hydrogen atom only needs to bring one
electron with it to form a new bond to the chlorine, and
so one electron is left behind on the carbon atom. A new
free radical is formed - this time a methyl radical, CH 3 .
39
Free Radical Propagation II
If a methyl radical collides with a chlorine
molecule the following occurs:
CH3. + Cl2 CH3Cl + Cl.
The methyl radical takes one of the chlorine
atoms to form chloromethane
In the process generates another chlorine free
radical.
This new chlorine radical can now go through
the whole sequence again, It will produce yet
another chlorine radical - and so on and so on.
40
Termination Steps
The free radical propagation does not
go on for ever.
If two free radicals collide the
reaction is terminated.
2Cl. Cl2
CH3. + Cl . CH3Cl
CH3 . + CH3. CH3CH3
41
Exercise
Write the steps in the free radical mechanism
for the reaction of chlorine with methyl
benzene. The overall reaction is shown below.
The methyl group is the part of methyl
benzene that undergoes attack.
42
Solution
Initiation
Cl2 2Cl.
Propagation
Termination
2Cl. Cl2
43
Electrophilic Addition
Addition Mechanisms
Electrophilic addition occurs in reactions
involving containing carbon-carbon double
bonds - the alkenes.
An electrophile is a molecule or ion that is
attracted to electron-rich regions in other
molecules or ions.
Because it is attracted to a negative
region, an electrophile carries either a
positive charge of a partial positive charge
45
Electrophilic Addition II
Electrophilic addition occur in molecules where there are delocalized
electrons. The electrophilic addition to alkenes takes the following
general form:
46
Electrophilic Addition II
The electrophilic addition of alkanes occurs in two stages
First there is the formation of a carbocation
Followed by the attack the chloride ion to form the addition product
47
Markovnikoffs Rule
Actually there are two possible carbocations that could be formed. In may
cases this would result in two possible products. However only one form is
preferred
Birds of a feather flock together!
The hydrogen ion will tend to migrate to the side with the
greater number of hydrogen atoms. This preference is known
as Markovnikoffs Rule.
48
Electrophilic Additions
An addition reaction is a reaction in which two
molecules join together to make a larger
molecule. There is only one product. All the
atoms in the original molecules are found in
the single product molecule.
An electrophilic addition reaction is an addition
reaction which happens because what we
think of as the "important" molecule is
attacked by an electrophile. The "important"
molecule has a region of high electron density
which is attacked by something carrying some
degree of positive charge.
49
Exercise
Write a mechanism for the electrophilic addition
of HBr to 1-butene.
50
Solution
Write a mechanism for the electrophilic addition
of HBr to 1-butene.
Solution
51
Condensation Reactions
The condensation of an acid and an alcohol
results in the formation of an ester and water.
The carbon chain from the alcohol is attached to the single
bonded oxygen of the acid. The hydrogen lost from the acid
and the OH from the alcohol combine to form a water
molecule.
52
Exercises Condensation
Reactions
Write chemical reactions for the
following esterification reactions:
1.
Ethanol and ethanoic acid
2.
Methanol and butanoic acid
3.
2-Pentanol and ethanoic acid
4.
Methanol and 2 hydroxybenzoic acid
5.
Ethanoic acid and 2-hydroxybenzoic acid
53
Solutions to exercises
54
Elimination Reactions
55
Elimination Reactions
An elimination reaction is a type of
organic reaction in which two
substituents are removed from a
molecule in either a one or two-step
mechanism
In most organic elimination reactions
the unsaturation level of the
molecule increases.
56
Elimination Reactions
Elimination reactions may be
either:
------ Unimolecular (Designated E1)
Two steps. The reaction rate depends on the
concentration of the substrate
------ Bimolecular (Designated E2)
One step. The reaction rate depends on the
concentration of both the substrate and
the other reacting species
57
E1Unimolecular
Elimination
Occurs in two steps
Reaction rate depends primarily on
the concentration of the substrate
58
E1 Unimolecular
elimination
Occurs in two steps: First there is the
formation of the intermediate and then the
formation of the C=C.
Occurs in tertiary and secondary
haloalkanes.
59
E2 Bimiolecular Elimination
Reaction occurs in essentially one
rate determining step
Reaction rate depends on the
concentration of both reactants
60
Example of E2
A strong base is used to remove a hydrogen atom
and a bromine atom from the haloalkane to form
the unsaturated alkene.
Occurs in primary haloalkanes
61
Example of E2
A strong base is used to remove a hydrogen atom
and a bromine atom from the haloalkane to form
the unsaturated alkene.
Occurs in primary haloalkanes
62
Electrophilic Substitution
The displacement reactions of the alkyl halides do
not usually work for aromatic (aryl) halides unless
a halogen is part of a side chain.
A halogen atom held to a double bonded carbon
atom is usually rather unreactive, Likewise a
halogen atom attached to a benzene ring is very
stable and unlikely to react.
Most aromatic substitution reactions proceed by a
mechanism known as electrophilic substitution
63
Electrophilic Substitution
An example of an electrophilic substitution is
the reaction of chlorine with a benzene ring.
The overall reaction is
The mechanism for this reaction involves 3 steps
64
Electrophilic Substitution
-3 Steps
The initial step is the formation of the electrophile. A
catalyst may be required.
FeCl3 + Cl2
FeCl4- +
Cl+
The second step is the attachment of the electrophile
to the benzene ring forming the carbocation.
The final step is the loss of hydrogen to form the product.
65
Electrophilic Substitutions
The delocalized electrons found in the benzene ring are
a source of electrons for electrophilic substitutions.
The reactivity of the benzene ring is related to the kind
of substituents attached to the ring.
For example:
Methyl benzene reacts much more rapidly with sulfuric
acid than benzene. The presence of the methyl group
attached to the ring changes the overall electron
density of the ring.
The methyl group in essence increases the electron
density of the ring.
Substances that increase the overallelectron density
fothe ring are called activators
66
Ring Substitution
The type of substituent on the ring influences where the
substitution will occur.
Case 1
The presence of the methyl group results in the
attachment of the sulfonate group at the second
and fourth carbons. It is known as an ortho/para
director.
67
Ring Substitution
Case 2
The presence of the presence of a carboxyl group
on the ring causes the chlorine to attach at
the third position. It is called a meta director
68
Ring Substitution
Certain groups to the benzene ring cause new groups
to attach at carbons 2 and 4. They are called
ortho/para directors. Other groups cause the new
group to attach at carbons 3 and They are known as
meta directors
69
Ring Activation
When certain groups are attached to a
benzene ring they tend to push electrons to
the ring.
The substituted benzene ring is more reactive
than benzene itself
These groups are known as ring activators
70
Ring Deactivation
When certain groups are attached to a
benzene ring they tend to pull electrons from
the ring.
The substituted benzene ring is less reactive
than benzene itself
These groups are known as ring deactivators
71
Electrophilic Substitution
Summary
72
Exercises
Propose a mechanism and
determine the products for the
reaction of
73
