ORGANIC CHEMISTRY 1

CHM 257

CHAPTER 3
ALKENES

NURUL AIN BINTI JAMION

 SUBTOPICS
Naming alkenes according to IUPAC and common names

Physical properties of alkenes:

i) boiling points and densities
ii) solubility
iii)polarity

Preparation of alkenes:
i) dehydration of alcohols
ii) dehydrohalogenation of haloalkanes
 Reactions of alkenes :
i) Addition reaction:
a) Catalytic hydrogenation
b) Addition of halogens
- In inert solvent
- In water / aqueous medium
c) Addition of hydrogen halides
d) Addition reaction with acidified water (H3O+): hydration of
alkenes
ii) Oxidation:
a) combustion
b) epoxidation
c) hydroxylation
d) Oxidative cleavage of alkenes (Ozonolysis and reaction
with hot/warm concentrated KMnO4)
Unsaturation tests of alkenes:
i) Reactions of alkenes with KMnO4
ii) Reactions of alkenes with bromine.

Sources of alkenes
Uses of alkenes:
i) PE
ii) PVC
 ALKENES
Also called olefins
Contain at least one carbon-carbon double bond
(C=C)
General formula, CnH2n (n=2,3,), n = no. of carbon
Classified as unsaturated hydrocarbons (compound
with double or triple carbon-carbon bonds that
enable them to add hydrogen atoms.
sp2 hybridization
Example:
C2H4 - ethylene

CH2 CH2
 NOMENCLATURE OF ALKENES
(IUPAC)
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 Nameisthe

This theparent
longest
contains 8 continuousoctene.
compound 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.
This end of the chain is closest to
the double bond. Begin numbering
here.
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.
 The ethyl group is attached to carbon 4.

4 3 2 1

5
This is an
ethyl group. 6
4-ethyl-1-octene
7
8
 NEW IUPAC NAMES
Placing numbers (location of double bond) before the
part of the name ene.
Examples:
1 2 3 4 1 2 3 4 5 6
CH2 C CH2 CH3 CH3 C C CH2 CH2 CH3
H H H
Old naming system: 1-butene Old naming system: 2-hexene
New naming system: but-1-ene New naming system: hex-2-ene

CH3
1 2 3 4
CH2 C C CH3
H H
Old naming system: 3-methyl-1-butene
New naming system: 3-methylbut-1-ene
 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 2 3 4 7 6 5 4 3 2 1
CH2 C C CH2 CH3 C C C C C CH2
H H H H H H H
IUPAC names: 1,3-butadiene 1,3,5-heptatriene
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 CH2
3-methylenecyclohexene IUPAC name: 3-vinyl-1,5-hexadiene
New IUPAC name: 3-vinylhexa-1,5-diene
 NOMENCLATURE OF cis-trans ISOMERS

H3C CH2CH3 H3C H

C C C C
H H H CH2CH3

cis-2-pentene 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
 NOMENCLATURE OF ALKENES
(COMMON NAMES)
For the simplest compounds.
Examples:
CH2=CH2 CH2=CHCH3
IUPAC names: ethene IUPAC names: propene
common names: ethylene common names: propylene

CH3 CH3

CH2=C CH3 CH2=CCH=CH2

IUPAC names: 2-methylpropene IUPAC names: 2-methylbuta-1,3-diene
common names: isobutylene common names: isoprene

IUPAC names: ethenylbenzene

common names: styrene
 exercises
Give the IUPAC name of the following alkenes:

b) CH3
a)
H3C CHCH3
C C
H CH3

c)
Cl
Cl
 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.

- Densities of alkenes: around 0.6 or 0.7 g/cm3.

- Boiling points of alkenes increase smoothly with

molecular weight.

- Increased branching leads to greater volatility and

lower boiling points.
 Solubilities:

- relatively nonpolar.

- insoluble in water but soluble in non-polar

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

Polarity:

- 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).
 Boiling point of cis and trans alkenes
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
Vector sum = Vector sum = 0
propene, = 0.35 D
cis-2-butene, = 0.33 D trans-2-butene, = 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.
H H3C CH3 H3C H
C C C C C C
H H H H CH3
Vector sum = Vector sum = 0
cis-2-butene, = 0.33 D trans-2-butene, = 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.

H H3C CH3 H3C H

C C C C C C
H H H H CH3
Vector sum = Vector sum = 0
cis-2-butene, = 0.33 D trans-2-butene, = 0
cis-2-butene, bp 4oC trans-2-butene, bp 1oC
 PREPARATION OF ALKENES

Dehydration of alcohols
Dehydrohalogenation of haloalkanes /
alkyl halides
 PREPARATIONS OF ALKENES
i) Dehydration of alcohols
- dehydration = removal of water
- Type of reaction: Elimination reaction (a small molecule is
removed from a larger molecule to produce a double bond or a
triple bond).

acidic catalyst, heat /

C C
C C + H2O
H OH

acidic catalyst / dehydrating agents: concentrated H2SO4 or concentrated H3PO4

- Example:
H H
concentrated H2SO4 H H
H C C H H C C H + H2O
H OH
ethene
ethanol
 Mechanism of dehydration of ethanol:
Conc. H2SO4
CH3CH2OH CH2=CH2 H2O
o
170 C

Step 1: Protonation of the hydroxyl group (fast equilibrium)

H
CH3CH2OH H OSO3H CH3CH2 O H HSO4-

Step 2: Ionization (slow; rate limiting)

H H
CH3CH2 O H H C C H H2O
H H

Step 3: Proton abstraction (fast)

H
H H
H C C H H2SO4
C C
H H
H H

HSO4-
 Mechanism of dehydration of 2-butanol:
OH
Conc. H2SO4
CH3CH2CHCH3 CH3CH=CHCH3 CH3CH2CH=CH2 H2O
Heat

Step 1: Protonation of the hydroxyl group (fast equilibrium)

OH H O H
CH3CH2CHCH3 H OSO3H CH3CH2CHCH3 HSO4-

Step 2: Ionization (slow; rate limiting)

H O H
H H H
CH3CH2CHCH3 H C C C C H H2O
H H H H
Step 3: Proton abstraction (fast)

H H H
H H H
H C C C C H
H C C C C H H2SO4
H H H H
H H H
major product
HSO4-

H H H H H H
H C C C C H H C C C C H H2SO4
H H H H H H H

- minor product
HSO4

** The major product were determined based on the Saytzeff rule.

 Mechanism of dehydration of 1-butanol:
Conc. H2SO4
CH3CH2CH2CH2OH CH3CH=CHCH3 CH3CH2CH=CH2 H2O
Heat (major, 70%) (minor, 30%)

Step 1: Protonation of the hydroxyl group (fast equilibrium)

H
CH3CH2CH2CH2 OH H OSO3H CH3CH2CH2CH2 O H HSO4-

Step 2: Ionization (slow; rate limiting), with rearrangement

H H H H
CH3CH2CH2CH2 O H H C C C C H H2O
H H H H
1o carbocation (less stable)

H H H
- H H H
H C C C C H H migrates
H C C C C H
H H H H
H H H H
2o carbocation
Step 3: Proton abstraction (fast)

H H H
H H H
H C C C C H
H C C C C H H2SO4
H H H H
H H H
major product
HSO4-

H H H H H H
H C C C C H H C C C C H H2SO4
H H H H H H H

- minor product
HSO4

** The major product were determined based on the Saytzeff rule.

ii) Dehydrohalogenation of haloalkanes / alkyl halides
- Dehydrohalogenation = the elimination of hydrogen and
halogen from an alkyl halides to form alkene
NaOH / ethanol
C C
reflux C C + HX
H X
alkyl halides alkene

X= halogen (F, Cl, Br or I)

* NaOH can be replaced by KOH

- Example:
H H
NaOH / ethanol
H H
H C C H
reflux H C C H + HBr
H Br
bromoethane ethene hydrogen bromide
 Saytzeff / Zaitsevs 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 (major product).

Dehydration of alcohols
H H H H
+
H
H C C C C H + H2O
H H 1 substituent
H H H H
1-butene (minor product)
H C C C C H
H OH H H H H H H
2-butanol H+
H C C C C H + H2O
H H 2 substituents
Location of double bond
2-butene (major product)
Dehydrohalogenation of haloalkanes

H H
KOH / alcohol
reflux H3C C C CH3 + HBr
2-butene
CH3CH-CH-CH2 (major product)
2 substituents
H Br H
2-bromobutane
H H
KOH / alcohol
reflux H C C CH2CH3 + HBr
1-butene (minor product)
1 substituent
 REACTIVITY OF ALKENES
More reactive than alkanes because:
i) A carbon-carbon double bond consists of a and a
bond. It is easy to break the bond while the bond
remains.
ii) The 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 electrons.
iii) bond will broken, each carbon atom becomes an
active site which can form a new covalent bond with
another atom. One bond is converted into 2 bonds.
 ADDITION REACTIONS
Addition reaction: a reaction in which an unsaturated
molecule becomes saturated by the addition of a molecule
across a multiple bond (C=C in alkenes, -CC- in alkynes,
C=O in aldehydes and ketones)
Addition reactions to double bonds have these 3
characteristics:
i) the bond of the double bond is broken and two single
bonds are formed
ii) only one product is obtained at the end of the reaction
iii) the product obtained is a saturated organic compound

addition reaction
C C E Y C C

unsaturated E Y
reagent saturated
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.

-
C C E Y C C Y-
+ E
carbocation

Step 2: Rapid reaction with a negative ion.

The negative ion (Y-) acts as nucleophile and attacks the
positively charged carbon atom to give product of the addition
reaction.

C C Y-
C C
E E Y
REACTIONS OF
ALKENES
 ADDITION REACTIONS
i) 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 H C C
25-90oC
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 H3C CH3
H2C CH2 H2
low pressure ethane
ethylene

Pt
CH3CH2CH2CH2CH CH2 H2 CH3CH2CH2CH2CH2CH3
low pressure
hexene hexane
 Mechanism of Catalytic Hydrogenation

The hydrogen and the alkene are adsorbed on the metal

surface.
Once adsorbed, the hydrogens insert across the same
face of the double bond and the reduced product is
released from the metal.
The reaction has a syn stereochemistry (addition of two
substituents to the same side (or face) of a double bond)
since both hydrogens will add to the same side of the
double bond.
ii) 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 H H
inert solvent (CCl4)
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=CH2 Cl2 CCl4
CH3CH CH2
propene 1,2-dichloropropane
 Mechanism of Halogen Addition to Alkenes
Step 1: Formation of a halonium ion

X
C C X X C C X

halonium ion

Step 2: Opening of the halonium ion

X X
C C C C
X

X X- attacks from the back side

The intermediate is a three-membered ring called the halonium ion.

ii) Addition of halogens:
ii) In water / aqueous medium:
- 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
propene OH Br Br Br
1-bromo-2-propanol 1,2-dibromopropane
(major product) (minor product)

* Halogen 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
 Mechanism: formation of halohydrins
Step 1: Formation of a halonium ion

X
C C X X C C X
X = Cl, Br or I halonium ion

Step 2: Water opens the halonium ion; deprotonation gives the halohydrin

X X X
C C C C C C H3O+X-
O OH
H H
Markovnikov orientation
H O H
H O H
back side attack
iii)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 / alkyl halides

- 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-Br CH3CH2CHCH3
2-butene 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.
1. H H H H
CH3 C C H H-I CH3 C C H
H I
1-iodopropane

2. H H H H
CH3 C C 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.

- In an electrophilic addition to an alkene, the

electrophile adds in such a way as to generate
the most stable intermediate.
ADDITION OF HYDROGEN HALIDES TO
UNSYMMETRICAL ALKENES AND
MARKOVNIKOVS RULE

CH3CHCH2
3 2 1 H Cl
CH3CH=CH2 HCl
1-chloropropane
Propene
CH3CHCH2
Cl H
2-chloropropane
(major product)
according to Markovnikov'
rules
 Mechanism: addition OF HYDROGEN HALIDES TO
UNSYMMETRICAL ALKENES
Step 1: Formation of carbocation
H H H H H H H H
H Cl H C C C H or H C C C H Cl-
CH3 C C 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 H H H H H
H C C C H Cl- H C C C H
H H H Cl H
2-chloromethane (major product)
 STABILITY OF CARBOCATIONS
A secondary carbocation is more stable than primary
carbocation due to the electron donating effect of alkyl
groups.
The greater the number of the alkyl groups on the carbon
atom that bears the positive charge, the greater its
stability.

H H R R
H CH R C H R CH R C R

primary secondary tertiary

carbocation carbocation carbocation

stability of the carbocation increases

iv) 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.
Example (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) H2O (g) o CH3CH2OH (g)
300 C, 60 atm
ethene ethanol

H+ H OH H+ = H2SO4 or H3PO4
C C H2O C C H2O/H+ = acidified water or dilute
alkene alcohol acid
 Markovnikovs rule is apply to the addition of a water
molecule across the double bond of an unsymmetrical
alkene.
Examples:

CH3 CH3
CH2 H OH H+
CH3 C CH3 C CH2
25oC
2-methylpropene
OH H
tert-butyl alcohol

H2SO4
CH3CH=CH2 + H2 O CH3CHCH3
propene OH
2-propanol
Mechanism of addition reaction of alkenes with H2o/H+
Step 1: Protonation to form carbocation

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

Step 2: Addition of H2O to form a protonated alcohol

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

CH3CHCH3
CH3CHCH3
H+
O H OH H+ = From acid
H
 ANTI-MARKOVNIKOVS RULE: FREE RADICAL
ADDITION OF HYDROGEN BROMIDE
When HBr is added to an alkene in the absence of peroxides
it obey Markovnikovs 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 Markovnikovs 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-Markovnikovs 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.
- examples of peroxide (R-O-O-R):

O O
1) CH3 C O O C CH3

2) CH3CH2 O O CH2CH3

3) di-t-butyl peroxide
 Formation of anti-Markovnikov alcohol
Alkenes goes to hydroboration reaction to form anti-
Markovnikov alcohol.
H2O2, -OH
C C B2H6 C C
H OH
anti-markovnikov

Examples:
H2O2, -OH
CH3CH=CH2 B2H6 CH3CHCH2-OH
propene propanol

CH3 H2O2, -OH

CH3
B2H6
CH3 C CH2 CH3 CH CH2 OH
isobutylene isobutyl alcohol

CH3 CH3
H2O2, -OH
B2H6 CH3CHCHCH3
CH3 CH C CH3
2-methyl-2-butene OH
3-methyl-2-butanol
 OXIDATION REACTIONS
Oxidation: reactions that form carbon-oxygen
bonds.

Oxidation reaction of alkenes:

i) combustion
ii) epoxidation
iii)hydroxylation
iv) Oxidative Cleavage of Alkenes (Ozonolysis
and reaction with hot/warm, acidified KMnO4)
 OXIDATION REACTIONS
i) 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 REACTIONS
ii) Epoxidation
Epoxide / oxirane: a three-membered cyclic ether.
O O O
C C C C R C OH
R C O OH

alkene peroxyacid epoxide (oxirane) acid

Examples of epoxidizing reagents:

O O H
O
Cl O
CH3 C O O H C O OH O

peroxyacetic acid peroxybenzoic acid m-chloroperoxybenzoic acid

(PhCO3H) (MCPBA)
 Examples:

CH3 H
MCPBA CH3 O H
C C
CH3
CH2CI2 C C
H
H CH3

MCPBA
O
CH2CI2
cyclohexene 1,2-epoxycyclohexane
 OXIDATION REACTIONS

iii) Hydroxylation:
- Converting an alkene to a glycol (diol) requires adding a
hydroxyl group to each end of the double bond.
Hydroxylation reagents:
i) cold, dilute, alkaline potassium permanganate (KMnO4)
- mild oxidation conditions
- known as Baeyers reagent

KMnO4 (aq), -OH

C C C C
cold OH OH
glycol / diol
Examples:

KMnO4 (aq), OH-

CH2 CH2 CH2 CH2 MnO2
cold, dilute
ethene OH OH
1,2-ethanediol

KMnO4 (aq), OH-

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

* Also known as Baeyers test

 OXIDATION REACTIONS
iv) Oxidative Cleavage 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' (CH3)2S R R'

C C O3 C C C O O C
R O O H or H2O, Zn/H+
R H R H
ozonide ketone aldehyde
 EXAMPLES:
H
H
i) O3
CH3 C C CH3 CH3C O O C CH3
ii) (CH3)2S
CH3 ethanal CH3
2-methyl-2-butene (aldehyde)
propanone
(ketone)
CH3
CH3
i) O3
CH3 C C CH3 O C CH3
ii) (CH3)2S CH3C O
CH3 CH3
2,3-dimethyl-2-butene propanone propanone
(ketone) (ketone)
H
i) O3 H
CH3CH2 C C CH3 O C CH3
ii) (CH3)2S
CH3CH2 C O
H H
2-pentene propanal ethanal
(aldehyde) (aldehyde)
* (CH3)2S can be replaced with H2O and Zn/H+
 Reaction with hot/warm, acidified KMnO4 (strong oxidizing agent)
- dilute H2SO4 is used to acidify the KMnO4.
- Hot, concentrated alkaline KMnO4 can also be used in this reaction.

1. Oxidation of alkenes
R R' + R R'
KMnO4/H
C C R'' C C H
R'' H OH OH

R R' R R'
C O O C C O
R'' R'' O C
OH H
ketone carboxylic acid ketone aldehyde

2. Oxidation of terminal alkenes

KMnO4/H+
R CH=CH2 R COOH + CO2 + H2O
terminal alkene
Examples:
H H OH OH
KMnO4/H+
CH3CH2C CCH3 CH3CH2C O O C CH3
2-pentene propanoic acid ethanoic acid

CH3 H +
CH3 OH
KMnO4/H
CH3CH2C CCH3 CH3CH2C O O C CH3
3-methyl-2-pentene 2-butanone ethanoic acid

CH3 CH3 +
CH3 CH3
KMnO4/H
CH3CH2C CCH3 CH3CH2C O O C CH3
2,3-dimethyl-2-pentene 2-butanone propanone

H +
OH
KMnO4/H
CH3CH2C=CH2 CH3CH2C=O CO2 H 2O
1-butene propanoic acid
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
KMnO4/H+ OH OH
R C C R' O C R'
R C O
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.

RCOOH and R'COOH RCH=CHR'

O O H H
CH3CH2CH2C-OH and CH3C-OH CH3CH2CH2C=CCH3

butanoic acid ethanoic acid 2-hexene

 UNSATURATION TESTS FOR ALKENES
1) 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 (Baeyers test).
b) Vigorous oxidation conditions using hot,
acidified KMnO4.
Reaction of alkenes with cold, dilute, alkaline KMnO4
(Baeyers 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 / glycol is formed (containing two hydroxyl

groups on adjacent carbon atoms).
 KMnO4 (aq), OH-
C C C C
cold, dilute MnO2
OH OH
a diol / glycol brown precipitate
2) Reactions of alkenes with bromine water or
bromine in inert solvents
- 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
alkene yellow-brown colour Br Br
colourless

H2O
C C Br2(aq) C C C C
alkene yellow-brown colour OH Br Br Br
colourless
 SOURCES OF ALKENES

Cracking of petroleum (refer to chapter alkanes)

The smaller alkenes fractional distillation
 USES OF ALKENES
Ethylene and propylene are the largest-volume industrial
organic chemicals.
Used to synthesis a wide variety of useful compounds.
H H
C C O O
oxidize
H H n CH3 C OH
CH3 C H
polyethylene acetaldehyde acetic acid

polymerize
oxidize
O O2 H H Cl2 CH2 CH2
H2C CH2 Ag catalyst C C
ethylene oxide H H CI CI
ethylene ethylene dichloride
H+ H2O NaOH
H2O catalyst
CH2 CH2 CH3 CH2 H CI
OH OH OH H C C H
ethylene glycol ethanol vinyl chloride
 SOME OF THE MOST IMPORTANT ADDITION POLYMERS

POLYMER POLYMER USES MONOMER POLYMER

FORMULA REPEATING UNIT
Polyethylene Bottles, bags, films
CH2=CH2 CH2 CH2 n

Polypropylene Plastics, olefin fibers H CH3

C C CH3
H H CH2 CH n

Polystyrene Plastics, foam

insulation H
C C H2C C n
H H H

Poly(isobutylene) Specialized rubbers

H CH3
CH3
C C CH2 C n
H CH3 CH3
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 polymerize H CI H CI H CI
H C C CI C C C C C C
vinyl chloride H H H H n H H
poly(vinyl chloride)
PVC, "vinyl"
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.
 Ethanol

Ethanol is used extensively as a

Solvent in the manufacture of varnishes and
perfumes;
Preservative for biological specimens
Preparation of essences and flavorings;
Medicines and drugs
Disinfectant and in tinctures (e.g., tincture of iodine)
uel and gasoline additive