Chapter 13
Unsaturated
Hydrocarbons
Chapter 13
Table of Contents
13.1Unsaturated Hydrocarbons
13.2 Characteristics of Alkenes and Cycloalkenes
13.3 IUPAC Nomenclature for Alkenes and Cycloalkenes
13.4 Line-Angle Structural Formulas for Alkenes
13.5 Constitutional Isomerism in Alkenes
13.6 Cis-Trans Isomerism in Alkenes
13.7 Naturally Occurring Alkenes
13.8 Physical Properties of Alkenes and Cycloalkenes
13.9 Chemical Reactions of Alkenes
13.10 Polymerization of Alkenes: Addition Polymers
13.11 Alkynes
13.12 Aromatic Hydrocarbons
13.13 Names for Aromatic Hydrocarbons
13.14 Aromatic Hydrocarbons: Physical Properties and Sources
13.15 Chemical Reactions of Aromatic Hydrocarbons
13.16 Fused-Ring Aromatic Hydrocarbons
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Section 13.1
Unsaturated Hydrocarbons
• Unsaturated hydrocarbon: a hydrocarbon with one or
more carbon–carbon multiple bonds (double bonds,
triple bonds, or both).
– Physical properties similar to those of saturated
hydrocarbons.
– Chemical properties are distinct.
– Chemically more reactive than saturated
hydrocarbons.
– Reactivity of unsaturated hydrocarbons is due
carbon–carbon multiple bond(s).
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Section 13.1
Unsaturated Hydrocarbons
Functional Group
• Functional group: Part of an organic molecule responsible
for most of its chemical reactions.
• Unsaturated hydrocarbon functional group: Carbon–
carbon multiple bonds.
• Subdivided into 3 groups:
– Alkenes: Contain one or more carbon–carbon double
bonds
– Alkynes: contain one or more carbon–carbon triple
bonds
– Aromatic hydrocarbons: A special type of “delocalized”
bonding that involves a six membered carbon ring
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Section 13.2
Characteristics of Alkenes and Cycloalkenes
• Alkenes: An alkene is an acyclic
unsaturated hydrocarbon that
contains one or more carbon –
carbon double bonds.
• Functional group: C=C group.
• Naming: Names end with an “-ene”
versus
–The -ene ending means a
double bond is present.
• General molecular formula: CnH2n
• Two simplest alkenes are ethene
(C2H4) and propene (C3H6).
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Section 13.2
Characteristics of Alkenes and Cycloalkenes
• The arrangement of bonds about the carbon atom in
alkanes is tetrahedral.
• The arrangement of bonds about carbon atoms with
double bonds in alkenes is trigonal planar.
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Section 13.2
Characteristics of Alkenes and Cycloalkenes
• Cycloalkanes: A cyclic unsaturated
hydrocarbon with one or more carbon–
carbon double bonds within the ring
system.
• Cycloalkenes with only one double bond
have the general molecular formula CnH2n-
2.
• The simplest cycloalkene: Cyclopropene
(C3H4), a three-membered carbon ring
system with one double bond.
• Cycloalkenes with more than one double
bond are possible but are not common.
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Section 13.3
IUPAC Nomenclature for Alkenes and Cycloalkenes
IUPAC Rules
Rule 1: Replace the alkane suffix -ane with the suffix -ene
Rule 2: Select as the parent carbon chain the longest
continuous chain of carbon atoms that contains both
carbon atoms of the double bond.
Rule 3: Number the parent carbon chain beginning at the
end nearest to the double bond. If the double bond is
equidistant from both ends of the parent chain, begin
numbering from the end closer to a substituent.
Rule 4: Give the position of the double bond in the chain as
a single number, which is the lower-numbered carbon
atom participating in the double bond.
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Section 13.3
IUPAC Nomenclature for Alkenes and Cycloalkenes
IUPAC Rules
Rule 5: Use the suffixes -diene, -triene, -tetrene, and so on when more
than one double bond is present in the molecule.
Rule 6: A number is not needed to locate the double bond in
unsubstituted cycloalkenes with only one double bond because
that bond is assumed to be between carbons 1 and 2.
Rule 7: In substituted cycloalkenes with only one double bond, the
double-bonded carbon atoms are numbered 1 and 2 in the
direction (clockwise or counterclockwise) that gives the first-
encountered substituent the lower number.
Rule 8: In cycloalkenes with more than one double bond within the ring,
assign one double with numbers 1 and 2 and the other double
bonds the lowest numbers possible.
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Section 13.3
IUPAC Nomenclature for Alkenes and Cycloalkenes
Practice Exercise
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Section 13.3
IUPAC Nomenclature for Alkenes and Cycloalkenes
Practice Exercise
Answers:
a. 5-Methyl-2-hexene
b. 3-Ethyl-4-methylcyclohexene
c. 1,3-Butadiene
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Section 13.3
IUPAC Nomenclature for Alkenes and Cycloalkenes
Common Names (Non-IUPAC Names)
Common Names (Non-IUPAC Names):
• Common names exist for alkenes
• There is no scientific basis for assigning such names
therefore one must have to memorize them
• Two most common names for alkenes are:
– CH2=CH2 - Ethylene (IUPAC name – Ethene)
– CH2=CH2-CH3 – Propylene (IUPAC name – propene)
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Section 13.3
IUPAC Nomenclature for Alkenes and Cycloalkenes
Alkenes as Substituents
• Alkenes substituents are called alkenyl groups
• Most Frequently encountered alkenyl groups:
– Methylidene (one- carbon)- Common name:
methylene
– Ethenyl (two- carbon) - Common name: vinyl
– 2-propenyl (three-carbon) - Common name: allyl
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Section 13.4
Line-Angle Structural Formulas for Alkenes
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Section 13.5
Constitutional Isomerism in Alkenes
• Constitutional isomerism possible in alkenes as well
• There are more alkene isomers possible for a given
number of carbon atoms than there are alkane isomers
• Constitutional isomerism: Same molecular formula but
different structural formulas
• Positional isomers: Same number of carbon and
hydrogen atoms but the position of the C=C is different
• Skeletal isomers (Cis-Trans): Each C atom in the double
bond contains the same groups but their position are
different
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Section 13.6
Cis-Trans Isomerism in Alkenes
• Cis–Trans isomerism in alkenes results from the
structural rigidity associated with C=C double bonds.
• Rotation about C=C (or CΞC) is not possible
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Section 13.6
Cis-Trans Isomerism in Alkenes
Isomers
• Isomers: Have same molecular formula and have
different structural formula.
• Cis-Trans Isomers:
– Conditions: Each carbon atom in the double bond contain two
different groups attached to it.
– Cis isomer: Two similar groups on same side of double bond
– Trans isomer: Similar groups on opposite sides of the double
bond
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Section 13.6
Cis-Trans Isomerism in Alkenes
Practice Exercise
• Identify the following as cis or trans isomers, or neither:
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Section 13.6
Cis-Trans Isomerism in Alkenes
Practice Exercise
• Identify the following as cis or trans isomers, or neither:
Trans
Neither
Neither
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Section 13.7
Naturally Occurring Alkenes
Pheromones
• A pheromone is a compound used by insects (and some
animals) to transmit a message to other members of the
same species.
• Pheromones are often alkenes or alkene derivatives.
• The biological activity of pheromones is C=C bonds
present in a cis or a trans configuration.
• Example: The sexual attractant of the female silkworm is
a 16-carbon alkene derivative containing an -OH group.
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Section 13.7
Naturally Occurring Alkenes
Terpenes
• Organic compounds whose carbon skeleton is
composed of two or more 5-carbon isoprene structural
units
• Isoprene (2-methyl-1,3-butadiene) is a five-carbon diene
• Terpenes are widely distributed in nature
• >22,000 Terpenes are found in biological systems and
are responsible for the characteristic odors of many trees
and plant fragrances
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Section 13.7
Naturally Occurring Alkenes
• Examples of
naturally occurring
terpenes
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Section 13.8
Physical Properties of Alkenes and Cycloalkenes
• Physical properties are similar to alkanes
• The boiling and melting point of an alkene is usually
lower than that of an alkane with same number of carbon
atoms
• Alkenes with 2 to 4 carbon atoms are gases at room
temperature
• Unsubstituted alkenes with 5 to 17 carbon atoms are
liquids
• Alkenes with >17 C atoms are solids
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Section 13.8
Physical Properties of Alkenes and Cycloalkenes
A Physical-State Summary
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Section 13.9
Chemical Reactions of Alkenes
Chemical Properties
• Combustion: Alkenes are very flammable and the
combustion products are carbon dioxide and water.
• Addition Reactions: Atoms or group of atoms are added
to each carbon atom of a multiple bond.
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Section 13.9
Chemical Reactions of Alkenes
Alkene Addition Reaction
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Section 13.9
Chemical Reactions of Alkenes
• Symmetric Addition Reactions:
• Hydrogenation reaction: In alkene hydrogenation a
hydrogen atom is added to each carbon atom of a
double bond.
– Catalyst (usually Ni or Pt)
• Halogenation reaction: In alkene halogenation a halogen
atom is added to each carbon atom of a double bond.
– No catalyst is needed
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Section 13.9
Chemical Reactions of Alkenes
Unsymmetrical Addition Reactions
• Markovnikov’s Rule: When an unsymmetrical molecule
HQ (e.g., H-Cl, H-OH, H-F) reacts with an unsymmetrical
alkene, the hydrogen atom from the HQ becomes
attached to the unsaturated carbon atom that already
has the most hydrogen atoms
• Two types of unsymmetrical addition reactions:
– Hydration: Addition of Water
• H2SO4 is a catalyst that is why written on arrow.
• Catalysts speed-up reactions.
– Hydrohalogenation
• Addition of H-X (X = F, Cl, Br, I)
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Section 13.10
Polymerization of Alkenes: Addition Polymers
• Polymers are macromolecules in which small units
(monomers) are repeated again and again.
• Examples: Polyethylene, polypropylene, polyester etc.
• Polymers are huge molecules so their molecular
formulas are not written.
• The simplest repeating unit in parenthesis with “n” as
subscript to shows the number of monomers.
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Section 13.10
Polymerization of Alkenes: Addition Polymers
• Alkenes and substituted alkenes form addition polymers.
• An addition polymer is a polymer in which the monomers
simply “add together” with no other products formed
besides the polymer.
• Addition polymerization is similar to the addition
reactions described previously except that there is no
reactant other than the alkene or substituted alkene.
• Example: Formation of polyethylene
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Section 13.10
Polymerization of Alkenes: Addition Polymers
Substituted-Ethene Addition Polymers
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Section 13.10
Polymerization of Alkenes: Addition Polymers
Butadiene-Based Addition Polymers
• Polymerization of 1,3-butadiene results in a butadiene
polymer
• These polymers contain double bonds (unsaturated
polymers)
• The polymers are flexible
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Section 13.10
Polymerization of Alkenes: Addition Polymers
Addition Copolymers
• A copolymer is a polymer in which two different
monomers are present.
• Examples:
– Saran Wrap: a polymer chloroethene (vinyl chloride)
and 1,1-dichloroethene.
– Styrene–butadiene rubber: Leading synthetic rubber -
contains 1,3-butadiene and styrene in a 3:1 ratio
(major ingredient in automobile tires)
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Section 13.11
Alkynes
• Alkyne: An acyclic unsaturated hydrocarbon that
contains one or more carbon–carbon triple bonds.
• Alkyne functional group: CΞC group
• Naming: Names end with a suffix -yne
• General formula: CnH2n-2
• Simplest alkynes: C2H2, C3H4
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Section 13.11
Alkynes
IUPAC Nomenclature for Alkynes
• The rules for naming alkynes are identical to those used
to name alkenes except the ending -yne is used instead
of -ene.
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Section 13.11
Alkynes
Isomerism and Alkynes
• cis–trans isomerism not possible because of the
linearity (180º angles) about an alkyne’s triple bond
• Constitutional isomers are possible—both relative to
the carbon chain (skeletal isomers) and to the position
of the triple bond (positional isomers).
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Section 13.11
Alkynes
Physical Properties of Alkynes
• Physical properties: Similar to those of alkenes and
alkanes
• Insoluble in water but soluble in organic solvents
• Densities less than that of water
• Boiling points increase with molecular mass
• Low-molecular-mass alkynes are gases at room
temperature
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Section 13.12
Aromatic Hydrocarbons
Benzene
• Contains benzene ring with
alternate double and single
bonds
• Double bonds are different than Usually written as
alkenes
• These are called delocalized (=)
bonds: All C-C bonds are similar
• Resonance structures (differ
only in arrangement of electrons
Resonance Structures
of Benzene
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Section 13.13
Names for Aromatic Hydrocarbons
• Name the substituent followed by the name benzene.
• When more than one substituent present, indicate the
position by number followed by name of the substituent
and the name benzene
– No need to indicate position if there is only one substituent
– Positions 1,2 are also know as Ortho positions
– Positions 1,3 are also know as Meta positions
– Positions 1,4 are also know as Para positions
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Section 13.14
Aromatic Hydrocarbons: Physical Properties and Sources
• Insoluble in water
• Soluble in non-polar solvents like hydrocarbons etc.
• Less dense than water therefore floats on water
• Benzene is colorless, flammable liquid, burns with sooty
flame
• Petroleum is the primary source of aromatic
hydrocarbons
– Gasoline has significant amount of benzene in it
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Section 13.15
Chemical Reactions of Aromatic Hydrocarbons
• Aromatic hydrocarbons do not readily undergo the addition
reactions because of delocalized bonding system (resonance)
• Benzene undergoes substitution reactions
• Two important types of substitution reactions for benzene and other
aromatic hydrocarbons are alkylation and halogenation
• Alkylation
• Halogenation
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Section 13.16
Fused-Ring Aromatic Hydrocarbons
• Fused-ring aromatic hydrocarbons: Aromatic
hydrocarbon whose structure contains two or more rings
fused together and two carbon rings share a pair of
carbon atoms
• Examples:
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