ORGANIC CHEMISTRY

CHM 207

CHAPTER 3
ALKENES
 SUBTOPICS
Naming alkenes and cycloalkenes according to IUPAC
and common names

Physical properties of alkenes:

a) boiling points and densities
b) solubility
c)polarity

Reactions of alkenes :
a) Addition reaction
b) Oxidation
c) Oxidation cleavage of alkenes by ozonolysis
Unsaturation tests of alkenes:
a) Reactions of alkenes with KMnO4
b) Reactions of alkenes with bromine.

Polimerization

Uses of alkenes:
a) PE
b) PVC
c) Ethanol
 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.
 Carbon: 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
 CYCLOALKENES
 Contains C=C in the ring

cyclopropene cyclobutene cyclopentene cyclohexene

 Nomenclature of cycloalkenes:
- Similar to that alkenes
- Number the cycloalkane so that the double bond is between
C1 and C2 and so that the first substituent has as low a
number as possible.
* Double bond always located between C1 and C2.
6 1
CH3 5 6 2 CH2CH3
5 1 4 1
4 2 5 3
3 2 4
3
1-methylcyclohexene 1,5-dimethylcyclopentene IUPAC name: 2-ethyl-1,3-cyclohexadiene
New IUPAC name: 2-ethylcyclohexa-1,3-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).
 1. 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
propene, μ = 0.35 D Vector sum = Vector sum = 0
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.

H H3C CH3 H3C H

C C C C C C
H H H H CH3
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.

H H3C CH3 H3C H

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

More reactive than alkanes because:

i) 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.

ii) 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.

iii) 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 :
a) Addition reaction:
i) Catalytic hydrogenation
ii) Addition of halogens
- In inert solvent
- In water / aqueous medium
iii) Addition of hydrogen halides ((Markovnikov’s rule and
anti-Markovnikov rule)
iv) Addition reaction with acidified water (H3O+):hydration
of alkenes (Markovnikov’s rule and anti-Markovnikov
rule)

b) Oxidation:
i) combustion
ii) epoxidation
iii) hydroxylation

c) Oxidation cleavage of alkenes by ozonolysis

 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, -C≡C- in alkynes,
C=O in aldehydes and ketones)
 Addition reactions to double bonds have these 3
characteristics:
i) the π 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
 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.

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

Pt
CH3CH2CH2CH2CH CH2 H2 CH3CH2CH2CH2CH2CH3
low pressure
hexene hexane
 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.

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
 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
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:
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
 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.
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)
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.

- 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
MARKOVNIKOV’S RULE

CH3CHCH2
3 2 1 H Cl
CH3CH=CH2 HCl
1-chloropropane
Propene
CH3CHCH2
Cl H
2-chloropropane
(major product)
according to Markov
rules
 4. ADDITION REACTION WITH ACIDIFIED WATER:
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 atm.
- 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
 Markovnikov’s 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
 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.
- 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
 1. 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

 2. 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
 3. 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 Baeyer’s reagent

KMnO4 (aq), -OH

C C C C
cold OH OH
glycol / diol
ii) Osmium tetroxide (OsO4) and H2O2

C C OsO4 H2O2 C C
OH OH
glycol
Examples:

KMnO4 (aq), OH-

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

OsO4, H2O2
CH3 CH CH2 CH3 CH CH2
propene OH OH
1,2-propanediol
 OXIDATION CLEAVAGE OF ALKENES BY
OZONOLYSIS
 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

H+ = acetic acid
 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+
 DETERMINATION OF THE POSITION OF THE
DOUBLE BOND
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
 UNSATURATION TESTS FOR ALKENES

1) Reactions of alkenes with KMnO4

- KMnO4 is a strong oxidizing 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 / 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
 POLIMERIZATION

 Polymer: A large molecule composed of many

smaller repeating units (the monomers) bonded
together.
 Alkenes serve as monomer for common
polymers such as polyethylene, polypropylene,
polystyrene and poly(vinyl chloride).
 Alkenes undergoes addition polymerization
(rapid addition of one molecule at a time to a
growing polymer chain and no other molecules
are formed.).
Examples:
Monomer Polymer repeating units
 SOME OF THE MOST IMPORTANT ADDITION POLYMERS

MONOMER POLYMER
POLYMER POLYMER USES
FORMULA REPEATING UNIT
Polyethylene Bottles, bags,
films CH2 CH2 n
CH2=CH2

Polypropylene Plastics, olefin H CH3

fibers C C CH3
H H CH2 CH n

Polystyrene Plastics, foam

insulation H
C C H2C C n
H H H

Poly(isobutylene) Specialized
H CH3
rubbers CH3
C C CH2 C n
H CH3 CH3
 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
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.
 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.