UNSATURATED

HYDROCARBONS
1
 • Unsaturated hydrocarbons
enhance our lives in many ways:
1. Polyethylene plastic bags and bottles
2. Polystyrene Styrofoam cups
3. Plastic wraps
4. Essential oils in plants contain multiple bonds
between carbon atoms.
– Cosmetics, medicines, flavorings, perfumes
5. Hydrocarbons also form rings of carbon atoms
(aromatics)
– Detergents, insecticides, and dyes 2
 Bonding in
Unsaturated
Hydrocarbons
3
• Alkenes contain carbon-carbon double
bonds.

• Alkynes contain carbon-carbon triple

bonds.

• Aromatic compounds contain

benzene rings.

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The four orbitals available for bonding in
alkenes are three sp2 orbitals and one p
orbital.

Figure 20.1 Schematic hybridization of 2s22px12py1

orbitals of carbon to form three sp2 electron orbitals
and one p electron orbital 5
Nomenclature
of Alkenes
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The general formula for alkenes is:

CnH2n

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 IUPAC RULES FOR NAMING
ALKENES
1. Select the longest continuous carbon-
carbon chain that contains the double bond.
2. Name this parent compound as you
would an alkane, but change the –ane
ending to –ene.

CH3CH2CH3 propane CH3CH=CH2 propene

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 IUPAC RULES FOR NAMING
ALKENES
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
atoms to indicate the position of the double
bond. Place this number in front of the
alkene name.
CH3CH=CHCH3
CH3CH2CH2CH=CH2 9
 IUPAC RULES FOR NAMING
ALKENES
4. Branch chains and other groups are
treated as in naming alkanes, by numbering
and assigning them to the carbon atom to
which they are bonded.
H2
CH3 H2C C CH3
H2 H H2 H2 H
H3C CH C C CH2 H3C C C CH C CH2
5 4 3 2 1 6 5 4 3 2 1
4-methyl-1-pentene 3-propyl-1-hexene 10
How would we write the structural
formula for 4-methyl-2-pentene?

CH3

H
C CH
H3C C CH3
H
11
 Write a structural formula for:
7-methyl-2-octene

H H2 H2
C C C CH3
H3C C C CH
H H2

CH3

12
 Name this compound:

H2 H2
C C CH3
H3C C C
H2

CH2
2-ethyl-1-pentene
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Geometric Isomerism
in Alkenes 14
 Geometric Isomerism in
Alkenes
• This restricted rotation in a molecule
gives rise to a type of isomerism known
as geometric isomerism.

• Isomers that differ from each other only

in the geometry of their molecules and
not in the order of their atoms are
known as geometric isomers.
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 Geometric Isomers in
Alkenes
Cl Cl H Cl

C C C C

H H Cl H

cis-1,2-dichloroethene trans-1,2-dichloroethene
(bp = 60.1 C) (bp = 48.4 C)
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An alkene shows cis-trans isomerism
when each carbon atom of the double
bond has two different kinds of groups
attached to it.
a a a b

C C C C

b b b a

cis isomer trans isomer

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 An alkene does not show cis-trans
isomerism if one carbon of the double
bond has two identical groups attached to
it.

H H H3C CH3

C C
two groups
C C
the same
H H H3C H

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 Draw a structure for
cis-5-chloro-2-hexene
• The compound contains 6 carbons with
a C=C between carbons 2 and 3, and a
Cl atom on carbon 5. CH 3

H3C H2C CH

C C Cl

H H
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Is the compound below the cis
or trans isomer?

H3C CH3

C C

H H2C CH3

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 DIENES
• A compound with two C=C is called a
diene.
H
C CH2
H2C C
H

1,3-butadiene
• A compound with three C=C is called a
triene. 21
CYCLOALKENES
22
 CYCLOALKENES

cyclohexene
1

2 2

1
cyclopentene
23
 CYCLOALKENES

CH3 CH3
5 4
1 3

4 2 5 2

3 6 1
1-methylcyclopentene CH3
1,3-dimethylcyclohexene
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SEATWORK

Draw the structure for the following

• 3,4-dimethyl-2-pentene
• 3-ethyl-2-methyl-1-hexene
• 3-isopropylcyclopentene
• 2-chloro-1,3-heptadiene
• 1,4,6-cyclohexatriene
Name the following:

1.

2. 3.

4.
 Preparation and
Physical Properties of
Alkenes

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 PREPARATION OF
ALKENES

• Cracking
• Dehydration of Alcohols

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 CRACKING

Alkane (CnH2n+2)Heat
→ Mixture of alkenes + Alkanes + H2 (g)
catalyst

~500°C
2CH3CH2CH3 → CH3CH=CH2 + CH2=CH2 + CH4 + H2

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 DEHYDRATION OF
ALCOHOLS
• Dehydration involves the elimination of
a molecule of water from a reactant
molecule.
H H H H
conc. H2SO4
H3C C C CH3 H3C C C CH3 + H2O
heat
H OH

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Physical Properties of Alkenes
• Alkenes have physical properties
very similar to the corresponding
alkanes.

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Chemical Properties
of Alkenes

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ADDITION REACTIONS OF
ALKENES

 H2
 Br2 and Cl2
 HBr, HCl
 H2SO4
 H20

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 HYDROGENATION
Addition of H2

H H H H

Pt, 25 C
H3C C C CH3 + H H3C C C CH3
2
1 atm
H H

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 ADDITION OF X2
• Bromination (Br2) or Chlorination (Cl2)

H H H H

H3C C C CH3 + Br H3C C C CH3

2

Br Br

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 ADDITION OF HX

• Hydrobromination (HBr) or Hydrochlorination

(HCl)

H H H H

H3C C C CH3 + HCl H3C C C CH3

H Cl
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 ADDITION OF H2SO4

H H H H

H3C C C CH3 + HOSO3H H3C C C CH3

H OSO3H

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 ADDITION OF H2O

H H H H
+
H
H3C C C CH3 + H2O H3C C C CH3

H OH

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 H
H3C C CH2

Cl H
H (about 100% yield)
H3C C CH2 + H-Cl

H
H3C C CH2

H Cl
(trace)
ADDITION OF HX TO AN
UNSYMMETRICAL ALKENE 39
 Reaction Mechanism

H H -
H3C C CH2 + H-Cl H3C C CH2 + Cl
3 2 1
H
isopropyl carbocation

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 Reaction Mechanism

H - H
H3C C CH2 + Cl H3C C CH2

H Cl H
2-chloropropane

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 CARBOCATION
• An ion in which a carbon atom has a
positive charge.

H H C C

H C C C C C C C

H H H C
methyl primary (1o) secondary (2o)
carbocation carbocation carbocation o
tertiary (3 )
carbocation
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• The order of stability of carbocations and
hence the ease with which they are
formed is:

H H C C

H C C C C C C C

H H H C
methyl primary (1o) o
secondary (2 )
carbocation carbocation carbocation tertiary (3 )
o

carbocation

increasing stability 43
 MARKOVNIKOV’S RULE

• When an unsymmetrical molecule

such as HX (HCl) adds to a carbon-
carbon double bond, the hydrogen
from HX goes to the carbon atom
that has the greater number of
hydrogen atoms.

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Markovnikov’s Rule
H
H3C C CH2

Cl H
H (about 100% yield)
H3C C CH2 + H-Cl

H
H3C C CH2

H Cl
(trace)
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 OXIDATION AT THE C=C
BOND
• Baeyer Test

H2C CH2 + KMnO4 (aq) + H2O H2C CH2 + MnO2 + KOH

ethene (purple) (brown)
(ethylene) OH OH
1,2-ethanediol
(ethylene glycol)
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 TEST FOR UNSATURATION
• Test with Bromine water

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• Write the equation and formulas for the
organic products formed when
2-methyl-1-butene reacts with:

1. H2, (Pt/25°C)
2. Cl2
3. HCl
4. H20, ( H+ )

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