Unsaturated Hydrocarbons

1
 Chapter Outline
Importance of Unsaturated Hydrocarbons
Bonding in Unsaturated Hydrocarbons
Nomenclature of Alkenes
Cycloalkenes

2
 Chapter Outline (continued)
Alkynes: Nomenclature and Polycyclic Aromatic
Preparation Hydrocarbons
Physical and Chemical Sources and Physical
Properties of Alkynes Properties of Aromatic
Aromatic Hydrocarbons: Hydrocarbons
Structure Chemical Properties of
Naming Aromatic Aromatic Hydrocarbons
Hydrocarbons

3
 • 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 4
Bonding in Unsaturated
Hydrocarbons

5
• Three Families of Homologous Compounds
that Contain Multiple Bonds

• Alkenes contain carbon-carbon double

bonds.
• Alkynes contain carbon-carbon triple
bonds.
• Aromatic compounds contain benzene
rings.

6
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 7
Figure 20.2 (a) A single sp2 electron orbital and (b) a
side view of three sp2 orbitals all lying in the same
plane with a p orbital perpendicular to the three sp2
8
orbitals.
• The carbon-carbon pi () bond is much weaker and,
as a consequence, much more reactive than the
carbon-carbon sigma () bond.

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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 2- butene
CH3CH2CH2CH=CH2 1-pentene
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 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

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How would we write the structural
formula for 4-methyl-2-pentene?
• The name indicates:
– Five carbons in the longest chain
– A double bond between carbons 2 and 3
– A methyl group on carbon 4
CH3

H
C CH
H3C C CH3
H 15
 Write a structural formula for:
7-methyl-2-octene
• Octene indicates an 8-carbon chain
• The chain contains a C=C between carbons
2 and 3.
• There is a –CH3 group on carbon 7

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

CH3 16
 Name this compound:
H2 H2
C C CH3
H 3C C C
H2

CH2
• Longest chain containing C=C is 5
carbons
• 2-ethyl-1-pentene
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Cycloalkenes

18
 Cycloalkenes
• As the name implies, cycloalkenes are cyclic
compounds that contain a C=C in the ring.
• The carbons of the double bond are assigned
numbers 1 and 2.
cyclohexene
1

2 2

1
cyclopentene
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 Cycloalkenes
CH3 CH3
5 4
1 3

4 2 5 2

3 6 1
1-methylcyclopentene CH3
1,3-dimethylcyclohexene
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 Physical Properties of Alkenes
• Alkenes have physical properties very
similar to the corresponding alkanes.

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Oxidation

22
 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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 Oxidizing Agents
• 1. KMnO4
• 2. Oxygen of the air

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 Some Effects of Oxidizing Agents

• 1. premature aging and cracking of

automobile tires in smoggy
atmospheres occur because ozone
attacks the double bonds in rubber
molecules.

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 Some Effects of Oxidizing Agents

• 2. Cooking oils and fats sometimes

develop disagreeable odors and flavors
because oxygen of the air reacts with
double bonds present

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 Some Effects of Oxidizing Agents

• 3. Potato chips, because of their large

surface area, are particularly subject to
flavor damage caused by oxidation of
the unsaturated cooking oils.

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Alkynes: Nomenclature and
Preparation

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• The formation of a triple bond between carbon
atoms, as in acetylene, CHCH, may be visualized
as shown below.
• These pi bond electrons are not as tightly held by the
carbon nuclei as the sigma bond electrons.
Acetylene, consequently, is a very reactive
substance.

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IUPAC Rules for Naming Alkynes
The rules for naming alkynes are the
same as those for alkenes, but the
ending –yne is used to indicate the
presence of a triple bond.
H2
H3C C C CH
1-butyne 30
31
 Preparation of Alkynes
• Acetylene can be prepared from
calcium carbide and water.
– CaC2 + 2H2O  HCCH + Ca(OH)2
• Acetylene is also prepared by the
cracking of methane at 1500 °C.
– 2CH4  HCCH + 3H2

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Physical and Chemical
Properties of Alkynes

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 Physical Properties of Alkynes
• Acetylene is a colorless gas with little
odor when pure.
• Acetylene is insoluble in water and is a
gas at normal temperature and
pressure.

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Aromatic Hydrocarbons:
Structure

35
 Benzene
• Benzene and all substances with
structures and chemical properties that
resemble benzene are classified as
aromatic compounds.

Representations of Benzene
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 Bonding in Benzene
• The electrons are not attached to particular
carbon atoms but are delocalized and
associated with the entire molecule.
• This electronic structure imparts unusual
stability to benzene and is responsible for
many of the characteristic properties of
aromatic compounds.

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 Bonding in Benzene

Figure 20.5 (a)

sp2-sp2 orbital
overlap to form
the carbon ring
structure.

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 Bonding in Benzene

Figure 20.5 (b)

carbon-
hydrogen bonds
formed by sp2-s
orbital overlap
and overlapping
p orbitals.

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 Bonding in Benzene

Figure 20.5 (c) pi electron clouds above and below

the plane of the carbon ring.
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Naming Aromatic
Compounds
41
Naming Substituted Benzene Compounds
• A substituted benzene is derived by
replacing one or more hydrogen atoms
of benzene by another atom or group
of atoms.
• Monosubstituted benzene has the
formula C6H5G, where G is the group
replacing a hydrogen atom.

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 Monosubstituted Benzenes
• Some monosubstituted benzenes are
named by adding the name of the
substituent group as a prefix to the
word benzene.
CH2CH3 Br

O2N Cl

nitrobenzene ethylbenzene chlorobenzene bromobenzene

43
 • Certain monosubstituted benzenes have
special names.
CH=CH2 OH

CH3

H2N
styrene phenol aniline
O O

C C toluene
OH H

benzoic acid benzaldehyde

44
 Phenyl Group
• The C6H5- group is known as the phenyl
group, and the name phenyl is used to name
compounds that cannot easily be named as
benzene derivatives.
1 C H 3
2 H 2
C H 3 4 5 C
C H C H 2 C H 3

C l

3 -c h lo r o -2 -p h e n y lp e n ta n e d ip h e n y lm e th a n e

Polychlorinated biphenyls (PCB)

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 Polysubstituted Benzenes
• When there are more than two
substituents on a benzene ring, the
carbon atoms in the ring are numbered
starting at one of the substituted
groups.
• Numbering must be done in the
direction that gives the lowest possible
numbers to the substituent groups.
46
 Polysubstituted Benzenes
CH3 OH

O2N 1 NO2 1 Cl
6 2 6 2

5 3 5 3
4 Br
4
NO2 5-bromo-2-chlorophenol
2,4,6-trinitrotoluene (TNT)

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Polycyclic Aromatic
Compounds

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Polycyclic Aromatic Hydrocarbons

naphthalene phenanthrene

49
anthracene
 Sources and Physical
Properties of Aromatic
Hydrocarbons

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Sources of Aromatic Hydrocarbons
• The aromatic hydrocarbons, such as
benzene, toluene, xylene, naphthalene,
and anthracene, were first obtained in
significant quantities from coal tar.
• Coal  Coke + Coal gas + Coal tar


• Because of the great demand for

aromatic hydrocarbons, processes were
devised to obtain them from petroleum.
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Properties of Aromatic Hydrocarbons
• Aromatic hydrocarbons are essentially
nonpolar substances, insoluble in water but
soluble in many organic solvents.
• They are liquids or solids and usually have
densities less than that of water.
• Aromatic hydrocarbons burn readily,
usually with smoky yellow flames as a
result of incomplete carbon combustion.

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