CHAPTER 3:
Unsaturated Hydrocarbon –
Alkenes, Alkynes &
Aromatic
3.1 Alkenes and Alkynes
3.2 Naming Alkenes and Alkynes
3.3 Cis-Trans Isomers
3.4 Addition Reactions
3.5 Polymerization
3.6 Aromatic Compounds
3.7 Properties of Aromatic Compounds
Alkenes are hydrocarbons that H H
contain a carbon-carbon double C C
bond.
H H
CycloAlkenes
Alkenes whose carbon atoms
are joined in rings.
ALKENES CYCLOALKENES
• Unsaturated hydrocarbon
• Contain carbon – carbon double
bonds
• Alkenes
• General formula
Cyclopentene C5H8
•Aliphatic hydrocarbons
Cyclobutene C4H6
Naming Alkenes
We must account for double bond:
1. Longest chain must contain the double bond
2. Number of carbons so that the double bond has the lowest number
3. Indicate the position of the double bond
4. Change ending to - ene
5. Use the same rules for the side chains and halides
• The ending of the alkenes with more than one double bond should be
changed from -ene to:
diene – if there are two double bonds
triene – if there are three double bonds
1 2 3 4
H2 C CH CH CH2 1,3-butadiene
1 2 3 4 5 6 7
H2C CHCH CHCH CHCH3
1,3,5-heptatriene
Naming Cycloalkenes
3 2
4 1
CH3 6-Ethyl-1-methylcyclohexene
5 6
CH2CH3
1) Replace the -ane ending of the cycloalkane
having the same number of carbons by -ene.
2) Number through the double bond in the
direction that gives the lower number to the
first-appearing substituent.
• Number substituted cycloalkenes in the way that gives the
carbon atoms of the double bond the 1 and 2 positions.
• That also gives the substituent groups the lower numbers at
the first point of difference.
1
CH3 6 2
1
5 3
5 2
H3C 4 CH3
4 3
1-methylcyclopentene 3,5-dimethylcyclohexene
Alkene Nomenclature
Write the name in the following order
If more than one substituent attached to main chain number of first
alphabetical substituent:-
use prefixes to indicate multiple identical substituents
repeat for other substituents
CH3 CH2CH3 CH3 CH3
CH3CHCH2CH CHCHCH2CH3 CH3CH2CHCH CHCHCH3
1 2 3 4 5 6 7 8 7 6 5 4 3 2 1
At C4 : double bond, 8-octene At C3 : double bond, 3-heptene
At C2 : substituent, CH3 (2-methyl) At C2 and C5 substituent, CH3 (2-methyl)
At C6 : substituent, CH2CH3 (6-ethyl)
6-Ethyl-2-methyl-4-octene 2,5-Dimethyl-3-heptene
8
Alkene Nomenclature
Newer naming system for alkenes : but this change has not been
widely accepted by the chemical community. However we’ll stay with
older name. But you may occasionally encounter the newer system.
CH3 CH2CH3 CH3 CH3
CH3CHCH2CH CHCHCH2CH3 CH3CH2CHCH CHCHCH3
1 2 3 4 5 6 7 8 7 6 5 4 3 2 1
Older naming system : 6-Ethyl-2-methyl-4-octene 2,5-Dimethyl-3-heptene
Newer naming system : 6-Ethyl-2-methyloct-4-ene 2,5-Dimethylhept-3-ene
9
Exercise: Give IUPAC names for the following compounds
CHCH
3 3 CH2CH2CH3 CH2CH3
H2C CHCHCCH3 CH3CH2C CCH2CH2CH3 HC CCH2CH2CHCH3
CH3 CH3 CH3 CH3
(a) (b) (c)
CH3 CH3
CH3
CH
CH3 CH3
CH3
(d) (e) (f)
a) 3,4,4-trimethylpentene d) 1,2-dimethylcyclohexene
b) 4-methyl-3-propyl-3-heptane/ e) 4,4-dimethylcycloheptene
5-ethyl-4-methyl-4-octane f) 3-isopropylcyclopentene
c) 2-ethyl-1, 5-dimethylhexene/
3-ethyl-6-methyl-2-heptene 10
Exercise : Draw structures to the following IUPAC names
a) 3-Ethyl-2,2-dimethyl-3-heptene
b) 3,4-Diisopropyl-2,5-dimethyl-3-hexene
c) 3-Ethyl-4,4-dimethylcyclopentene
d) 6-Chloro-3,4-dimethylcyclohexene
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• Alkenes nomenclature must specify whether a given
molecule is cis or trans if it is a geometric isomer
However, cis – trans stereoisomerism (geometric isomer) in
alkenes is not possible when :
When one of the doubly bonded carbons bears two identical
substituents
The cis and trans isomers
are different molecules
with different properties.
15
Relative Stabilities of Alkenes
The stability of alkenes depends upon number of
substituents bonded to sp2 carbon
R H R H R R R H R H R R
C C < C C < C C < C C < C C < C C
H H R H H H H R R R R R
The more substituents, the more stable
16
Relative Stabilities of Alkenes
Steric repulsion is responsible for energy differences
among the disubstituted alkenes
H3C H H3C CH3 H3C H
C C > C C > C C
H3C H H H H CH3
1-butene trans 2-butene
C
C C
C
mono-substituted disubstituted
17
Cycloalkene Nomenclature with Cis and Trans
H3CH2CH2C CH3 H3CH2CH2C H
C C C C
H H H CH3
Cis-2-hexene Trans-2-hexene
CH3 CH3
CH2CH3 CH2CH3
Trans-1-ethyl-2-methylcyclopent-1-ene Cis-1-ethyl-2-methylcyclopent-1-ene
18
Cycloalkene Nomenclature with Cis and Trans
How to give a name to the alkenes with more than two
substituents
H3CH2CH2C CH3 H3CH2CH2C H
C C C C
H3C H H3C CH3
Cis-3-methyl-2-hexene Trans-3-methyl-2-hexene
This compound is cis This compound is trans
but the two methyl but the two methyl
groups are trans to each other. groups are cis to each other.
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Physical Properties of Alkenes and Cycloalkenes
20
Reactions of Alkenes
Alkenes are relatively more reactive than alkanes.
The electron-rich double bond is the ‘active site’ or the
functional group of the molecule .
Electrophilic Addition Reactions
An addition reaction is a reaction in which an
unsaturated molecule becomes saturated by the
addition of a molecule across a multiple bond.
21
Reactions of Alkenes
Electrophilic Addition Reactions
1. Catalytic Hydrogenation
2. Halogenation
3. Halohydrin
4. Hydration
5. Hydrohalogenation
C C + X-Y C C
X Y
22
1. Catalytic Hydrogenation of Alkenes
Alkenes and hydrogen react in the presence of a
catalyst to form alkanes.
H H H H
H2
C C H C C H
Ni
H H H H
Ethene Ethane
• Addition of H-H across C=C
• Reduction in general is addition of H2 or its equivalent
• Requires Pt /Pd/Ni/Rh as powders on carbon and H2
• Hydrogen is first adsorbed on catalyst
• Reaction is heterogeneous (process is not in solution)
23
2. Halogenation of Alkenes
Addition of Halogen in inert solvent
Halogens dissolved in an inert solvent such as
carbon tetrachloride, react readily with alkenes at
room temperature and even in the dark.
H H H H
Br2
C C Br C C Br
H H inert solvent
H H
• Bromine and chlorine add rapidly to alkenes to give
1,2-dihalides, a process called halogenation
• F2 is too reactive and I2 does not add
• Cl2 reacts as Cl+ Cl- same goes to Br2
24
2. Halogenation of Alkenes
Addition of Br2 to Cyclopentene
• Addition is exclusively trans
.. .. H Br Br Br
Br
.. Br
..
.. ..
H H
Br H H H
trans-1,2-Dibromo- cis-1,2-Dibromo-
cyclopentane cyclopentane
sole product NOT formed
25
3. Halohydrin of Alkenes
Addition of Halogen in water
• This is formally the addition of HO-X to an alkene to
give a 1,2-halo alcohol, called a halohydrin
• The actual reagent is the dihalogen (Br2 or Cl2 in
water in an organic solvent)
H H H H
Br2
C C HO C C Br
H H H2O H H
Ethene 2-bromoethanol
(Bromohydrin)
26
3. Halohydrin of Alkenes
Chlorine or bromine dissolved water reacts with
alkene to produce halohydrin as the major product.
Br2(aq) + H2O(l) ⇄ HBr(aq) + HOBr(aq)
Note: The red-brown colour of the bromine solution will disappeared.
For asymmetric alkene such as propene, the addition of
bromide ion to the carbon less substituent and addition
of hydroxide ion to the highly substituted carbon
H CH3 H CH3
Br2
C C Br C C OH
H H H2O
H H
27
3. Halohydrin of Alkenes
• Halogen addition in presence of water is regioselective
: Markonikov’s rule
• The electrophile (Cl or Br) adds to the less substituted
end of double bond, and nucleophile (H2O) adds to the
more substituted end
Carbon with more substituted, OH attached
(H3C)2HC H OH Br
Br2
C C (H3C)2HC C C H
H2O
H H H H
3-methylbutene 1-bromo-3-methyl-2-butanol
Carbon with less substituted, Br attached
28
4. Hydration of Alkenes
Addition with acidified water (H3O+) :
Addition of H and OH groups from a water molecule to a
double bond will produce an alcohol. The reaction is
facilitated by using an acid as a catalyst.
H H +
H H
H3O
C C H C C OH
H H H H
Ethene Ethanol
Note: Hydration of alkenes using concentrated H2SO4
followed by hydrolysis, would give the same results.
29
4. Hydration of Alkenes
For asymmetric alkene such as propene, the addition of
hydrogen atom to the carbon less substituent and
addition of hydroxide ion to the highly substituted carbon
H3CH2C H +
OH H
H3O
C C H3CH2C C C H
H H H H
1-butene 2-butanol
30
Mechanism of Hydration of Alkenes
The E+ adds to the
sp2 carbon that H3CH2C H H3CH2C H
H O+ H
bonded to greater C C C+ C H + H2O
numbers of H H
H
H H
hydrogens
The Nu- adds to
H H
carbocation, H3CH2C H
+
H O H
H O H H3CH2C O H
forming a C+ C H
protonated H H C C H
alcohol. H H
Protonated alcohol is
very strong acid, so it HO H
loses a proton, so form H3CH2C C C H + H3O+
final product is alcohol.
S.A.I.S.A.Kadir H H
31
5. Hydrohalogenation
Addition of Hydrogen Halides
Addition reaction of alkenes with hydrogen halides (HX)
form haloalkanes (alkyl halides)
Relative reactivity of HX towards alkenes increases in
the order of HF < HCl < HBr < HI
H H H H
HBr
C C Br C C H
H H H H
Ethene Bromoethane
32
5. Hydrohalogenation
Addition of Hydrogen halides
H H H H
H Br
C C H C C Br
H H CCl4 H H
H Br
Br
aqueous
H
H3CH2C H H Br H
H Br
C C H3C C C C H
H3C H CCl4
H CH3H
33
Mechanism of Hydrohalogenation
• General reaction
mechanism: electrophilic
addition H3C H
H Br
H3C H
C C C+ C H
• Attack of electrophile
H3C H H3C H
(such as HBr) on bond
of alkene 2-methylpropene Carbocation
• Produces carbocation
and bromide ion
• Carbocation is an H3C H -
Br H
Br
electrophile, reacting with C+ C H H3C C C H
nucleophilic bromide ion H3C H CH3H
Carbocation 2-bromo-2-methylpropane
34
Mechanism of Hydrohalogenation
H H
..
.. Br-..
H H H H
H Br ..
C C H C C+ H C C Br
H H CCl4 H H H H
..
.. Br-..
H Br
..
+
Br
aqueous
H H
35
Reactions of Alkenes and Cycloalkenes
If HX prepared in aqueous, the same product also
formed,
Br
CH3 CH3
H Br
H2O
H H
H
1-methylcyclohexene 1-bromo-1-methylcyclohexane
H Br Br
H2O
ethylidenecyclopentane 1-bromo-1-ethylcyclopentane
36
Reactions of Alkenes and Cycloalkenes
• The reaction is successful with HCl as well as HI
• HI is generated from KI and phosphoric acid
H3CH2C H Cl
Br H
HCl
C C H3CH2C C C H
H3C H Ether CH3H
2-methyl-1-butene 2-bromo-2-methylbutane
H3CH2CH2C H I H
C C KI H3CH2CH2C C C H
H H H3PO4 H H
1-pentene 2-iodopentane
37
Carbocation Structure and Stability
• Carbocations are planar and the tricoordinate carbon is surrounded
by only 6 electrons in sp2 orbitals
• The fourth orbital on carbon is a vacant p-orbital
• The stability of the carbocation (measured by energy needed to form
it from R-X) is increased by the presence of alkyl substituents
S.A.I.S.A.Kadir 38
Inductive Stabilization of Cation Species
• In tertiary carbocation, all H3C CH3
alkyl groups stabilize C +
carbocations by releasing
electron density to the CH3
positively charged carbon, Tertiary carbocation
thereby dispersing the CH3 releases electrons, stabilizes carbocation
positive charge.
• However, in secondary H3C CH3
carbocation, only two alkyl C+
groups will releases
H
electron but in the Secondary carbocation
presence of one proton will
withdraws electron from H withdraws electron, destabilizes carbocation
positively charged carbon.
39
Orientation of Electrophilic Addition: Markovnikov’s Rule
• In an unsymmetrical alkene, HX reagents can add in two
different ways, but one way may be preferred over the
other
• If one orientation predominates, the reaction is
regiospecific
• Markovnikov that in the addition of HX to alkene, the H
attaches to the carbon with the most H’s and X attaches to
the other end (to the one with the most alkyl substituents)
• This is Markovnikov’s rule
H Br H H H
CH3CH2CH2CH C HBr CH3CH2CH2CH C H + CH3CH2CH2CH C Br
Ether
H H H
1-pentene 2-bromopentane 1-bromopentane
40
Sole product NOT FORMED
Reactions of Alkenes and Cycloalkenes
• Addition of HBr to 1-pentene
• Regiospecific – one product forms where two are possible
H H
H
CH3CH2CH2CH2 C+ CH3CH2CH2CH C Br
H H
H Primary carbocation 1-bromopentane
HBr NOT FORMED
CH3CH2CH2CH C
Ether Br H
H H
1-pentene CH3CH2CH2C+HCH CH3CH2CH2CH C H
H H
Secondary carbocation 2-bromopentane
Sole product
41
Markovnikov’s Rule
• Addition HBr to 2-methylpropene
• More highly substituted carbocation forms as intermediate rather
than less highly substituted one
• Tertiary cations and associated transition states are more stable
than primary cations
H H H
H
H3C C C+ H3C C C Br
CH3 H CH3 H
H3C H Primary carbocation 1-bromo-2-methylpropene
HBr NOT FORMED
C C H
Ether Br H
H3C H +
H3C C C H
2-methylpropene H3C C C H
CH3 H
Tertiary carbocation CH3 H
2-bromo-2-methylpropane
42
Sole product
Markovnikov’s Rule
• Addition HBr to 2-methyl-2-butene
• If both ends have similar substitution, then not
regiospecific –two products formed
This carbon contains
two alkyl groups H H CH3
CH3
This carbon contains H3C C C Br
one alkyl group H3C C C+
CH3 H CH3 H
H3C CH3 Secondary carbocation 2-bromo-3-methylbutane
C C HBr
H Br H
Ether
H3C H
H3C C+ C CH3 H3C C C CH3
2-methyl-2-butene
CH3 H CH3 H
Tertiary carbocation 2-bromo-2-methylbutane
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Mechanism of Electrophilic Addition:
Rearrangements of Carbocations
• Carbocations undergo structural rearrangements following set
patterns - hydride shifts occur
• Goes to give more stable carbocation
• Can go through less stable ions as intermediates
CH3 Secondary carbocation Tertiary carbocation
H3C CH H CH3 H CH3 H H
C C HBr H3C C C+ C H H3C C+ C C H
Ether
H H H H H H H
3-methyl-1-butene
CH3 Br H CH3 H H
H3C C C C H H3C C C C H
H H H Br H H
2-bromo-3-methylbutane 2-bromo-2-methylbutane
50% 50%
44
Predicting Major and Minor Addition Products
When an HX molecule is added to an unsymmetrical
alkene, two possible products can be formed:
If we do not run the experiment, but still we can predict
the major and minor from two possible products based
on
-Markovnikov’s rule
-Rearrangement of carbocations (Hydride shifts)
H Cl Cl H
H3C
HCl
C CHCH3 H3C C CHCH3 H3C C CHCH3
Ether
H3C CH3 CH3
2-methyl-2-butene 2-chloro-3-methylbutane 2-chloro-2-methylbutane
Minor product Major product
45
Predicting Major and Minor Addition Products
..
.. Cl-..
H ..
H CH3 CH3 H CH3
C C + H C C+ + C+ C H
H Cl
H3C CH3 CH3 CH3 H3C CH3
2-methyl-2-butene 3o carbocation 2o carbocation
CH3 CH3
CH3CH2C CH3 + CH3CH C CH3
Cl Cl H
2-chloro-2-methylbutane 2-chloro-3-methylbutane
Major product Minor product
46
1.3 Alkenes And Alkynes
Exercise 21 : What would the major and minor product
obtained from the addition of HBr to each the following
alkenes?
(b)
(a)
(c) (d)
47
Synthesis of Alkenes via Elimination Reactions
Unsaturation Tests for Alkenes
Alkenes or unsaturated organic compounds may be
identified using simple lab tests
1. Br2 in inert solvent or dilute bromine water are yellow
brown in colour. The solution is decolorised when added to
an alkene (See: Addition reactions with halogens)
2. Reaction with cold, dilute, alkaline KMnO4 (Baeyer’s test)
Alkenes are oxidised readily by the Baeyer’s reagent. The
purple colour of the KMnO4 solution disappears, and a
brown precipitate of Mn(IV) oxide appears. The organic
product is a diol.
H3C OH OH
KMnO4/OH-
C CHCH3 H3C C CHCH3
H3C CH3
2-methyl-2-butene 2-methylbutane-2,3-diol
50
Unsaturation Tests for Alkenes
3. Reaction of Alkenes with hot, acidified KMnO4
Vigorous oxidation of alkenes results in the cleavage of
the double bonds producing ketones, carboxylic acids
or CO2
Potassium permanganate (KMnO4) works if H’s are
present on C=C
In this reaction, the KMnO4 solution is decolourised.
By identifying the products, the position of the double
bond in the alkene can be determined.
51
Unsaturation Tests for Alkenes
Example Reaction of Alkenes with hot, acidified KMnO4
H3C CH2CH3 H CH2CH3
C C C C
H3C H H H
KMnO4/H+ KMnO4/H+
H3C CH2CH3 CH2CH3
C O O C O C O O C
H3C OH OH
52
Unsaturation Tests for Alkenes
4. Ozonolysis
- Alkene is oxidised by ozone in tetrachloromethane to form
unstable ozonide.
- The ozonide is further hydrolysed to produce aldehydes
and/or ketones.
- Ozonolysis is used to identify the location of the C=C.
H3C CH2CH3 O O
O3 H3C CH2CH3
C C C C
H3C H CH2Cl2, -78 o
cold C H3C O H
ozonide
Zn/H2O
H3C CH2CH3
C O + O C + byproduct
H3C H
2-propanone propanal 53
Exercise 22: What product(s) formed when each of
compound treated with the following reagents
i) Cold, dilute alkaline KMnO4
ii) Hot acidified KMnO4
iii) O3/CH2Cl2 (cold) and Zn/H2O
54
