Organic Chemistry,

9th Edition
L. G. Wade, Jr.

Chapter 7
Lecture
Structure and
Synthesis
of Alkenes

Chad Snyder, PhD

Grace College
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 Introduction

• Alkenes are hydrocarbons with carbon–carbon

double bonds.
• Alkenes are also called olefins, meaning
“oil-forming gas.”
• The functional group of alkenes is the
carbon–carbon double bond, which gives this
group its reactivity.

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 Sigma Bonds of Ethylene

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 Orbital Description

• Sigma bonds around the double-bonded

carbon are sp2 hybridized.
• Angles are approximately 120° and the
molecular geometry is trigonal planar.
• Unhybridized p orbitals with one electron will
overlap, forming the double bond (pi bond).

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 Bond Lengths and Angles

• sp2 hybrid orbitals have more s character than the

sp3 hybrid orbitals.
• Pi overlap brings carbon atoms closer, shortening the C—C
bond from 1.54 Å in alkanes down to 1.33 Å in alkenes.

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 Pi Bonding in Ethylene

• The pi bond in ethylene is formed by overlap of the

unhybridized p orbitals of the sp2 hybrid carbon atoms.
• Each carbon has one unpaired electron in the p orbital.
• This overlap requires the two ends of the molecule to be
coplanar.

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 Cis-Trans Interconversion

• Cis and trans isomers cannot be interconverted.

• No rotation around the carbon–carbon bond is possible
without breaking the pi bond (264 kJ/mole).

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 Elements of Unsaturation

• Unsaturation is a structural element that decreases the

number of hydrogens in the molecule by two.
• It is also called index of hydrogen deficiency.
• Double bonds and rings are elements of unsaturation.

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 Calculating Unsaturations

• To calculate the number of unsaturations, first

find the number of hydrogens the carbons
would have if the compounds were saturated.
Then subtract the actual number of hydrogens
and divide by 2.
• This calculation cannot distinguish between
unsaturations from multiple bonds and those
from rings.

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 Degrees of Unsaturation:
The Nitrogen Atom

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 Example: Calculate the Unsaturations
for a Compound with Formula C5H8.
• First calculate the number of hydrogen atoms for a
saturated compound with five carbons:
(2 × C) + 2
(2 × 5) + 2 = 12

• Now subtract from this number the actual number

of hydrogen atoms in the formula and divide by 2:
12 – 8 = 4 = 2 unsaturations
2 2
• The compound has two unsaturations. They can be
two double bonds, two rings, or one double bond
and one ring.
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 Elements of Unsaturation:
Heteroatoms

• Halogens replace hydrogen atoms in

hydrocarbons, so when calculating unsaturations,
count halides as hydrogen atoms.
• Oxygen does not change the C:H ratio, so ignore
oxygen in the formula.
• Nitrogen is trivalent, so it acts like half a carbon.
Add the number of nitrogen atoms when
calculating unsaturations.

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 Example: Calculate the Unsaturations
for a Compound with Formula C4H7Br.
• First calculate the number of hydrogens for a
saturated compound with four carbons:
(2 × C) + 2 + N
(2 × 4) + 2 = 10

• Now subtract from this number the actual number

of hydrogens in the formula and divide by 2.
Remember to count halides as hydrogens:
10 – 8 = 2 = 1 unsaturation
2 2
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 Example: Calculate the Unsaturations
for a Compound with Formula C6H7N.
• First calculate the number of hydrogens for a
saturated compound with six carbons. Add the
number of nitrogens:
(2 × C) + 2 + N
(2 × 6) + 2 + 1 = 15

• Now subtract from this number the actual number

of hydrogens in the formula and divide by 2:
15 – 7 = 8 = 4 unsaturations
2 2
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 IUPAC Nomenclature

• Find the longest continuous carbon chain that

includes the double-bonded carbons.
• Ending -ane changes to -ene.
• Number the chain so that the double bond has the
lowest possible number.
• In a ring, the double bond is assumed to be
between carbon 1 and carbon 2.

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 IUPAC and New IUPAC

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 Ring Nomenclature
In a ring, the double bond is assumed to be between
carbon 1 and carbon 2.

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 Multiple Double Bonds

• Give the double bonds the lowest numbers

possible.
• Use di-, tri-, or tetra- before the ending -ene to
specify how many double bonds are present.
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 Alkenes As Substitutents

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 Cis-Trans Isomers

• Also called geometric isomerism

• If there are similar groups on same side of the double
bond, alkene is cis.
• If there are similar groups on opposite sides of the
double bond, alkene is trans.
• Not all alkenes show cis-trans isomerism.

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 Cyclic Compounds

• Trans cycloalkenes are not stable unless the ring has at

least eight carbons.
• All cycloalkenes are assumed to be cis unless otherwise
specifically named trans.

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 Biochemistry Application

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 E-Z Nomenclature

• Use the Cahn–Ingold–Prelog rules to assign

priorities to groups attached to each carbon
in the double bond.
• If high-priority groups are on the same side,
the name is Z (for zusammen).
• If high-priority groups are on opposite sides,
the name is E (for entgegen).

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 Example

• Assign priority to the

substituents according
to their atomic number
(1 is highest priority).
• If the highest priority
groups are on opposite
sides, the isomer is E.
• If the highest priority
groups are on the same
side, the isomer is Z.

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 Cyclic Stereoisomers

• Double bonds outside the ring can show stereoisomerism.

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 Stereochemistry in Dienes

• If there is more than one double bond in the molecule,

the stereochemistry of all the double bonds should be
specified.

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 Commercial Uses of Ethylene

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 Commercial Uses of Propylene

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 Addition Polymers

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 Physical Properties of Alkenes

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 Polarity and Dipole Moments of
Alkenes
• Cis alkenes have a greater dipole moment than trans
alkenes, so they will be slightly polar.
• The boiling point of cis alkenes will be higher than the
trans alkenes.

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 Heat of Hydrogenation
• Combustion of an alkene and hydrogenation of an
alkene can provide valuable data as to the stability of
the double bond.
• The more substituted the double bond, the lower its
heat of hydrogenation.

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 Relative Heats of
Hydrogenation

More substituted double bonds are usually more stable.

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 Relative Stabilities

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 Cycloalkenes

• A ring makes a major difference only if there is ring strain, either

because of a small ring or because of a trans double bond.
• Rings that are five-membered or larger can easily accommodate
double bonds, and these cycloalkenes react much like straight-
chain alkenes.
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 Cyclopropene
• Cyclopropene has bond angles of about 60°, compressing the
bond angles of the carbon–carbon double bond to half their usual
value of 120°.
• The double bond in cyclopropene is highly strained.

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 Stability of Cycloalkene

• Cis isomer is more stable than trans in small cycloalkenes.

• Small rings have additional ring strain.
• It must have at least eight carbons to form a stable trans
double bond.
• For cyclodecene (and larger), the trans double bond is almost
as stable as the cis.
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 Bredt’s Rule

• A bridged, bicyclic compound cannot have a double bond at

a bridgehead position unless one of the rings contains at
least eight carbon atoms.

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 Solved Problem 1
Which of the following alkenes are stable?

Solution
Compound (a) is stable. Although the double bond is at a bridgehead, it is not a bridged
bicyclic system. The trans double bond is in a ten-membered ring. Compound (b) is a Bredt’s
rule violation and is not stable. The largest ring contains six carbon atoms, and the trans
double bond cannot be stable in this bridgehead position.
Compound (c) (norbornene) is stable. The (cis) double bond is not at a bridgehead
carbon. Compound (d) is stable. Although the double bond is at the bridgehead of a bridged
bicyclic system, there is an eight-membered ring to accommodate the trans double bond.
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 Physical Properties of Alkenes

• Low boiling points, increasing with mass

• Branched alkenes have lower boiling points.
• Less dense than water
• Slightly polar
– Pi bond is polarizable, so instantaneous dipole–dipole
interactions occur.
– Alkyl groups are electron-donating toward the pi bond,
so they may have a small dipole moment.

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 Alkene Synthesis
Overview

• E2 dehydrohalogenation (–HX)
• E1 dehydrohalogenation (–HX)
• Dehydration of alcohols (–H2O)

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 Elimination Reactions

• Elimination reactions produce double bonds.

• Also called dehydrohalogenation (–HX)

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 The E1 Reaction

• Unimolecular elimination
• Two groups are lost: a hydrogen and the halide.
• Nucleophile acts as base.
• The E1 and SN1 reactions have the same
conditions, so a mixture of products will be
obtained.

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 E1 Mechanism
Step 1: Ionization to form a carbocation

Step 2: Solvent abstracts a proton to form an alkene.

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 A Closer Look

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 E1 Energy Diagram

The E1 and the SN1 reactions have the same first step: Carbocation
formation is the rate-determining step for both mechanisms.

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 Zaitsev’s Rule
• If more than one elimination product is possible, the
most-substituted alkene is the major product (most
stable).

major product
(trisubstituted)
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 Alkene Stability

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 The E2 Reaction
• Elimination, bimolecular
• Requires a strong base
• This is a concerted reaction: The proton is
abstracted, the double bond forms, and the
leaving group leaves, all in one step.

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 The E2 Reaction

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 The E2 Mechanism

• Order of reactivity for alkyl halides

3° > 2° > 1°
• A mixture may form, but the Zaitsev product
predominates.

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 Bulky Bases in E2 Eliminations;
Hofmann Orientation

• If the substrate in an E2 elimination is prone to substitution, we

can minimize the amount of substitution by using a bulky base.
• Bulky bases can accomplish dehydrohalogenations that do not
follow the Zaitsev rule. They form the Hofmann product.
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 Zaitsev and Hofmann Products

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 E2 Stereochemistry
• The halide and the proton to be abstracted
must be anti-coplanar ( = 180º) to each
other for the elimination to occur.
• The orbitals of the hydrogen atom and the
halide must be aligned so they can begin to
form a pi bond in the transition state.
• The anti-coplanar arrangement minimizes
any steric hindrance between the base and
the leaving group.
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 E2 Stereochemistry

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 Stereochemistry of E2
Elimination

• Most E2 reactions go through an anti-coplanar

transition state.
• This geometry is most apparent if we view the
reaction with the alkyl halide in a Newman
projection.
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 Solved Problem 2
Show that the dehalogenation of 2,3-dibromobutane by iodide ion is stereospecific by showing
that the two diastereomers of the starting material give different diastereomers of the product.

Solution
Rotating meso-2,3-dibromobutane into a conformation where the bromine atoms are anti and
coplanar, we find that the product will be trans-2-butene. A similar conformation of either
enantiomer of the (±) diastereomer shows that the product will be cis-2-butene. (Hint: Your
models will be helpful.)

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 E2 Reactions on Cyclohexanes

• An anti-coplanar conformation (180°) can only be achieved

when both the hydrogen and the halogen occupy axial
positions.
• The chair must flip to the conformation with the axial halide
in order for the elimination to take place.

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 Solved Problem 3
Explain why the following deuterated 1-bromo-2-methylcyclohexane undergoes
dehydrohalogenation by the E2 mechanism, to give only the indicated product. Two other
alkenes are not observed.

Solution
In an E2 elimination, the hydrogen atom and the leaving group must have a trans-diaxial
relationship. In this compound, only one hydrogen atom—the deuterium—is trans to the
bromine atom. When the bromine atom is axial, the adjacent deuterium is also axial, providing
a trans-diaxial arrangement.

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 Substitution or Elimination?

• The strength of the nucleophile determines

the order: Strong nucleophiles or bases
promote bimolecular reactions.
• Primary halides usually undergo SN2.
• Tertiary halides are a mixture of SN1, E1, or
E2. They cannot undergo SN2.
• High temperature favors elimination.
• Bulky bases favor elimination.
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 Secondary Alkyl Halides
• Secondary alkyl halides are more challenging:
– Strong nucleophiles will promote SN2/E2.
– Weak nucleophiles promote SN1/E1.
• Strong nucleophiles with limited basicity favor SN2. Bromide
and iodide are good examples of these.

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 Solved Problem 4
Predict the mechanisms and products of the following reaction.

Solution

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 Solved Problem 5
Predict the mechanisms and products of the following reaction.

Solution

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 E1 and SN1 Mechanisms

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 Dehydration of Alcohols

• Use concentrated H2SO4 or H3PO4 and remove low-boiling

alkene as it forms to shift the equilibrium and increase the
yield of the reaction.
• E1 mechanism
• Rearrangements are common.
• The reaction obeys Zaitsev’s rule.

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 Dehydration Mechanism: E1
Step 1: Protonation of the hydroxyl group (fast equilibrium)

Step 2: Ionization to a carbocation (slow; rate limiting)

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 Dehydration Mechanism: Step 3

Step 3: Deprotonation to give the alkene (fast)

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 Solved Problem 6
Propose a mechanism for the sulfuric acid-catalyzed dehydration of t-butyl alcohol

Solution
The first step is protonation of the hydroxyl group, which converts it to a good leaving group.

The second step is ionization of the protonated alcohol to give a carbocation.

Abstraction of a proton completes the mechanism.

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