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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