WILLIAM H.
BROWN
THOMAS POON
www.wiley.com/college/brown
CHAPTER FOUR
Alkenes and
Alkynes
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Unsaturated Hydrocarbons
• Unsaturated Hydrocarbon: A hydrocarbon that
contains one or more carbon-carbon double or triple
bonds or benzene-like rings.
– Alkene: contains a carbon-carbon double bond and has
the general formula CnH2n.
– Alkyne: contains a carbon-carbon triple bond and has the
general formula CnH2n-2.
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Unsaturated Hydrocarbons
• Arene: benzene and its derivatives (Ch 9)
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Benzene and Phenyl Groups
• We do not study benzene and its derivatives until
Chapter 9.
– However, we show structural formulas of compounds
containing a phenyl group before that time.
– The phenyl group is not reactive under any of the
conditions we describe in chapters 5-8.
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Structure of Alkenes
• The two carbon atoms of a double bond and the
four atoms bonded to them lie in a plane, with bond
angles of approximately 120°.
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Cis-Trans Isomerism
• Because of restricted rotation about a C–C double
bond, groups on the carbons of a double bond are
either cis or trans to each other.
– Because of nonbonded interaction strain between alkyl substituents
on the same side of the double bond, a trans alkene is more stable
than an isomeric cis alkene.
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Structure of Alkynes
• The functional group of an alkyne is a carbon-
carbon triple bond.
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Nomenclature of Alkenes
• IUPAC Nomenclature of alkenes
– Use the infix -en- to show the presence of a carbon-
carbon double bond.
– Number the parent chain to give the first carbon of the
double bond the lower number.
– Follow IUPAC rules for numbering and naming
substituents.
– For a cycloalkene, number the atoms of the ring
beginning with the two carbons of the double bond.
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Nomenclature of Alkenes
• IUPAC nomenclature of alkenes
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Nomenclature of Alkenes
• Some alkenes, particularly low-molecular-weight
alkenes, are known almost exclusively by their
common names.
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Nomenclature of Alkynes
• IUPAC nomenclature of alkynes
– Use the infix -yne to show the presence of a carbon-
carbon triple bond.
– Number the parent chain to give the first carbon of the
triple bond the lower number.
– Follow IUPAC rules for numbering and naming
substituents.
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Configuration: Cis-Trans
• The cis-trans system: Configuration is determined
by the orientation of atoms of the main chain.
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Configuration: E,Z
• To Assign an E,Z configuration, first assign a priority to the
substituents on each carbon of the double bond.
– If the groups of higher priority are on the same side of the double
bond, the configuration is Z (German: zusammen, together).
– If the groups of higher priority are on opposite sides of the double
bond, the configuration is E (German: entgegen, opposite).
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Configuration: E,Z
• Priority rules
1. Priority is based on atomic number; the higher the atomic number, the
higher the priority.
2. If priority cannot be assigned on the basis of the atoms bonded
directly to the double bond, look to the next set of atoms; priority is
assigned at the first point of difference.
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Cis-Trans Isomerism
• Dienes, trienes, and polyenes
– For an alkene with n carbon-carbon double bonds, each of which can
show cis-trans isomerism, 2n cis-trans isomers are possible.
– Consider 2,4-heptadiene; it has four cis-trans isomers, two of which
are drawn here.
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Cis-Trans Isomerism
– Vitamin A has five C-C double bonds, four of which can
show cis-trans isomerism.
– Vitamin A is the all-trans isomer.
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Physical Properties
• Alkenes and alkynes are nonpolar compounds.
– The only attractive forces between their molecules are
dispersion forces.
• The physical properties of alkenes and alkynes are
similar to those of alkanes with similar carbon
skeletons.
– Those that are liquid at room temperature are less dense
than water (1.0 g/mL).
– They dissolve in each other and in nonpolar organic
solvents.
– They are insoluble in water.
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The Acidity of Terminal Alkynes
• One of the major differences between the chemistry
of alkenes and alkynes is that the hydrogen atom of
a terminal alkyne is sufficiently acidic (pKa 25) that it
an be removed by a strong base such as sodium
amide, NaNH2, to give an alkyne anion.
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The Acidity of Terminal Alkynes
• The pKa values for alkane and alkene hydrogens
are so large that no base is strong enough to
remove a hydrogen from either of these classes of
compounds.
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Alkenes and Alkynes
End Chapter 4
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