CHAPTER 12

HYDROCARBONS

12.2 Alkenes
 Learning Outcomes
At the end of this topic, students should be able to:
a) Describe alkenes as unsaturated
hydrocarbon with the general formula
CnH2n, n≥2.
(b) Draw the structures and name the
compunds according to the IUPAC
nomenclature for:
i) straight chain and branched alkenes
(parent chain ≤ C10)
ii) cyclic alkenes (C3-C6)
iii) simple dienes (C4-C6)
2
 Learning Outcomes
At the end of this topic, students should be able to:
c) Show the preparation of alkenes through:
i) dehydration of alcohols
ii) dehydrohalogenation of haloalkanes
d) Write the mechanism for c(i)
e) State Saytzeff’s Rule.
f) Deduce the major product of elimination
reaction.

3
 Alkenes
- General formula CnH2n , n  2. (it is a functional
group isomerism with cyclic alkane)
- Functional group  ………………………………….
- ……………………… hydrocarbon
- C═C  …… σ bond and …… π bond

A A
C=C
B B

Restricted rotation of carbon-carbon double

bond causes ……………………………. 4
 Alkenes
Cycloalkenes
- General formula …………………..
- Isomeric to ……………………..
Example : C4H6

CH2 CH Functional group

isomerism

CH2 CH

5
 Alkenes
Common Names Of Alkenes
Many older names for alkenes are still in use …
example: CH3

CH2 CH2 CH3 C CH2

CH3
CH2 CH CH3
CH3 C CH CH2
 Alkenes
IUPAC Nomenclature
1. Determine the parent name by selecting the
longest chain that contains the double bond
and change the ending ‘-ane’ in alkane to‘-ene’.
2. When the chain contains more than three carbon
atoms, numbering is needed to indicate the location
of the double bond.
3. The chain is numbered starting from the end closest
to the double bond.
4. Indicate the position of the substituent by the number
of the carbon atoms to which they are attached to.
5. If the structure shows the cis-trans isomerism, label
cis- or trans- at the beginning of the name of the
compound!!
7
 Alkenes
IUPAC Nomenclature
Cl
Try this … 1
CH CH CH3
H3C CH
CH

CH3

CH3

CH CH CH2
H3C CH Br
CH2

8
 Alkenes
IUPAC Nomenclature
Try this … 2
CH3

HC
Br CH3

C C

Br
H3C

9
 Alkenes
IUPAC Nomenclature
5. If more than one double bond present,
change from - ene to :
diene – 2 double bonds
triene – 3 double bonds
CH3

CH C CH3
H3C C CH

Cl
10
 Alkenes
IUPAC Nomenclature
Test Yourself…..1

1.

2.
 Alkenes
IUPAC Nomenclature
Test Yourself…..1
3.
Br

Cl

4.
 Alkenes
IUPAC Nomenclature
Test Yourself…..1
5.
Br

Cl
 Alkenes
IUPAC Nomenclature
Test Yourself…..1
6.

Cl
Cl
Cl
Cl
 Alkenes
IUPAC Nomenclature
6. In Cycloalkenes :
CH3
Number the carbon
atoms with a double Br C CH
bond as 1 and 2, in
the direction that
gives the substituent H2C
CH
encountered first
with a small number.
CH
CH3
 Alkenes
IUPAC Nomenclature
6. In Cycloalkenes :
Cl
Carbon atoms
with a double bond
will be number 1 if it
has substituent on it
 Alkenes
IUPAC Nomenclature
If more than one double bond present,
1. Change from - ene to :
cycloalkadiene – 2 double bonds
cycloalkatriene – 3 double bonds
2. Priorities the numbering to the CLOSEST
double bonds

Br

17
 Alkenes
IUPAC Nomenclature
Try this …

Br

CH3
 Alkenes
IUPAC Nomenclature
Test Yourself…..2
1.

Br

2.

Cl
Br
 Alkenes
IUPAC Nomenclature
Test Yourself…..2

3. Br
Cl

Br
 Alkenes
IUPAC Nomenclature
Test Yourself…..2
4.

Br

I
 Alkenes
IUPAC Nomenclature
Test Yourself…..2
5.
Br

Cl
 Alkenes
IUPAC Nomenclature
Try this …
Br
H3C CH3 CH3
C C C C
H3C
Br Br Br

Cis isomers have …………….. boiling points.

23
 Alkenes
IUPAC Nomenclature
Try this …

Reason :
Cis is a …………… molecular and trans is a
…………………
Cis – isomers have ………………….. Van der
Waals forces, …………… boiling point.
Alkyl group is …………………………………..,

24
CHAPTER 12
HYDROCARBONS

12.2 Alkenes

Moving on …
 Alkenes
Preparations of Alkenes
Two main types of elimination reactions for
preparation of alkenes :
a) Dehydration of alcohols
 loss of ………… from alcohol

b) Dehydrohalogenation of alkyl halide

 loss of ………… from alkyl halide

26
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Elimination of water molecule from alcohol.
Reagent needed – concentrated acid and
heat!!!
H2C CH2 conc. acid (H2SO4 or H3PO4)
H2C CH2 + H2O
H OH heat or 

ethanol ethene

Acidic catalysts.
Catalyst and dehydrating agents can either
be concentrated sulphuric acid (H2SO4) or
phosphoric acid (H3PO4). 27
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Temperature and concentration of acid required to
dehydrate alcohol depend on the structure (class) of
alcohol.

R R R

H C OH R C OH R C OH

H H R

1o alcohol 2o alcohol 3o alcohol

 Alkenes
Preparations of Alkenes

H C OH

1o alcohol
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
The Saytzeff’s Rule
In an elimination reaction, the ………………… is
the ……………….. alkene, commonly the most
highly ………………………………………………….

H3C H H3C H H3C CH3

H H H3C H
C C C C C C
C C C C
H H CH3 H3C CH3 H3C CH3
H H H
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
The Saytzeff’s Rule : example

CH3 CH3
H2SO4 (conc)
H2C CH CH H3C CH CH
H OH H 
butan-2-ol
+ CH3

H2C CH CH2

31
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Reaction mechanism – for major product
Step 1:
Protonation of –OH group
H H
H H
+

H3C  H3C C C O H
C C O H +

H CH3
H CH3 H

-
+ OSO3H
32
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Reaction mechanism – for major product
Step 2:
Formation of carbocation

H H H H
+ O
H3C  H3C C C+ + H
C C O H
H CH3 H
H CH3 H

33
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Reaction mechanism – for major product
Step 3:
Carbocation loses proton, H+. The carbon next to
C+ will donates its proton
Proton that lose will be from the most stable
neighbouring carbon (3o > 2o > 1o)- Saytzeff Rule

H H
H3C C C+

H CH3

carbocation
34
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Reaction mechanism – for major product
Step 3:
HSO4- ion (OSO3H ion) will attack the selected
proton and form H2SO4 once again
The C-C+ bond will become C=C (alkene is formed)
H H H H
H3C C C+ H3C C=C + H2SO 4

H CH3 CH3

35
36
example :

CH3 CH2 CH CH3

 OH
2–butanol 

37
example :

CH3 C CH CH3
+
H
2o carbocation

H
CH3 CH2 CH C H
+
1o carbocation H
38
 Alkenes
Try this …
Dehydration of 2–propanol occurs in 75% H2SO4
at 100oC.
a) Using curved arrows, write all steps in
a mechanism for the dehydration.

b) Explain the essential role performed in

alcohol dehydrations by the acid catalyst.
(Hint: Consider what would have to happen
if no acid were present)

39
CH3—CH—CH3

● O●
● ●
H
propan-2-ol

40
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Rearrangement during Dehydration of Alcohol
Some 1o and 2o alcohol undergo
rearrangement to form a …………………………..
…………………………………………………………..

CH3 H
H2SO4 (concentrate)
H3C C C CH3

CH3 OH
41
 Alkenes

H3C CH3

C C
H3C CH3
CH3 H

+ H3C C C CH2

CH3
42
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Rearrangement during Dehydration of Alcohol

Step 1 and Step 2 are similar to the previous

example.

Step 3 :
- rearrangement occurs.
- The less stable, secondary carbocation
rearrange to form more stable tertiary
carbocation.
43
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Rearrangement during Dehydration of Alcohol

The rearrangement occurs through the

migration of a group from the carbon atom
adjacent to the carbocation.
Because a group shift from the one carbon to
the next, this kind of rearrangement is often
called a 1,2 shift.
- 1,2-methyl shift
- 1,2 –hydride shift
44
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Rearrangement during Dehydration of Alcohol

1,2-CH3 shift

CH3
+
CH3 C CH CH3

CH3

2o carbocation

45
 Alkenes
Preparations of Alkenes
a) Dehydration of alcohols
Rearrangement during Dehydration of Alcohol

1,2-H shift

CH3 C CH CH3
+
CH3

2o carbocation

46
Example 1 :
CH
(a) 3
H C C CH CH
2 3
CH
3
CH3 H
H3 C C C CH3 -H2O
CH3 OH

H C CH
3 3
C C
(b) CH CH
3 3
48
Example 1 :
CH3
CH3
CH3–C—CH–CH3
CH3–C—CH–CH3
CH3OH2
CH3OH +

3,3–dimethyl–2–butanol

49
 H CH3

H C–C–CH–CH3
+
H CH3
3o carbocation

CH3 H

CH3–C C–CH3
+
CH3
3o carbocation

50
 Alkenes
Test yourself … 1

Show how the hydration of alcohol X forms

alkene Y using a 1,2–hydride shift.

OH

CH–CH3 H2SO4 CH2–CH3

+ H 2O

X Y

51
52
 Alkenes
Test yourself … 2
Dehydration of 2–methylcyclopentanol gives a
mixture of three alkenes.
Propose mechanisms to account for these three
products.
CH3 CH3 CH3
H2SO4
+
heat
OH
major minor
CH2

+
minor

53
54
55
56
 Alkenes
Preparations of Alkenes
b) Dehydrohalogenation of alkyl halide
Follow Saytzeff rule !
• Major product - remove H from carbon
with less hydrogen @ H is preferred to
remove from 3o carbon > 2o carbon > 10
carbon.
• Reagent needed – KOH or NaOH, ethanol
(solvent) and heat under reflux
H H KOH / ethanol H H
H C C H H C C H
reflux
H Br
alkyl halide alkene 57
 Alkenes
Preparations of Alkenes
b) Dehydrohalogenation of alkyl halide

H H H H H H
KOH / ethanol
H3C C C C H H3C C C C H
reflux
H Br H H
+ major

H H H
H3C C C C H
H
minor 58
 Alkenes
Preparations of Alkenes
b) Dehydrohalogenation of alkyl halide

Br
KOH, alcohol CH
HC
CH reflux CH
3 3

(major product)

CH
+
CH
2

(minor product)
59
 Alkenes
Preparations of Alkenes
b) Dehydrohalogenation of alkyl halide

CH3 CH3
KOH / ethanol
H3C C CH CH3 H3C C CH CH2
reflux CH3
CH3 Cl

60
 Alkenes
Preparations of Alkenes
b) Dehydrohalogenation of alkyl halide
Draw the structure of the major and minor product(if any) for all of
these molecules below
Br

conc. H2SO4 , ethanol

reflux +
major minor

conc. H2SO4 , ethanol

+
reflux
Cl major minor

conc. H2SO4 , ethanol

+

Br
reflux

major minor 61
 Alkenes
Homework!!
Propose mechanisms for the formation of the
products A,B, C, D, E and F

OH
conc. H2SO4
A B C
(major) + (major)
+ (minor)

conc. H2SO4
D E F
(major) + (minor)
+ (minor)
OH

62