CHAPTER 3: UNSATURATED HYDROCARBON

ALKENES

Unsaturated Hydrocarbon
Hydrocarbons that do not contain the maximum
amount of hydrogen
NOT all carbon atoms have four single covalent
bonds
One or more double bonds or triple bonds
between carbon atoms
Alkenes
hydrocarbons that contain double covalent
bonds
General formula for alkenes with one double
bond is CnH2n

Properties of Alkenes
Alkenes are nonpolar
show trends in properties similar to those of alkanes in
boiling points and physical states.
H2
H
H
H
H
EX:H C
C
C
C
C
C
3

C
CH3

C
H2

C
CH3

C
H2

CH2

CH3

-farnesene, a solid at room temperature, is found in

the natural wax covering of apples

Systematic Names of Alkenes

Rules similar to naming alkanes
parent hydrocarbon
longest continuous chain of carbon atoms that
contains the double bond
H2C
H2C

CH3
H2 H2
C
C

H2C
CH3

not:

H2C

pentene

CH3
H2 H2
C
C

hexane

Number so the double bond has the lowest

number
H2C

H2C

CH3
H2 H2
C
C

2 3 4
1-pentene

CH3

CH3

IUPAC RULES
RULE 1. Select the longest continuous carbon chain that
contains a double bond.

This chain
contains 6
carbon atoms

RULE 2. Name this compound as you would an alkane,

but change ane to ene for an alkene.

This chain
contains 8
carbon atoms

Nameisthe
This
theparent
longest
continuous octene.
compound
chain.
Select it as the parent
compound.

RULE 3. Number the carbon chain of the parent

compound starting with the end nearer to the
double bond. Use the smaller of the two
numbers on the double-bonded carbon to
indicate the position of the double bond. Place
this number in front of the alkene name.

IUPAC RULES
This end of the chain is closest to the double
bond. Begin numbering here.

IUPAC RULES
The name of the parent compound is
1-octene.

5
6
7

RULE 4. Branched chains and other groups are

treated as in naming alkanes. Name the
substituent group, and designate its position on
the parent chain with a number.

IUPAC RULES
The
is attached to carbon 4.
Thisethyl
is an group
ethyl group.
4

5
6
7

4-ethyl-1-octene

 A compound with more than one double bond.

- Two double bond: diene
- Three double bond: triene
- Four double bond: tetraene
* Numbers are used to specify the locations of the double
bonds.
1

CH2 C
H

C CH2
H

CH3 C C
H H

IUPAC names: 1,3-butadiene

new IUPAC names: buta-1,3-diene
1

4
6

IUPAC names: 1,3, 5, 7-cyclooctatetraene

new IUPAC names: cycloocta-1,3,5,7-tetraene

C
H

C
H

C
H

1,3,5-heptatriene
hepta-1,3,5-triene

CH2

CYCLOALKENES
Contains C=C in the ring

cyclopropene

cyclobutene

cyclohexene

cyclopentene

Nomenclature of cycloalkenes:
- Similar to that alkenes
General formula CnH2n-2 where n =3,4,5..
6
5
4

1
2

CH3

1-methylcyclohexene

5
4

1
3

1,5-dimethylcyclopentene

NAMING CYCLOALKENES
3

1
5

CH3

6-Ethyl-1-methylcyclohexene

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 firstappearing 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

2
4

H3C

CH3

1-methylcyclopentene

3,5-dimethylcyclohexene

NOMENCLATURE OF cis-trans
ISOMERS
H3C
H

CH2CH3
H

cis-2-pentene
geometric isomers

H3C

H
C

C
CH2CH3

trans-2-pentene
(diastereomers)

cis two particular atoms (or groups of atoms) are

adjacent to each other
trans the two atoms (or groups of atoms) are
across from each other

C=C are called vinyl carbons

If either vinyl carbon is bonded to two
equivalent groups, then no geometric
isomerism exists.

CH3CH=CHCH3

CH3CH2CH=CH2

YES

NO

(CH3)2C=CHCH3
NO

CH3
CH3CH=CCH2CH3
YES

Confusion about the use of cis- and trans-.

According to IUPAC rules it refers to the parent
chain.
H3C
CH2CH3
C C
cis-
H
CH3

H3C
Cl
C C
H
Br

????????

E/Z system is now recommended by IUPAC for the

designation of geometric isomerism.
1. Use the sequence rules to assign the higher
priority * to the two groups attached to each
vinyl carbon.
2. *

*
(Z)- zusammen
together

(E)- entgegen
opposite

H3C
CH2CH3
C C
H
CH3

(Z)-

H3C
Cl
C C
H
Br

(E)-

H3C
CH2CH3
C C
H
CH3

(Z)-3-methyl-2-pentene
(3-methyl-cis-2-pentene)

H3C
Cl
C C
H
Br

(E)-1-bromo-1-chloropropene

CH3
CH3CH2
CHCH2CH3

/
C=C
/

CH3CH2

3-ethyl-5-methyl-3-heptene

(NOT a geometric isomer)

SYNTHESIS OF ALKENES

SYNTHESIS OF ALKENES

Removal of Water
DeHydration

Removal of Hydrogen
Halides
DeHydrohalogenation

SYNTHESIS OF ALKENES
Alkenes can be prepared in the following ways:
i) Dehydration of alcohols
conc. H2SO4

R-CH2-CH2-OH

R-CH=CH2 + H2O

Loss of H and OH from adjacent carbons.

Acid catalyst is necessary. (H2SO4 / H3PO4)
The reactions are carried out at high temperature;
depending on type of alcohols used.

SYNTHESIS OF ALKENES
Alkenes can be prepared in the following ways:
ii) Dehydrohalogenation of haloalkanes
R-CH2-CH2-X

*CH3CH2O-Na+ in
ethanol
(reflux)

R-CH=CH2 + HX

*Potassium ethoxide

Loss of H and halogen (X) from an alkyl halide

In the presence of strong base in solvent

 Saytzeff rule:
- A reaction that produces an alkene would favour the
formation of an alkene that has the greatest number
of substituents attached to the C=C group.
Dehydration of alcohols
H+

CH3CH2-CH-CH3
OH

CH3CH2-CH=CH2 + H2O
1-butene

CH3CH=CH-CH3 + H2O

2-butanol

2-butene
major product

Dehydrohalogenation of haloalkanes
CH3CH-CH-CH2
H

Br H

2-bromobutane

KOH

alcohol
reflux

CH3CH=CH-CH3
2-butene
(major product)

CH3CH2CH=CH2
1-butene

REACTION OF ALKENES

REACTION OF ALKENES
Hydrogenations

Addition of Hydrogen

Addition of Halogen
Halogenation
Hydrohalogenati
on

Addition of Hydrogen
Halides
Addition of Water

Hydration
Ozonolysis

Reaction of Alkenes
Primarily reactions involve the double bond
The key reaction of double bond is addition reaction
(Breaking the bond and adding something to each
carbon)
The major alkene reactions include additions of
hydrogen (H2),halogen ( CI2 or Br2), water (HOH) or
hydrogen halides (HBr or HCI)
+

A-B
A

Addition Reactions
Why do alkenes undergo addition reactions?

Carbon-carbon double bonds in alkenes are reactive.

readily undergoes addition reactions

Unsaturated
hydrocarbon

Saturated organic
compound

In an addition reaction, carbon-carbon double bonds

become single bonds. This means that an unsaturated
hydrocarbon becomes a saturated organic compound.

Reaction of Alkenes
(1) Catalytic hydrogenation:
- hydrogenation: addition of hydrogen to a double bond and
triple bond to yield saturated product.
- alkenes will combine with hydrogen in the present to catalyst
to form alkanes.

C C

HH

Pt or Pd
o

25-90 C

C C
HH

- Plantinum (Pt) and palladium (Pd) Catalysts

- Pt and Pd: temperature 25-90oC
- Nickel can also used as a catalyst, but a higher temperature of
140oC 200oC is needed.

EXAMPLES:
H2C CH2
ethylene

CH3CH2CH2CH2CH CH2
hexene

H2

H2

Pt
low pressure

Pt
low pressure

H3C CH3
ethane

CH3CH2CH2CH2CH2CH3
hexane

Reaction of Alkenes
(2) Addition of halogens:
i) In inert solvent:
- alkenes react with halogens at room temperature and in dark.
- the halogens is usually dissolved in an inert solvent such as
dichloromethane (CH2Cl2) and tetrachloromethane (CCl4).
- Iodine will not react with alkenes because it is less reactive than
chlorine and bromine.
- Fluorine is very reactive. The reaction will produced explosion.

C C

X X

inert solvent

X X = halogen such as Br2 or Cl2

Inert solvent = CCl4 or CH2Cl2

C C
X X

EXAMPLES:
H H
H C C H

H H
H C C H
Br Br

inert solvent (CCl4)

Br Br

ethene

1,2-dibromoethane
* the red-brown colour of the bromine solution will fade and the
solution becomes colourless.

Br2

CCl4

Br
1,2-dibromocyclohexane

cyclohexene
CH3CH=CH2
propene

Br

Cl2

CCl4

Cl Cl
CH3CH CH2
1,2-dichloropropane

Reaction of Alkenes
(3) Addition of hydrogen halides:
- Addition reaction with electrophilic reagents.
- Alkenes react with hydrogen halides (in gaseous state or in
aqueous solution) to form addition products.
- The hydrogen and halogen atoms add across the double bond to
form haloalkanes (alkyl halides).
- General equation:

C C
alkene

HX

H X
C C

haloalkane

- Reactivity of hydrogen halides : HF < HCl < HBr < HI

* Reaction with HCl needs a catalyst such as AlCl3

H2C CH2

HCl

AlCl3

CH3CH2Cl

EXAMPLES:

H-I
cyclopentene

CH3CH=CHCH3 + H-Br
2-butene

I
iodocyclopentane

Br
CH3CH2CHCH3
2-bromobutane

MARKOVNIKOVS RULE
There are 2 possible products when hydrogen halides
react with an unsymmetrical alkene.
It is because hydrogen halide molecule can add to the
C=C bond in two different ways.
H H
CH3 C C H

H H
H-I

CH3 C C H
H I
1-iodopropane

H H
CH3 C C H

H H
H-I

CH3 C C H
I H
2-iodopropane
(major product)

Markovnikovs rules:
- the addition of HX to an unsymmetrical
alkene, the hydrogen atom attaches itself
to the carbon atom (of the double bond)
with the larger number of hydrogen atoms.

(5) Addition reaction with acidified water (H3O+): hydration of

alkenes

Hydration: The addition of H atoms and OH groups from water

molecules to a multiple bond.
Reverse of the dehydration reaction.
Direct hydration of ethene:
- passing a mixture of ethene and steam over phosphoric (v) acid
(H3PO4) absorbed on silica pellets at 300oC and a pressure of 60
atmospheres.
- H3PO4 is a catalyst.

CH2=CH2 (g)

H2O (g)

ethene

C C
alkene

H3PO4
o

300 C, 60 atm

H2O

H+

CH3CH2OH (g)
ethanol

H OH
C C
alcohol

 Markovnikovs rule is apply to the addition of a water

molecule across the double bond of an unsymmetrical
alkene.
For examples:

CH3
CH3 C

CH2

CH3

H
25oC

H OH

CH3 C

2-methylpropene

CH2

OH H
tert-butyl alcohol

CH3CH=CH2 + H2O

H+

CH3CHCH3
OH

propene

2-propanol
H+ = catalyst

OZONOLYSIS OF ALKENES
(5) Ozonolysis:
- The reaction of alkenes with ozone (O3) to form an ozonide, followed
by hydrolysis of the ozonide to produce aldehydes and /or ketone.
- Widely used to determine the position of the carbon-carbon double
bond.
- Ozonolysis is milder and both ketone and aldehydes can be
recovered without further oxidation.
R

R'
O3

C C
R

R'

(CH3)2S

C C
R O O H or H2O, Zn/H+
ozonide

R'
C O

R
ketone

O C
H
aldehyde

EXAMPLES:
i) O3
ii) (CH3)2S

3-nonene

CH3O
H

OCH3
H

i) O3
ii) (CH3)2S

H
O
CH3O

H
OCH3

O
O

O
O

USES OF ALKENES
Ethylene and propylene are the largest-volume industrial
organic chemicals.
Used to synthesis a wide variety of useful compounds.
H H
H H n

CH2

ethylene oxide
H

H2O

CH2 CH2
OH

OH

ethylene glycol

CH3 C OH

acetaldehyde

polymerize

H 2C

oxidize

CH3 C

polyethylene

C C

acetic acid

oxidize

O2

Ag catalyst

H
C C
ethylene

Cl2

CH2 CH2
CI CI
ethylene dichloride

H2O
catalyst

CH3 CH2
OH
ethanol

NaOH

H
H C

CI
C H

vinyl chloride

POLYETHENE (PE)
The most popular plastic.
Uses:
i) Grocery bags
ii)Shampoo bottles
iii)Children's toy
iv)Bullet proof vests
v)Film wrapping
vi)Kitchenware

POLYVINYL CHLORIDE
(PVC)

H H
H C C CI

vinyl chloride

polymerize

H
C
H

CI H
C C
H H

CI H
C
C
H n H

CI
C
H

poly(vinyl chloride)
USES OF PVC:
PVC, "vinyl"
Clothing
- PVC fabric has a sheen to it and is waterproof.
- coats, shoes, jackets, aprons and bags.
As the insulation on electric wires.
Producing pipes for various municipal and industrial
applications. For examples, for drinking water distribution and
wastewater mains.
As a composite for the production of accessories or housings for
portable electronics.
uPVC or Rigid PVC is used in the building industry as a lowmaintenance material.
Ceiling tiles.

USES OF ETHANOL
Motor fuel and fuel additive.
As a fuel to power Direct-ethanol fuel cells (DEFC) in order to
produce electricity.
As fuel in bipropellant rocket vehicles.
In alcoholic beverages.
An important industrial ingredient and use as a base chemical
for other organic compounds include ethyl halides, ethyl esters,
diethyl ether, acetic acid, ethyl amines and to a lesser extent
butadiene.
Antiseptic use.
An antidote.
Ethanol is easily miscible in water and is a good solvent.
Ethanol is less polar than water and is used in perfumes, paints
and tinctures.
Ethanol is also used in design and sketch art markers.
Ethanol is also found in certain kinds of deodorants.

In short, cracking is used to

produce:

Hydrogen (fuel and raw material

for Haber process)

Petrol (fuel)
Short-chain alkenes
(starting materials for
making ethanol and
plastics)

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