ORGANIC CHEMISTRY 1

CHAPTER 3
ALKENES
 ALKENES
• Also called olefins
• Contain at least one carbon-carbon double bond
(C=C)
• General formula, CnH2n (n=2,3,…)
• Classified as unsaturated hydrocarbons
(compound with double or triple carbon-carbon
bonds that enable them to add hydrogen atoms.
• sp2-hybridized
• For example:
C2H4 - ethylene
CH2
Naming Alkenes
 IUPAC
RULE 1.
RULES
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 Name

This isthe
theparent
longest
contains 8 compound
continuous octene.
chain.
carbon atoms 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
ThisRULES
end of the chain is closest to the
double bond. Begin numbering here.
 IUPAC
RULES
The name of the parent compound is
1-octene.
4 3 2 1

5
6
7
8
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
The
This ethyl RULES
is an group
ethyl is attached to carbon 4.
group.
4 3 2 1

5
6
4-ethyl-1-octene
7
8
• 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 7 6 5 4 3 2 1
2 3 4
CH2 C C CH2 CH3 C C C C
C CH2
H H H H H
IUPAC names: 1,3-butadiene H 1,3,5-heptatriene
H
new IUPAC names: buta-1,3-diene hepta-1,3,5-triene

1 2
8 3

7 4
6 5
IUPAC names: 1,3, 5, 7-cyclooctatetraene
new IUPAC names: cycloocta-1,3,5,7-tetraene
 ALKENES AS SUBSTITUENTS
• Alkenes names as substituents are called alkenyl groups.
• Can be named systematically as ethenyl, propenyl, etc. or
by common names such as vinyl, ally, methylene and
phenyl groups.

CH2 -CH=CH2 -CH2-CH=CH2

methylene group vinyl group allyl group

(methylidene group) (ethenyl group) (2-propenyl group)

CH=CH2
CH2 CHCHCH2CH
3-methylenecyclohexene CH2
3-vinyl-1,5-hexadiene
3-vinylhexa-1,5-
diene
 CYCLOALKENES
• Contains C=C in the ring

cyclopropene cyclobutene cyclopentene cyclohexene

• Nomenclature of cycloalkenes:
- Similar to that alkenes
- Carbons atoms in the double bond are designated
C1 and C2
6 CH3 5
5 1 4 1
4 2 3 2
3
1-methylcyclohexene 1,5-dimethylcyclopentene
 NOMENCLATURE OF cis-trans
ISOMERS

H3C
H3C CH2CH3
C H
C H C
H H CH2CH3

cis-2-pentene C
trans-2-pentene

•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
 PHYSICAL PROPERTIES OF ALKENES
• Boiling points and densities:

- Most physical properties of alkenes are similar to

those alkanes.

- Example: the boiling points of 1-butene, cis-2-butene,

trans-2-butene and n-butane are close to 0oC.

- Boiling points of alkenes increase smoothly with

molecular weight.

- Increased branching leads to greater volatility and

lower boiling points.
• Polarity:

- relatively nonpolar.

- insoluble in water but soluble in non-polar

solvents such as hexane, gasoline, halogenated
solvents and ethers.

- slightly more polar than alkanes because:

i)electrons in the pi bond is more polarizable
(contributing to instantaneous dipole
moments).
ii)the vinylic bonds tend to be slightly polar
(contributing to a permanent dipole moment).
 Alkyl groups are electron donating toward double
bond, helping to stabilize it. This donating slightly
polarizes the vinylic bond, with small partial positive
charge on the alkyl group and a small negative charge
on the double bond carbon atom.
 For example, propene has a small dipole moment of
0.35 D.
Vinylic bonds

H3C H H3C CH3 H3C H

C C C C C C
H H H H H CH3
propene, μ = 0.35 Vector sum = Vector sum = 0
D propene, μ = 0.33 D propene, μ = 0
cis-2-butene, bp 4oC trans-2-butene,
bp 1oC
• In a cis-disubstituted alkene, the vector sum of the two
dipole moments is directed perpendicular to the
double bond.
• In a trans-disubstituted alkene, the two dipole
moments tend to cancel out. If an alkene is
symmetrically trans-disubstituted, the dipole moment
is zero.

Vector sum = Vector sum = 0

propene, μ = 0.33 D propene, μ = 0
cis-2-butene, bp 4oC trans-2-butene,
bp 1oC
• Cis- and trans-2-butene have similar van der Waals
attractions, but only cis isomer has dipole-dipole
attractions.

• Because of its increased intermolecular attractions,

cis-2-butene must be heated to a slightly higher
temperature (4oC versus 1oC) before it begins to boil.

Vector sum = Vector sum = 0

propene, μ = 0.33 D propene, μ = 0
cis-2-butene, bp 4oC trans-2-butene,
bp 1oC
 PREPARATION OF ALKENES

• Alkenes can be prepared in the following ways:

i) Dehydration of alcohols
conc. H2SO4
R-CH2-CH2-OH R-CH=CH2 + H2O

ii) Dehydrohalogenation of haloalkanes

NaOH/ethanol
R-CH2-CH2-X R-CH=CH2 + HX
reflux

NaOH can be replaced by KOH

 • 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=CH2 + H2O
CH3CH2-CH-CH3 1-butene
OH H+
CH3CH=CH-CH3 + H2O
2-butanol
2-butene
major product

Dehydrohalogenation of haloalkanes

CH3CH-CH-CH2 alcohol CH3CH=CH-CH3 CH3CH2CH=CH2

KOH reflux
H Br H 2-butene
2-bromobutane 1-butene
(major product)
 REACTIVITY
OF
ALKENES
More reactive than alkanes because:
• A carbon-carbon double bond consists of a σ and a π
bond. It is easy to break the π bond while the σ bond
remains intact.
• The π electrons in the double bond act as a source of
electrons (Lewis base). Alkenes are reactive towards
electrophiles which are attracted to the negative charge
of the π electrons.
• π bond will broken, each carbon atom becomes an
active site which can form a new covalent bond with
another atom. One π bond is converted into 2 σ bonds.
 REACTIONS OF ALKENES
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.

Pt or Pd
C C H o
C
25-90 C
H C
H H
- 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:
Pt
H2C CH2 H2 H3C CH3
low
ethylene ethane
pressure

Pt
CH3 CH2 CH2 CH2 CH CH2 H2 CH3CH 2CH 2CH 2CH 2CH3
low
hexene hexane
pressure
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.

inert solvent
C C X X C
C
X X
X X = halogen such as Br2 or
Cl2 Inert solvent = CCl4 or CH2Cl2
EXAMPLES:

H H inert solvent (CCl4) H H

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

Br
CCl4
Br2
Br
cyclohexene
1,2-dibromocyclohexane
Cl Cl
CH3CH=CH 2 Cl2 CCl4
CH3CH
propene CH2
 Addition of halogens:
ii) In water / aqueous medium:
- chlorine dissolves in water to form HCl and chloric (l)
acid
(HOCl).
Cl2 (aq) + H2O(l) HCl(aq) + HOCl (aq)

- same as bromine
Br2 (aq) + H2O(l) HBr(aq) + HOBr(aq)

* Reaction of alkenes with halogens in water (eg.

chlorine water and bromine water) produced
halohydrins (an alcohol with a halogen on the adjacent
carbon atom).
 EXAMPLES:

H2O
CH3CH=CH2 + Br2 CH3 CH CH2 CH3 CH CH2
OH Br Br Br
propene
1-bromo-2-propanol 1,2-dibromopropane
(major product) (minor product)
* Br atom attached to the carbon atom of the double bond which has the greater
number of hydrogen atoms.

Cl2, H2O CH3 CH2 CH CH2

CH3CH2CH=CH2
OH Cl
1-butene 1-chloro-2-butanol
• 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:

H X
C C HX C
C
alkene
haloalkane
-
Reactivity of hydrogen halides : HF < HCl < HBr < HI
 * Reaction with HCl needs a catalyst such as AlCl3
AlCl3
H2C CH2 HCl CH3CH2Cl

EXAMPLES:

H-I I
cyclopentene iodocyclopentane

Br
CH3CH=CHCH3 + H- CH3CH2CHCH3
Br 2-
bromobutane
2-butene
 MARKOVNIKOV’S 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.

HH HH
CH3 C H-I CH3 C
CH CH
1-iodopropane
H
HH HH
I
CH3 C H-I CH3 C
CH CH
2-iodopropane
I
(major product)
 Markovnikov’s 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.
When unsymmetrical alkene react with unsymmetrical reagent
The positive part of the reagent becomes attached itself to that
Boubly bonded carbon atom which has more number of
Hydrogen atoms and negative part of reagent goes to doubly
Bonded carbon atom which bears less number of hydrogen atoms
Mechanism of electrophilic addition reactions:
- C=C : electron rich part of the alkene molecule
- Electrophiles: electron-seeking

Step 1: Formation of carbocation.

Attack of the pi bond on the electrophile to form carbocation.

δ+ δ-
C C E C Y-
Y
E
C
c
a
r
b
o
c
C a
Y- Ct
Ci
 ADDITION OF HYDROGEN HALIDES TO
UNSYMMETRICAL ALKENES AND
MARKOVNIKOV’S RULE

CH3CHCH2
1
3 2
HCl H Cl
CH3CH=CH2
1-chloropropane
Propene
CH3CHCH2
Cl H
2-
chloropropane
(major product)
according to Markovnikov's
rules
MECHANISM:

Step 1: Formation of carbocation

H H HH H H HH
H Cl HCCCH or H C C C Cl-
CH3 C C H
H H H H H
less stable carbocation more stable carbocation
(1o carbocation) (2o carbocation)

- 2o carbocation is more stable than 1o carbocation.

- 2o carbocation tends to persist longer, making it more likely to combine with
Cl- ion to form 2-chloromethane (basis of Markovnikov's rule).

Step 2: Rapid reaction with a negative ion

H HH H HH
HCC CH Cl- HCCCH
H H H Cl H
2-chloromethane
(major product)
Addition reaction with concentrated sulfuric
acid: hydration of alkenes

-the alkene is absorbed slowly when it passed

through concentrated sulfuric acid in the cold
(0-15oC).
-involves the addition of H atom and HSO4
group across the carbon-carbon double bond.
- follows Markovnikov’s rule.
 H H H H
H C CH H OSO3H H C C H
(H2SO4) H
OSO3H
ethyl hydrogensulphate
When the reaction mixture is added(CH
to water and warmed,
3CH2HSO4)
ethyl hydrogensulphate is readily hydrolysed to ethanol

CH3CH2OSO3H + H-OH CH3CH2OH + H2SO4

(H2O)

*ethene reacts with concentrated H 2SO4 to form

ethanol*

or
• 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.

H3PO4
CH2=CH2 (g) H 2O (g) o CH3CH2OH (g)
300 C, 60 atm
ethene ethanol
H
C C H2O OH
alkene alcohol
• Markovnikov’s rule is apply to the addition of a water
molecule across the double bond of an unsymmetrical
alkene.
• For examples:

CH3 CH3
CH3 C CH2 H OH H+
2-methylpropene
CH3 C
25oC
CH2
O
HH
CH3CH=CH2 + H2O H+ CH3CHCH3 tert-
butyl alcohol
propene OH
2-propanol
H+ = catalyst
MECHANISM OF ACID CATALYSED HYDRATION OF ALKENES

Step 1: Protonation to form carbocation

H H HHH
CH3 C C H H+ HCCCH
H
more H
stable carbocation
(2o carbocation)

Step 2: Addition of H2O to form a protonated alcohol

HHH
H C C C
O H CH3CHCH3
H H O H
H
H
H
Step 3: Loss of a proton (deprotonated) to form alcohol

CH3CHCH3
CH3CHCH3 +
O H H
OH
H+ = catalyst
 ANTI-MARKOVNIKOV’S RULE: FREE RADICAL
ADDITION OF HYDROGEN BROMIDE

• When HBr is added to an alkene in the absence of peroxides

it obey Markovnikov’s rule.
• When HBr (not HCl or HI) reacts with unsymmetrical alkene
in the presence of peroxides (compounds containing the O-
O group) or oxygen, HBr adds in the opposite direction to
that predicted by Markovnikov’s rule.
• The product between propene and HBr under these
conditions is 1-bromopropane and not 2-bromopropane.

peroxide
CH3CH=CH2 HBr CH3CH2CH2Br
1-bromopropane
(major product)
anti-Markovnikov's orientation
• Anti-Markovnikov’s addition:

- peroxide-catalysed addition of HBr occurs

through a free radical addition rather than a
polar electrophilic addition.

- also observed for the reaction between HBr

and many different alkenes.

- not observed with HF, HCl or HI.

 Combustion of alkenes:

 The alkenes are highly flammable and burn

readily in air, forming carbon dioxide and
water.
 For example, ethene burns as follows :
C2H4 + 3O2 → 2CO2 + 2H2O
 OXIDATION
• Oxidation: reactions that form carbon-
oxygen bonds.

• Oxidation reaction of alkenes:

i)epoxidation
ii)hydroxylation
iii)Ozonolysis
 EPOXIDATION OF ALKENES
• Epoxide / oxirane: a three-membered cyclic ether.
O O O
C R C OH
R C OOH C C
C
peroxyacid epoxide (oxirane) acid
alkene

• Examples of epoxidizing reagent:

O O
O
Cl
CH3 C O O H COOH H
peroxyacetic acid peroxybenzoic acid O
m-chloroperoxybenzoic
O acid
(PhCO3H) (MCPBA)
Examples:

MCPBA
O
CH2CI2, 25oC
cyclohexene 1,2-epoxycyclohexane

MCPBA
O
CH2CI2, 25oC
cycloheptene 1,2-epoxycycloheptane
 HYDROXYLATION
OF ALKENES
• Hydroxylation:
- Converting an alkene to a glycol requires adding a
hydroxyl group to each end of the double bond.
• Hydroxylation reagents:
i) Osmium tetroxide (OsO4)
ii)Potassium permanganate (KMnO4)

C C OsO4 H2 O2 C
(or KMnO4, -OH) C OH
OH
glycol
 KMnO4 (aq), OH-
CH2 CH2 CH2 CH 2 MnO2
cold
ethene OH OH
1,2-ethanediol

KMnO4 (aq), OH-

CH3 CH CH2 CH3 CH CH2 MnO2
cold
propene
OH OH
1,2-propanediol

* Also known as Baeyer’s test

 OZONOLYSIS OF ALKENES
• 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' R O R' R R'

(CH3)2S
C C O3 C C + C O O C
O O or H2O, Zn/H
R H R H
R ozonide H ketone aldehyde
 EXAMPLES:

i) O3 H O
3-nonene ii) (CH3)2S
O H

CH3O OCH3 CH3O

i) O3
ii) (CH3)2S O
H H OCH3 O
O O
H H
REACTIONS OF ALKENES WITH HOT, ACIDIFIED
KMnO4

R R' +
R
KMnO4/H
C C R'
R H R OH
C C H
OH
R R' R R'
C
O C C O O C
O OH H
Rketone acid Rketone aldehyde

Example:
KMnO4/H+ O HO
C C
O
4-methyl-4-octene 2-pentanone b
u
 POLYMERIZATION OF ALKENES
• Polymer: A large molecule composed of many smaller
repeating units (the monomers) bonded together.

• Alkenes serves as monomers for some of the most

common polymers such as polyethylene (polyethene),
polypropylene, polystyrene, poly(vinyl chloride) and
etc.

• Undergo addition polymerization /chain-growth

polymer:
- a polymer that results from the rapid addition of one
molecule at a time to a growing polymer chain, usually
with a reactive intermediate (cation, radical or anion) at
the growing end of the chain.
 repeating unit

CI H CI H CI Cl
H H Cl H
CI H
C C C C C C C C C
H C C
H H H H H
C
vinyl chloride H poly(vinyl
H H chloride)
H H
H
n
UNSATURATION TESTS FOR ALKENES
• Reactions of alkenes with KMnO4

- KMnO4 is a strong oxidising agent.

-alkenes undergo oxidation reactions with
KMnO4 solution under two conditions:
a)Mild oxidation conditions using cold,
dilute, alkaline KMnO4 (Baeyer’s test).
b)Vigorous oxidation conditions using hot,
acidified KMnO4.
• Reaction of alkenes with cold, dilute, alkaline
KMnO4 (Baeyer’s test)

- the purple colour of KMnO4 solution disappears

and a cloudy brown colour appears caused by the
precipitation of manganese (IV) oxide, MnO2.

- test for carbon-carbon double or triple bonds.

- a diol is formed (containing two hydroxyl groups

on adjacent carbon atoms).
 KMnO4 (aq), OH-
C C C C MnO2
cold
OH
OH
a diol
b) Bromine

-A solution of bromine in inert solvent (CH2CI2 or CCI4)

and dilute bromine water are yellow in colour.

-The solution is decolorised when added to alkenes or

organic compounds containing C=C bonds.
 CH2CI2
C C Br2 C
C
Br Br

H2O
C C Br2(aq) C C C C
OH Br Br
Br
 DETERMINATION OF THE POSITION
OF THE DOUBLE BOND
a) Ozonolysis of alkenes:
- For example, ozonolysis of an alkene produces
methanal and propanone.
H CH3
H C O O C CH3
methanal propanone

remove the oxygen atoms from the carbonyl compounds and

joining the carbon atoms with a double bond.

H CH3 H CH3
H C C CH3
H C C CH3
2-methylpropene
b) Reaction of alkenes with hot, acidified KMnO4

-by using hot, acidified KMnO4, the diol obtained is

oxidised further.
-cleavage of carbon-carbon bonds occurs and the
final products are ketones, carboxylic acids or
CO2.

CH3
KMnO4/H+ CH3
CH3 CH2
CH3 C O CO2 + H2 O
C2-methylpropene
propanone
(ketone)
 • Example:
An alkene with the molecular formula C6H12 is oxidised with
hot KMnO4 solution. The carboxylic acids, butanoic acid
(CH3CH2CH2COOH) and ethanoic acid (CH3COOH), are
produced. Identify the structural formula of the alkene.

i) cleavage of the double bond gives a mixture of carboxylic acids

H H
KMnO 4/H+ OH OH
R C C
R C C
R' O R'
ii) location of the double bond is done by taking away the oxygen atoms from the
carboxylic acids and then joining the carbon atoms by the double bond.
O

RCOOH and R'COOH RCH=CHR'

CH3CH2CH2COOH CH3COOH CH3CH2CH2CH=CHCH3

and ethanoic acid 2-hexene
butanoic acid
 USES OF ALKENES
• Ethylene and propylene are the largest-volume industrial
organic chemicals.
• Used to synthesis a wide variety of useful compounds.
HH
C C O O
oxidize
HH n CH3 C OH
CH3 C H
polyethylene acetaldehyde acetic acid
polymerize
oxidize
O H
O2 Cl 2 CH2
H2C CH2 Ag catalyst
ethylene oxide CH2 CI
CI
H+ H2OH ethylene NaOH
catalyst dichloride
H2O
C
CH2 CH2 H H
CH3 CH2
C CI
OH OH OH
ethylene glycol ethanol H vinyl
C chloride
C
H
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)
HH polymerize H CI CI H
H C C CI H C CI
vinyl chloride C C C
C
poly(vinyl H C
chloride)
H PVC,
H "vinyl"
H n H H
USES OF PVC:
 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
low-maintenance 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.