Organic Chemistry - Alkenes, Alkynes, and Aromatic Compounds

Outline
13.1 Alkenes and Alkynes

13.2 Naming Alkenes and Alkynes
13.3 The Structure of Alkenes: Cis–Trans Isomerism
13.4 Properties of Alkenes and Alkynes
13.5 Types of Organic Reactions
13.6 Reactions of Alkenes and Alkynes
13.7 Alkene Polymers
13.8 Aromatic Compounds and the Structure of Benzene
13.9 Naming Aromatic Compounds
13.10 Reactions of Aromatic Compounds
© 2013 Pearson Education, Inc.
Goals
1. What are alkenes, alkynes, and aromatic compounds?
Be able to recognize the functional groups in these three families of
unsaturated organic compounds and give examples of each.
2. How are alkenes, alkynes, and aromatic compounds named?
Be able to name an alkene, alkyne, or simple aromatic compound
from its structure, or write the structure, given the name.
3. What are isomers?
Be able to recognize and draw constitutional isomers.
4. How are organic molecules drawn?
Be able to convert between structural formulas and condensed or line
structures.
5. What are alkanes and cycloalkanes, and how are they named?
Be able to name an alkane or cycloalkane from its structure, or write the
structure, given the name.
6. What are the general properties and chemical reactions of
alkanes?
Be able to describe the physical properties of alkanes and the products
formed in the combustion and halogenation reactions of alkanes.
• Alkanes are saturated, as they have as many

hydrogens as possible.
• Alkenes and alkynes are unsaturated because they
contain carbon–carbon multiple bonds.
• Alkenes are hydrocarbons that contain carbon–carbon
double bonds.
• Alkynes are hydrocarbons that contain carbon–carbon
triple bonds.
• Most of the organic chemicals used in

making drugs, explosives, paints, plastics,
and pesticides are synthesized by routes
that begin with alkenes.
• More than 28 million tons of ethylene were
produced in 2010, most of it used for
making polyethylene plastic.
• Ethylene is also formed in the leaves,
flowers, and roots of plants, where it acts
as a hormone.
• STEP 1: Name the parent compound.

Find the longest chain containing the
double or triple bond, and name the parent
compound by adding the suffix -ene or
-yne to the name for the main chain. If
there is more than one double or triple
bond, the number of multiple bonds is
indicated using a numerical prefix.


• STEP 2: Number the carbon atoms in the
main chain so that those with multiple bonds
have the lowest index numbers possible.
Begin numbering at the end nearer the multiple
bond. If the multiple bond is an equal distance
from both ends, begin numbering at the end
nearer the first branch point.

• Cycloalkenes are quite common. The

double-bonded carbon atoms in
substituted cycloalkenes are assigned
index numbers of 1 and 2 so as to give the
first substituent the next lowest possible
index number.

• STEP 3: Write the full name. Assign

numbers to the branching substituents,
and list the substituents alphabetically.
Use commas to separate numbers and
hyphens to separate words from numbers.
Indicate the position of the multiple bond in
the chain by giving the number of the first
multiple-bonded carbon. If more than one
double bond is present, identify the
position of each and use the appropriate
name ending.

• Common Names: For historical reasons, there
are a few alkenes and alkynes whose names do
not conform to the IUPAC rules.
– The 2-carbon alkene should properly be called
ethene, but the name ethylene is accepted by the
IUPAC.
– The 3-carbon alkene propene is usually called
propylene.
– The 4-carbon diene 2-methyl-1,3-butadiene is more
commonly known as isoprene.
– The simplest alkyne, should be known as ethyne, but
is almost always called acetylene.

• Alkenes and alkynes differ from alkanes in

shape because of their multiple bonds.
• The two carbons and four attached atoms
that make up the double-bond functional
group lie in a plane.
• There is no rotation around a
double bond, and the
molecules are more rigid.
• As a consequence of their
rigid nature, alkenes possess
ends and sides.
• In a cis isomer, the two

groups are on the same
side of the double bond.
• In a trans isomer, they
are on opposite sides of
the double bond.
• Cis–trans isomerism is
possible whenever an
alkene has two different
substituent groups on
each of its ends.

• The two substituents that are on the same

side of the double bond in an alkene are said
to be cis to each other.
• Those on opposite sides of the double bond
are said to be trans to each other.
• The terms cis and trans are used in two ways:
– as a relative term to indicate how various groups
are attached to the double-bond carbons, and
– as a way to indicate how the longest chain in the
molecule goes in, through, and out of the double
bond.

13.4 Properties of Alkenes and Alkynes
• Nonpolar; insoluble in water; soluble in

nonpolar organic solvents
• Less dense than water
• Flammable; nontoxic
• Alkenes display cis–trans isomerism when
each double-bond carbon atom has
different substituents.
• Chemically reactive at the multiple bond

• An addition reaction is a general reaction

type in which a substance X—Y adds to
the multiple bond of an unsaturated
reactant to yield a saturated product that
has only single bonds.

• An elimination reaction is a general

reaction type in which a saturated reactant
yields an unsaturated product by losing
groups from two adjacent atoms.

• A substitution reaction is a general

reaction type in which an atom or group of
atoms in a molecule is replaced by
another atom or group of atoms.

• A rearrangement reaction is a general

reaction type in which a molecule
undergoes bond reorganization to yield an
isomer.

The Chemistry of Vision and Color
• Vitamin A, an important biological alkene, is critical to the ability to see.
• A vitamin is an organic molecule required in trace amounts obtained
through diet.
• Beta-carotene is a purple-orange alkene that provides our main dietary
source of vitamin A. The enzymatic conversion of beta-carotene to vitamin
A takes place in the small intestine.
• In the eye, vitamin A is oxidized to retinal, which undergoes cis–trans
isomerization of its C11–C12 double bond to produce 11-cis-retinal.
• Reaction with the protein opsin then produces the light sensitive substance
rhodopsin.
• The eye has two kinds of light-sensitive cells, rod cells and cone cells.
• When light strikes the rod cells, cis–trans isomerization of the C11–C12
double bond occurs and 11-trans-rhodopsin, also called metarhodopsin II, is
produced. This causes a nerve impulse to be sent to the brain where it is
perceived as vision.
• Metarhodopsin II is then changed back to 11-cis-retinal for use in another
vision cycle.


The Chemistry of Vision and Color (Continued)
• Beta-carotene is a purple-orange color; other organic compounds such as
the purple dye, mauve, and the plant pigment, cyanidin, are also brightly
colored.
• Each of these compounds has numerous alternating double and single
bonds (known as conjugation).

The Chemistry of Vision and Color (Continued)
• Whenever there is conjugation in a molecule, a delocalized region of
electron density is formed that is capable of absorbing light.
• Organic compounds with small numbers of delocalized electrons, such as
benzene, which has three conjugated double bonds, absorb in the
ultraviolet region of the electromagnetic spectrum.
• Compounds with longer stretches of alternating double and single bonds
(10 or more) absorb in the visible region.
• The color that we see is
complementary to the color that is
absorbed; the plant pigment, cyanidin,
absorbs greenish-yellow light and
thus appears reddish-blue.
• Observed and absorbed colors are
complementary. Thus, if a substance
absorbs red light, it has a green color.

• Most of the reactions of carbon–carbon

multiple bonds are addition reactions.
• A generalized reagent X-Y adds to the
multiple bond to yield a saturated product
that has only single bonds:

Addition of H2 to Alkenes and Alkynes: Hydrogenation
• Alkenes and alkynes react with hydrogen in the
presence of a metal catalyst to yield the corresponding
alkane product:
• This process is used commercially to convert

unsaturated vegetable oils to saturated fats used in
margarine and cooking fats.
• This process has come under intense scrutiny in
recent years because it creates trans fatty acids.
Addition of Cl2 and Br2 to Alkenes and Alkynes: Halogenation
• Alkenes and alkynes react with halogens to yield 1,2-
dihaloalkane addition products:
• The reaction between ethylene and chlorine provides the

starting point for the manufacture of PVC plastic.
• Bromine (Br2) can be used as a test for multiple bonds and
unsaturation of fats:
– A few drops are added to a sample of an unknown compound.
– Immediate disappearance of the color reveals the presence of a
multiple bond, as the bromine reacts to form a colorless
dibromide.

Addition of HBr and HCl to Alkenes
• Alkenes react with hydrogen bromide (HBr) to
yield alkyl bromides and with hydrogen chloride
(HCl) to yield alkyl chlorides in
hydrohalogenation reactions.

• The addition of HBr to 2-methylpropene is an
example.
• Only one of the two possible addition products is

obtained. 2-methylpropene could add HBr to give
1-bromo-2-methylpropane, but it does not; it gives
only 2-bromo-2-methylpropane as the major
product.
• Markovnikov’s rule—In the addition of HX to an
alkene, the major product arises from the H
attaching to the double-bond carbon that has the
larger number of H atoms directly attached to it,
and the X attaching to the carbon that has the
smaller number of H atoms attached.

• If an alkene has equal numbers of H atoms
attached to the double-bond carbons (a
symmetrically-substituted double bond), both
possible products are formed in approximately
equal amounts.

Addition of Water to Alkenes: Hydration
• An alkene will not react with pure water alone. If
a small amount of strong acid catalyst is added,
an addition reaction takes place to yield an
alcohol.
• Markovnikov’s rule can be used to predict the

product when water adds to an unsymmetrically
substituted alkene.


How Addition Reactions Occur
• Detailed studies show that alkene addition reactions take place in
two distinct steps.
– In the first step, two electrons move from the C=C double bond to form
a C–H bond.
– In the second step, X2 uses two electrons to form a bond to the
positively charged carbon.
• Almost all organic reactions occur between an electron-rich species
and an electron-poor species.
• In the first step, the electron-rich alkene reacts with the electron-
poor acid. The C=C bond partially breaks, and two electrons move
from the double bond to form a new single bond.
• The remaining double-bond carbon has only six electrons in its outer
shell and bears a positive charge.
• Carbons that possess a positive charge, or carbocations, are highly
reactive. As soon as this carbocation is formed, it immediately reacts
with the halogen to form a neutral product.

How Addition Reactions Occur
• The more carbons attached to a carbocation, the more stable it will
be, making its formation more favorable.
• Tertiary (3°) carbocations are more stable than secondary (2°)
carbocations.
• Secondary (2°) carbocations are much more stable than primary
(1°) carbocations.
• Primary (1°) carbocations are so unstable that they almost never
form.
• This provides the scientific basis for Markovnikov’s rule: the major
product arises because the intermediate it is derived from is more
stable than any other intermediate.
• A description of the individual steps by which old bonds are broken
and new bonds are formed in a reaction is called a reaction
mechanism.

• A polymer is a large molecule formed by the
repetitive bonding together of many smaller
molecules called monomers.
• Many simple alkenes undergo polymerization
reactions when treated with the proper
catalyst.
– Ethylene yields polyethylene.
– Propylene yields polypropylene.
– Styrene yields polystyrene.
• The polymer might have anywhere from a few
hundred to a few thousand units incorporated
into a long, repeating chain.

• The reaction begins by addition of an initiator to an
alkene; this results in the breaking of one of the bonds
making up the double bond.
• A reactive intermediate that contains an unpaired
electron (known as a radical) is formed in this step, and
this reactive intermediate adds to a second molecule.
• This produces another reactive intermediate, which adds
to a third alkene molecule.
• The result is continuous addition of one monomer after
another to the end of the growing polymer chain.
• Polymers formed in this way are called chain-growth
polymers. The basic repeating unit is enclosed in
parentheses, and the subscript n indicates how many
repeating units are in the polymer.


• Variations in the substituent group attached to the
double bond impart different properties to the product.
• Polymer rigidity is controlled by addition of a cross-linking
agent, typically 1–2% of a dialkene (an alkene containing
two double bonds), whose role is to covalently link two
chains of monomer units together.
• The properties of a polymer depend on the monomer, the
average size of the molecules in a sample and how
extensively they cross-link and branch.
• The molecules in straight-chain polyethylene pack closely
together, giving a rigid material called high-density
polyethylene.
• Branched polyethylene cannot pack together as tightly and
instead forms a flexible material called low-density
polyethylene.
• In the early days of organic chemistry,

aromatic was used to describe fragrant
substances from natural sources.
• Substances grouped as aromatic behave

differently from most other organic
compounds.
• Aromatic—The class of compounds

containing benzene-like rings
• Benzene is a flat, symmetrical molecule with the

molecular formula C6H6.
• Benzene and other aromatic compounds are
much less reactive than alkenes and do not
normally undergo addition reactions.
• Experimental evidence shows that all six
carbon–carbon bonds in benzene are identical.

• The double-bond electrons are free to move

over the entire ring.
• Each carbon–carbon bond is intermediate
between a single bond and a double bond. The
name resonance is given to this phenomenon.
• Simple aromatic hydrocarbons are nonpolar,
insoluble in water, volatile, and flammable.
• Several aromatic hydrocarbons have biological
effects: benzene has been implicated as a
cause of leukemia, and dimethyl-substituted
benzenes are central nervous system
depressants.
Polycyclic Aromatic Hydrocarbons and Cancer

• Polycyclic aromatic compounds are substances that have two or
more benzene-like rings joined together by a common bond.
• Naphthalene, familiar for its use in mothballs, is the simplest and
best-known polycyclic aromatic compound.
• Benz[a]pyrene contains five benzene-like rings joined together;
ordinary graphite (the “lead” in pencils) consists of enormous
two-dimensional sheets of benzene-like rings stacked one on top
of the other.
• Exposure to even a tiny amount is sufficient to induce a skin
tumor in susceptible mice.
• After benz[a]pyrene is taken into the body, the body converts it
into a water-soluble metabolite called a diol epoxide.
• The diol epoxide metabolite reacts with and binds to cellular
DNA, altering the DNA and leading to mutations or cancer.

• Substituted benzenes are named using -

benzene as the parent.
• No number is needed for monosubstituted
benzenes because all the ring positions
are identical.

• Disubstituted benzenes are unique in that the

relational descriptors o- (ortho), m- (meta), and
p- (para) may be used in place of 1,2-, 1,3-, and
1,4-.
• The terms ortho-, meta- or para- are then used
as prefixes.

• Many substituted aromatic compounds have
common names in addition to their systematic
names.
– Methylbenzene is toluene.
– Hydroxybenzene is phenol.
– Aminobenzene is aniline.
• Frequently, these common names are used with
o- (ortho), m- (meta), or p- (para) prefixes.

• The benzene ring itself may be considered a
substituent group attached to another parent
compound.
• When this happens, the name phenyl is used.

• Aromatic compounds usually undergo a
special type of substitution reaction known
as an electrophilic aromatic substitution
reaction.
• A group Y substitutes for a hydrogen on the
ring.
• It does not matter which of the ring hydrogens
is replaced because all are equivalent.
• The mechanism responsible for this type of
reaction is similar to that seen for alkenes.

• Nitration is the substitution of a nitro group
NO2 for a hydrogen on an aromatic ring.
• Halogenation is the substitution of a

halogen group, X, for a hydrogen on an
aromatic ring.
• Sulfonation is the substitution of a sulfonic

acid group, SO3H, for a hydrogen on an
aromatic ring.

Chapter Summary
1. What are alkenes, alkynes, and aromatic
compounds?
• Alkenes are hydrocarbons that contain a carbon–
carbon double bond.
• Alkynes are hydrocarbons that contain a carbon–
carbon triple bond.
• Aromatic compounds contain six-membered, benzene-
like rings and are written with three double bonds.
• There is equal bonding between neighboring carbon
atoms in benzene rings because the double-bond
electrons are spread around the entire ring.
• All three families are said to be unsaturated because
they have fewer hydrogens than corresponding
alkanes.
Chapter Summary, Continued
2. How are alkenes, alkynes, and
aromatic compounds named?
• Alkenes use the family ending -ene.
• Alkynes use the family ending -yne.
• Disubstituted benzenes have the suffix
-benzene as the parent name.
• Positions of the substituents are indicated
with the prefixes ortho- (1,2 substitution),
meta- (1,3 substitution), or para- (1,4
substitution).
3. What are cis–trans isomers?
• Cis–trans isomers are seen in

disubstituted alkenes as a consequence
of the lack of rotation around carbon–
carbon double bonds.
• In the cis isomer, the two substituents are
on the same side of the double bond.
• In the trans isomer, they are on opposite

sides of the double bond.
4. What are the categories of organic reactions?
• The four categories of organic reactions are
addition, elimination, substitution, and
rearrangement reactions.
– Addition reactions occur when two reactants add together
to form a single product with no atoms left over.
– Eliminations occur when a single reactant splits into two
products.
– Substitution reactions occur when two reactants exchange
parts to give two new products.
– Rearrangement reactions occur when a single reactant
undergoes a reorganization of bonds and atoms to yield a
single isomeric product.
5. What are the typical reactions of alkenes, alkynes,
and aromatic compounds?
• Alkenes and alkynes undergo addition reactions to their multiple bonds.
• Addition of hydrogen to an alkene (hydrogenation) yields an alkane
product.
• Addition of Br2 or Cl2 (halogenation) yields a 1,2-dihaloalkane product.
• Addition of HBr and HCl (hydrohalogenation) yields an alkyl halide
product.
• Addition of water (hydration) yields an alcohol product.
• Markovnikov’s rule predicts that in the addition of HX or H2O to a double
bond, the H becomes attached to the carbon with more H’s and the X or
OH becomes attached to the carbon with fewer H’s.
• Aromatic compounds are unusually stable but can be made to undergo
substitution reactions, in which one of the ring hydrogens is replaced by
another group.
• Among these substitutions are nitration, halogenation, and sulfonation.

6. How do organic reactions take place?
• A description of the individual steps by which
old bonds are broken and new bonds are
formed in a reaction is called a reaction
mechanism.
• The addition reaction of an alkene with HX
takes place in two steps.
– In the first step, the alkene uses two electrons to
bond to giving a positively charged species
called a carbocation.
– In the second step, the carbocation reacts with
the halide ion to give the final product.

Organic Chemistry - Alkenes, Alkynes, and Aromatic Compounds

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Outline

13.1 Alkenes and Alkynes

• Alkanes are saturated, as they have as many

• Most of the organic chemicals used in

• STEP 1: Name the parent compound.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

• Cycloalkenes are quite common. The

© 2013 Pearson Education, Inc.

• STEP 3: Write the full name. Assign

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

• Alkenes and alkynes differ from alkanes in

• In a cis isomer, the two

© 2013 Pearson Education, Inc.

• The two substituents that are on the same

© 2013 Pearson Education, Inc.

• Nonpolar; insoluble in water; soluble in

© 2013 Pearson Education, Inc.

• An addition reaction is a general reaction

© 2013 Pearson Education, Inc.

• An elimination reaction is a general

© 2013 Pearson Education, Inc.

• A substitution reaction is a general

© 2013 Pearson Education, Inc.

• A rearrangement reaction is a general

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

• Most of the reactions of carbon–carbon

© 2013 Pearson Education, Inc.

• This process is used commercially to convert

• The reaction between ethylene and chlorine provides the

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

• Only one of the two possible addition products is

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

• Markovnikov’s rule can be used to predict the

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

• In the early days of organic chemistry,

• Substances grouped as aromatic behave

• Aromatic—The class of compounds

• Benzene is a flat, symmetrical molecule with the

© 2013 Pearson Education, Inc.

• The double-bond electrons are free to move

Polycyclic Aromatic Hydrocarbons and Cancer

© 2013 Pearson Education, Inc.

• Substituted benzenes are named using -

© 2013 Pearson Education, Inc.

• Disubstituted benzenes are unique in that the

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.

© 2013 Pearson Education, Inc.