Goals

1. Be able to name straight chain and branch chain alkenes

2. Be able to draw geometric (cis-trans) isomers when given
formula
3. Be able to identify geometric (cis-trans) isomers when given
structures
4. Be able to classify the typical reactions of alkenes and alkynes
(addition, elimination, substitution, and rearrangement)
5. Be able to predict reactants, or products of the typical
reactions of alkenes and alkynes (hydrogenation,
halogenation, hydrohalogenation, and hydration)
6. Know Markovnikov’s rule and how it applies to
hydrohalogenation and hydration reactions

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13.1 Alkenes and Alkynes

• 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.
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 Alkane, alkene, or alkyne?

Is there a way to predict the type of hydrocarbon?

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Review

Continued

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 Review

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Review
• Substituents such as —CH3 and —CH2CH3, that
branch off the main chain are called alkyl
groups.
• The situation is more complex for larger alkanes.

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 13.2 Naming Alkenes and Alkynes

• 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.

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13.2 Naming Alkenes and Alkynes

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 13.2 Naming Alkenes and Alkynes
• 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.

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13.2 Naming Alkenes and Alkynes

• 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.
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 13.2 Naming Alkenes and Alkynes

(Organic Nomenclature Worksheet)

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13.3 The Structure of Alkenes: Cis–Trans Isomerism

• 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.
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 13.3 The Structure of Alkenes: Cis–Trans Isomerism

• 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.
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13.3 The Structure of Alkenes: Cis–Trans Isomerism

Geometric Isomers: Isomers that occur when you
have restricted rotation around a double bond
(cis/trans)

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 13.3 The Structure of Alkenes: Cis–Trans Isomerism

• 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.
(Organic Nomenclature Worksheet)
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Active Learning Exercise

Draw and name 2 geometric isomers of

2-heptene

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 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
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Active Learning Exercise-Nomenclature

Formula:

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 13.5 Types of Organic Reactions

• 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.

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13.5 Types of Organic Reactions

• An elimination reaction is a general

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

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 13.5 Types of Organic Reactions

• 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.

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13.5 Types of Organic Reactions

• A rearrangement reaction is a general

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

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 13.6 Addition Reactions of Alkenes

• 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:

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13.6 Addition Reactions of Alkenes

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.
© 2013 Pearson Education, Inc.
 13.6 Addition Reactions of Alkenes
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.

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13.6 Addition Reactions of Alkenes

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.

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 13.6 Addition Reactions of Alkenes
• 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.
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13.6 Addition Reactions of Alkenes

• 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.

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 13.6 Addition Reactions of Alkenes
• 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.

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13.6 Addition Reactions of Alkenes

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.

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 13.6 Addition Reactions of Alkenes

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13.6 Addition Reactions of Alkenes

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.
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 13.6 Addition Reactions of Alkenes

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13.6 Addition Reactions of Alkenes

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.

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 Review
• There are four possible substitution patterns for carbons
attached to four atoms.
– A primary (1°) carbon atom is a carbon atom with
1 other carbon attached to it.
– A secondary (2°) carbon atom is a carbon atom
with 2 other carbons attached to it.
– A tertiary (3°) carbon atom is a carbon atom with 3
other carbons attached to it.
– A quaternary (4°) carbon atom is a carbon atom
with 4 other carbons attached to it.

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Active Learning-Alkene Reactions

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