CHAPTER 5

Hydrocarbons
Alkenes
Part 1
Prepared by: Cik Suhaila
For F5
 Introduction
 Unsaturated hydrocarbons

 General formula : CnH2n (n = 2, 3, 4…)

 Contains at least one C = C double bond
 Functional group : double bond
 Each C atoms ( at C = C) is sp2 hybridised
 Simplest alkene : ethene or ethylene
 Restricted rotation of C = C double bond causes
cis-trans isomerism

2
 Nomenclature
 Alkenes are named according to rules similar to
alkanes
 Change the suffix from “ane” to “ene”
 Ethene and propene usually called by their common
name

Structural formula IUPAC name

CH2 = CH2 Ethene (ethylene)
CH2 = CHCH3 Propene (propylene)
CH2 = CHCH2CH3 1-butene
CH2 = CHCH2CH2CH3 1-pentene 3
 Rules Of IUPAC
1 Identify and name the parent chain
 Select the longest carbon chain that contain double
bond
 Name the alkene with suffix ‘ene’

2 Number the carbon atoms in the main chain

 The longest carbon chain are numbered, beginning
from the end closet to the double bond
 So that, the C=C have the lowest possible number
 Give the position for the double bond
4
 1 2 3 4 5 6

CH3 C CH CH2 CH CH3

CH3 CH3

2,5-dimethyl-2-hexane

3 4 5 6

CH3 CH2 CH CH2 CH2 CH3

2 C CH2
1
CH3

3-ethyl-2-methyl-1-hexene 5
 Exercise
H CH3
CH3CH2CHCH2CH2CH2Br
C C
CH=CH2
ClCH2CH2CH2 CH3
6-chloro-2-methyl-2-hexene 6-bromo-3-ethyl-1-hexene

CH2
CH

CH3 CH2 CH2 CH CH2 CH2 CH2 CH3

3-propyl-1-heptane 6
 If more than 1 double bond present
 Give the position for each double bond
 Change the suffix from “ene” to
 “diene” if there 2 double bond
 “triene” if there 3 double bond

1 2 3 4 1 2 3 4 5 6 7
CH2 CHCH CH2 CH2 CHCH CHCH CHCH3

1,3-butadiene 1,3,5-heptatriene

7
 Cycloalkenes
 Position 1 is always given to one of the C=C
 For single double bond, location didn’t have to be
written

cyclopentane cyclohexane 1,3-cyclohexadiene

8
 For cycloalkenes with substitution

CH3
CH3

1-methylcyclohexene
CH3

1,5-dimethylcyclopentene

CH2 CH3

1-ethyl-1,5-cyclohexadiene 9
 Exercise
CH2 CH3

H 3C CH3 H 3C

3,5-dimethylcyclohexene 1-ethyl-3-methylcyclopropene

3-hexene
4-ethyl-2-methyl-1-hexene10
 Exercise
Cl Cl

C C

H H Cl CH2CH2CH3

cis-1,2-dichloroethene C C

H Cl

trans-1,2-dichloro-1-pentene

11
 Physical Properties Of Alkenes
 Alkenes have similar properties as alkanes
 C2 to C4 : colourless gases at room condition
 C5 to C16 : liquids
 C17 and above : solids

Boiling Point
 Boiling point is directly proportional to the size
of the molecules
 The bigger the size, the higher the boiling point,
due to increase in the Van der Waals attraction
forces in the molecules 12
 Similar to alkanes, branching leads to lower b. p.
 However, alkene has a slightly lower boiling and
melting point than the corresponding alkane

Structural formula Boiling point (oC)

C5H12 (pentane) 36

C5H10 (1-pentene) 30

 Cis-isomers gave higher b. p. compared to trans-

isomer.
Reason: Cis-isomer have greater moment dipole
that leads to stronger Van der Waals forces.
13
 Solubility
 Alkenes are very slightly soluble in water
 However, alkene is more soluble in water than the
corresponding alkane
 Their solubility in water decrease as the number of
carbon atoms increase
 Alkenes are soluble in non-polar solvent such as
tetrachloromethane, ether and toluene

14
 Preparation Of Alkenes
 Simple alkenes are normally obtain from petroleum
 More complex alkenes can be easily prepared in the
laboratory
 2 methods to prepare alkenes are
 Dehydration of alcohol
 Dehydrohalogenation of alkyl halide/
haloalkanes

15
 1 Dehydration Of Alcohols
 Dehydration means elimination of water
 Alcohols reacts with strong acids in presence of heat
to form alkenes and water
 General Rxn

C C H2SO4 (conc) C C + H2O

H OH
alkene
alcohol
16
 Concentration sulphuric acid or phosphoric acid are
often used as reagents for dehydration because
these acids act both as acidic catalysts and as
dehydrating agents.
 Example

H H H H H H
H C C C H H2SO4 (conc) H C C C H
H H OH H
1-propanol 1-propene

+ H2O

17
  Example

CH2 CH2
H
CH2 CH2
H2 C C H2 C C H
OH H2SO4 + H2O
CH2 C (conc) CH2 C
H H
H
cyclohexanol cyclohexene

18
 For some alcohols (C > 3), water molecule can be
eliminated from the adjacent C atoms in more than
one way
 Mixture of alkenes obtained
 Major products can be predict by Saytzeff’s
Rule

Saytzeff’s Rule
The major product is the most stable alkenes.
The most stable is the alkenes that has greater
number of alkyl group bonded to the double bond

19
 For example ; 2-butanol

Adjacent C

H H H H
4 3 2 1
H C C C C H

H H OH H

Use the Saytzeff’s Rule to

predict the major
product 20
 Elimination from H H H H
C2 and C1
H C C C C H + H2O

O
S )
4 H H
H nc
2
1-butene
o
(c
H H H H MINOR
4 3 2 1
H C C C C H
H
2S
H H OH H (co O4
nc
)
H H H H
2-butanol
H C C C C H + H2O
H H
Elimination from 2-butene
C2 and C3
MAJOR 21
 Mechanism Of Dehydration Of Alcohol
Case #1 Mechanism Of Dehydration of 1-propanol
Step 1
 Dehydration of alcohol is initiate by addition of H +
ion from acid (protonation) to –OH of the alcohol.

H H H H H H
protonation
H C C C H + H+ H C C C H
+
H H O-H H H O-H





H
1-propanol Protonated alcohol
22
Step 2
 Loss of a water molecule to form a carbocation
1o
H H H H H H
H C C C H H C C C H
+ +
H H O-H - H2O H H 2o


H 1o carbocation
LESS STABLE

 The less stable primary carbocation rearrange to

form more stable secondary carbocation.
 The arrangement are called 1,2 Hydrogen shift
23
Step 3 – Rearrangement and loss of H+ ion to form
double bond
H H H H H H
1,2 Hydrogen
H C C C H H C C C H
+ shift +
H H H H

10 carbocation 20 carbocation
MORE STABLE
H H H - H+
H C C C H
H Eliminate H+ from
neighboring Carbons
1-propene 24
Case #2 Mechanism Of Dehydration of 2-butanol
Step 1 – Protonation of alcohol
H
CH3 CH2 C CH3 + H+ pro
to nat
ion
O-H


 H

2-butanol CH3 CH2 C CH3

+
O-H


H
Protonated alcohol
25
Step 2 – Loss of a water molecule to form a carbocation
H H
CH3 CH2 C CH3 CH3 CH2 C CH3
+ +
O-H


- H2O
H 2o carbocation
STABLE

No need to do rearrangement because

2o carbocation is already stable in this molecule

26
Step 3 – Loss of H+ ion from neighboring Carbons to
form double bond

H
2o H 1o H - H+ (1o)
CH3 CH2 C CH2
H
1-butene
CH3 CH2 C CH3
+ MINOR PRODUCT

2o carbocation H

- H+ (2o) CH3 CH C CH3

2-butene
MAJOR PRODUCT
27
 In this reaction, 2-butene is a major product while
1-butene is a minor product
 This is because elimination of secondary H atoms is
easier than elimination of primary H atom.

Primary H < Secondary H < Tertiary H

Increasing ease of elimination

28
 Case #3 Dehydration of 3,3-dimethyl-2-butanol
CH3 H
CH2 C C CH3
CH3
CH3 H 2,3-dimethyl-1-butene
CH3 C C CH3 H2SO4
MINOR PRODUCT
(conc)
CH3 OH
CH3
3,3-dimethyl-2-butanol
CH3 C C CH3
CH3
Use Saytzeff’s Rule to 2,3-dimethyl-2-butene
predict the major product 29
MAJOR PRODUCT
 Mechanism of dehydration of 3,3-dimethyl-2-butanol

Step 1 – Protonation of alcohol

CH3 H
pro
CH3 C C CH3 + H + ton
ati
on
CH3 O-H



CH3 H

3,3-dimethyl-2-butanol CH3 C C CH3

+
CH3 O-H


H
Protonated alcohol30
Step 2 – Loss of a water molecule to form a carbocation
2o
CH3 H CH3 H

CH3 C C CH3 CH3 C C CH3

+
+
CH3 O-H CH3 3o


- H2O
H 2o carbocation
LESS STABLE

 Now the rearrangement occur.

 The less stable secondary carbocation rearrange to
form more stable tertiary carbocation.
31
Step 3 – Rearrangement and loss of H+ ion to form
double bond
 The rearrangement occurs through the migration
of methyl group to the adjacent carbon

CH3 H rearrangement CH3 H

CH3 C C CH3 1,2 Methyl CH3 C C CH3
+ shift +
CH3 CH3

20 carbocation 30 carbocation

 The arrangement are called 1,2 Methyl shift

32
 - H+ at C3 CH3
(tertiary C)
CH2 C C CH3
CH3
CH3 H
2,3-dimethyl-2-butene
CH3 C C CH3
+ MAJOR PRODUCT
CH3
CH3 H
30 carbocation
CH2 C C CH3
STABLE
CH3
- H at C1
+

(primary C) 2,3-dimethyl-1-butene
33
MINOR PRODUCT
 2 Dehydrohalogenation Of Alkyl Halide
 Dehydrohalogenation is the elimination of hydrogen
halide (HX) .
 The elimination rxn is achieve by heating haloalkanes
with KOH or NaOH in alcohol
 General Rxn

C C KOH/alcohol C C + HX

H X
alkene
Alkyl halide
34
 Example : 1-chloropropane

H H H H H H
KOH/alcohol
H C C C H H C C C H + HCl

H H Cl H
1-chloropropane 1-propene

 Example : 2-bromo-2-methylbutane
35
 Elimination from H H CH3 H
C2 and C1
H C C C C H
H H
H H CH3 H 2-methyl-1-butene
KOH/alcohol
H C C C C H + HBr MINOR
4 3 2 1 
H H Br H

2-bromo-2-methylbutane H H CH3 H

H C C C C H
Use Saytzeff’s Rule
H H
Elimination from 2-methyl-2-butene
C2 and C3
MAJOR 36
 Example : 2-chloropentane

Cl
KOH/alcohol
CH3-CH-CH2-CH2-CH3

2-chloropentane

MINOR CH2=CH-CH2-CH2-CH3
1-pentene
+
MAJOR CH3-CH=CH-CH2-CH3
2-pentene
Use Saytzeff’s Rule
to predict the major + HCl
product 37
 Mechanism Of Dehydrohalogenation
Of Alkyl Halide
Case #1 Mechanism Of Dehydrohalogenation of
2-chloropentene
Step 1 – Formation of carbocation
 It involves the elimination of X - ion to form carbocation
Cl
+
CH3-CH-CH2-CH2-CH3 CH3-CH-CH2-CH2-CH3

- Cl 20 carbocation
STABLE 38
 Step 2 – Elimination of H+ from adjacent carbon to
Form double bond

Eliminate H+ CH2=CH-CH2-CH2-CH3
from C1
1-pentene

+ MINOR PRODUCT
CH3-CH-CH2-CH2-CH3

20 carbocation

CH3-CH=CH-CH2-CH3
Eliminate H+ 2-pentene
from C3
MAJOR PRODUCT
39
Case #2 Mechanism Of Dehydrohalogenation of
2-bromo-3-methylbutane

Step 1 – Formation of carbocation

2o
H CH3 H H H CH3 H H
H C C C C H H C C C C H
+
H H Br H - Br H H H
3o
2-bromo-3-methylbutane 20 carbocation
LESS STABLE
 Now the rearrangement occur.
40
Step 2 – Rearrangement

H CH3 H H H CH3 H H
1,2 Hydrogen
H C C C C H shift H C C C C H
+ +
H H H H H H

20 carbocation 30 carbocation
LESS STABLE STABLE

41
Step 3 – Elimination of H+ from adjacent carbon to
form double bond
CH3 H H
Eliminate H+ H C C C C H
from C1
H H H
H CH3 H H
2-methyl-1-butene
H C C C C H MINOR PRODUCT
+
H H H
H CH3 H H
30 carbocation H C C C C H
Eliminate H+ H H
from C3 2-methyl-2-butene
MAJOR PRODUCT
42