Bettelheim / Brown / Campbell / Farrell / Torres
Introduction to General, Organic, and Biochemistry 11e
Chapter 12
Alkenes and
Alkynes
William H. Brown Beloit College www.cengage.com/chemistry/bettelheim
1
Objectives
At the end of 3 hours class, the students must:
•can draw line-angle formula for alkenes and alkynes.
•name alkenes and alkynes according to the IUPAC system
given the structural formula and vice versa.
•enumerate the characteristic reactions of unsaturated
hydrocarbons.
•draw the structure of benzene and discuss its resonance
properties.
•They can use the IUPAC system to give correct names for
benzene and its derivatives and describe the characteristics
of an antioxidant.
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Alkenes and Alkynes
Alkene: A hydrocarbon that contains one or more carbon-
carbon double bonds.
• Ethylene is the simplest alkene.
Alkyne: A hydrocarbon that contains one or more carbon-
carbon triple bonds.
• Acetylene is the simplest alkyne.
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Alkenes
Cis-trans isomerism
• Because of restricted rotation about a carbon-carbon
double bond, an alkene with two different groups on
each carbon of the double bond shows cis-trans
isomerism.
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Alkenes—IUPAC Names
To name an alkene;
• The parent name is that of the longest chain that
contains the C=C.
• Number the chain from the end that gives the lower
numbers to the carbons of the C=C.
• Locate the C=C by the number of its first carbon.
• Use the ending -ene to show the presence of the C=C
• Branched-chain alkenes are named in a manner similar
to alkanes in which substituted groups are located and
named.
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Alkenes—IUPAC Names
Examples
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Alkynes—IUPAC Names
Follow the same rules as for alkenes, but use the ending
-yne to show the presence of the triple bond.
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Common Names
Common names are still used for some alkenes and
alkynes, particularly those with low molecular weight.
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Cycloalkenes
To name a cycloalkene:
• Number the carbon atoms of the ring double bond 1
and 2 in the direction that gives the lower number to
the substituent encountered first.
• Note that it is not necessary to explicitly number the
position of the double bond in a cycloalkene as in
linear alkenes.
• Number and list substituents in alphabetical order.
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Cycloalkenes
• Alkenes that contain more than one double bond are
named as alkadienes, alkatrienes, and so forth.
• Those that contain several double bonds are referred
to more generally as polyenes (Greek: poly, many).
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Physical Properties
• Alkenes and alkynes are nonpolar compounds.
• The only attractive forces between their molecules are
London dispersion forces.
• Their physical properties are similar to those of
alkanes with the same carbon skeletons.
• Alkenes and alkynes are insoluble in water but soluble
in one another and in nonpolar organic liquids.
• Alkenes and alkynes that are liquid or solid at room
temperature have densities less than 1.0 g/mL; they
float on water.
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Reactions of Alkenes
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Reactions of Alkenes
Most alkene addition reactions are exothermic.
• the products are more stable (lower in energy) than the
reactants.
• Just because they are exothermic does not mean that
alkene addition reactions occur rapidly.
• Reaction rate depends on the activation energy.
• Many alkene addition reactions require a catalyst.
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Addition of HX
Addition of HX (HCl, HBr, or HI) to an alkene gives a
haloalkane.
• H adds to one carbon of the C=C and X to the other.
• Reaction is regioselective. One direction of bond
forming (or bond breaking) occurs in preference to all
other directions.
• Markovnikov’s rule: H adds to the less substituted
carbon and X to the more substituted carbon.
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Addition of HX
Chemists account for the addition of HX to an alkene by a
two-step reaction mechanism.
• We use curved arrows to show the repositioning of
electron pairs during a chemical reaction.
• The tail of an arrow shows the origin of the electron
pair (either on an atom or in the double bond).
• The head of the arrow shows its new position.
• Curved arrows show us which bonds break and which
new ones form.
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Common Mechanism Steps
Pattern 1: Add a proton
An acid is a proton donor and a base is a proton acceptor.
We can use curved arrows to show how a proton transfer
occurs.
Patterns 2: Take a proton away.
If we run the above reaction, in reverse it corresponds to
taking a proton away.
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Common Mechanism Steps
• Pattern 3: Reaction of an electrophile and a nucleophile
to form a new covalent bond.
• An electrophile is an electron-poor species that can
accept a pair of electrons to form a new covalent bond.
• A nucleophile is an electron-rich species that can donate
a pair of electrons to form a new covalent bond.
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Common Mechanism Steps
• Pattern 4: Reaction of a proton donor with a carbon-
carbon double bond to form a new covalent bond. The
double bond provides both of the electrons that forms the
new covalent bond. In the following reaction we show the
hydronium ion as the proton donor.
• While the above equation is the most accurate way to
show the proton transfer, we will simplify the equation to
just show the proton and formation of the new covalent
bond.
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Addition of H2O
Addition of water is called hydration.
• Hydration is acid catalyzed, most commonly by H2SO4.
• Hydration follows Markovnikov’s rule; H adds to the
less substituted carbon and OH adds to the more
substituted carbon.
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Addition of H2O
• Step 1: Add a proton
• Step 2: Reaction of an electrophile and a nucleophile to
form a new covalent bond.
Step 3: Take a proton away.
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Addition of Cl2 and Br2
Addition takes place readily at room temperature.
• Reaction is generally carried out using pure reagents,
or mixing them in a nonreactive organic solvent.
• Addition of Br2 is a useful qualitative test for the
presence of a carbon-carbon double bond.
• Br2 has a deep red color; dibromoalkanes are colorless.
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Addition of H2—Reduction
Virtually all alkenes add H2 in the presence of a transition
metal catalyst, commonly Pd, Pt, or Ni.
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Polymerization
From the perspective of the organic chemical industry,
the single most important reaction of alkenes is
polymerization:
• polymer: Greek: poly, many, and meros, part; any long-
chain molecule synthesized by bonding together many
single parts, called monomers.
• monomer: Greek: mono, single and meros, part.
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Polymerization
• Show the structure of a polymer by placing
parentheses around the repeating monomer unit.
• Place a subscript, n, outside the parentheses to
indicate that this unit repeats n times.
• The structure of a polymer chain can be reproduced by
repeating the enclosed structure in both directions.
• The following is a section of polypropene
(polypropylene).
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Ethylene Polymers
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Polyethylene
Low-density polyethylene (LDPE):
• A highly branched polymer; polymer chains do not
pack well and London dispersion forces between them
are weak.
• Softens and melts above 115°C.
• Approximately 65% of all LDPE is used for the
production of films for packaging and for trash bags.
High-density polyethylene (HDPE):
• Only minimal chain branching; chains pack well and
London dispersion forces between them are strong.
• Has higher melting point than LDPE and is stronger
• Can be blow molded to squeezable jugs and bottles.
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Polyethylene
Figure 12.2 Fabrication
of LDPE film.
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Polyethylene
Figure 12.3 Blow molding an HDPE container.
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Chapter 12 Alkenes and Alkynes
End
Chapter 12
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Bettelheim / Brown / Campbell / Farrell / Torres
Introduction to General, Organic, and Biochemistry 11e
Chapter 13
Benzene and Its
Derivatives
William H. Brown Beloit College www.cengage.com/chemistry/bettelheim
30
Aromatic Compounds
Aromatic compound: A hydrocarbon that contains one or
more benzene-like rings.
Arene: A term used to describe aromatic compounds.
• Ar-: A symbol for an aromatic group derived by
removing an -H from an arene.
• Kekulé structure for benzene (1872).
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Benzene
Resonance structure for benzene (1930s)
• The theory of resonance developed by Linus Pauling
provided the first adequate description of the structure
of benzene.
• According to the theory of resonance, certain
molecules and ions are best described by writing two
or more Lewis structures. The real molecule or ion is a
resonance hybrid of these structures.
• Each individual Lewis structure is called a contributing
structure.
• We show that the real molecule is a resonance hybrid
of the two or more Lewis structures by using a double-
headed arrow between them.
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Benzene
• Here are two contributing structures for benzene;
• The resonance hybrid has some of the characteristics
of each Lewis contributing structure.
• The length of a carbon-carbon bond in benzene, for
example, is midway between that of a carbon-carbon
single bond and a double bond.
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Nomenclature
• Monosubstituted alkylbenzenes are named as
derivatives of benzene; for example, ethylbenzene.
• The IUPAC system retains certain common names for
several of the simpler monosubstituted alkylbenzenes.
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Nomenclature
• The common names for these monosubstituted
benzenes are also retained
• Phenyl group (C6H5- or Ph-): The substituent group
derived by removal of an H from benzene.
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Nomenclature
When two substituents occur on a benzene ring, three
isomers are possible; they may be located by:
• numbering the atoms of the ring or
• using the locators ortho (o), meta (m), and para (p).
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Nomenclature
For three or more substituents:
• If one of the substituents imparts a special name, name
the molecule as a derivative of that parent.
• If none of the substituents imparts a special name,
number the substituents to give the smallest set of
numbers, and list them in alphabetical order before the
ending "benzene".
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PAHs
Polynuclear Aromatic Hydrocarbon (PAH)
• A hydrocarbon that contains two or more benzene
rings, with each pair of rings sharing two adjacent
carbon atoms.
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Reactions of Benzene
By far the most characteristic reaction of aromatic
compounds is substitution at a ring carbon.
• This reaction is called aromatic substitution.
substitution
• Some groups that can be introduced directly on the
ring are the halogens, the nitro (-NO2) group, and the
sulfonic acid (-SO3H) group.
Halogenation:
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Reactions of Benzene
Nitration:
• A value of nitroarenes is that the nitro group can be
reduced to a primary amino group.
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Reactions of Benzene
Sulfonation:
• An application of sulfonation is in the preparation of
synthetic detergents.
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Phenols
The functional group of a phenol is a hydroxyl ( -OH)
group bonded to a benzene ring.
• Name substituted phenols either as derivatives of
phenol or by common names.
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Phenols
• Most phenols are weak acids, with pKa values
approximately 10.
• They are insoluble in water but react with strong bases,
such as NaOH and KOH to form water-soluble salts.
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Phenols
Some phenols found in nature.
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Chapter 13 Benzene and Its Derivatives
End
Chapter 13
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