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CHM 257
CHAPTER 3
ALKENES
SUBTOPICS
Naming alkenes according to IUPAC and common names
Preparation of alkenes:
i) dehydration of alcohols
ii) dehydrohalogenation of haloalkanes
iii) dehalogenation of dihalides
iv) reduction of alkynes
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.
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.
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
cis-2-pentene trans-2-pentene
CH3 CH3
b) CH3
a)
H3C CHCH3
C C
H CH3
c)
Cl
Cl
PHYSICAL PROPERTIES OF
ALKENES
Boiling points and densities:
- relatively nonpolar.
Polarity:
Vinylic bonds
Dehydration of alcohols
Dehydrohalogenation of haloalkanes /
alkyl halides
Dehalogenation of dihalides
Reduction of alkynes
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).
H
H H
H C C H C C H2SO4
H H
H H
HSO4-
Mechanism of dehydration of 2-
butanol:
OH
Conc. H2SO4
CH3CH2CHCH3 CH3CH=CHCH3 CH3CH2CH=CH2 H2O
Heat
OH H O H
CH3CH2CHCH3 H OSO3H CH3CH2CHCH3 HSO4-
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
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
- Example:
H H
NaOH / ethanol
H H
H C C H
reflux H C C H + HBr
H Br
bromoethane ethene hydrogen bromide
Saytzeff / Zaitsev’s 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
iii) Dehalogenation of dihalides
Example
Br H
Ph NaI Ph H
C C C C + Br2
Ph Acetone H
H Br Ph
iv) Reduction of alkynes
alkynes to cis-alkenes
Lindlar's catalyst R R'
R C C R' + H2 C C
or Ni2B (Nickel boride) H H
alkynes
cis-alkene
alkynes to trans-alkenes
Na, NH3 R H
R C C R' C C
H R'
trans-alkene
Na, NH3 = sodium metal in liquid ammonia
EXAMPLES:
CH3CH2 CH2CH3
H2, Pd/BaSO4, quinoline
CH3CH2 C C CH2CH3 C C
or Ni2B (Nickel boride)
3-hexyne H H
cis-3-hexene
CH3CH2 H
Na, NH3
CH3CH2 C C CH2CH3 C C
3-hexyne
H CH2CH3
trans-3-hexene
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.
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
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-
C C E Y C C Y-
δ+ E
carbocation
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
Pt
CH3CH2CH2CH2CH CH2 H2 CH3CH2CH2CH2CH2CH3
low pressure
hexene hexane
Mechanism of Catalytic Hydrogenation
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
X X
C C C C
X
* 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
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:
CH3CHCH2
3 2 1 H Cl
CH3CH=CH2 HCl
1-chloropropane
Propene
CH3CHCH2
Cl H
2-chloropropane
(major product)
according to Markovni
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)
H H R R
H C H R C H R C H R C R
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
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)
CH3CHCH3
CH3CHCH3
H+
O H OH H+ = From acid
H
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.
peroxide
CH3CH=CH2 HBr CH3CH2CH2Br
1-bromopropane
(major product)
anti-Markovnikov's orientation
Anti-Markovnikov’s addition:
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 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.
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 Baeyer’s reagent
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
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.
O O H H
CH3CH2CH2C-OH and CH3C-OH CH3CH2CH2C=CCH3
H2O
C C Br2(aq) C C C C
alkene yellow-brown colour OH Br Br Br
colourless
SOURCES OF ALKENES
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
Poly(isobutylene) Specialized
H CH3
rubbers CH3
C C CH2 C n
H CH3 CH3
POLYETHENE (PE)