Alkenes

Organic Chemistry
Second Edition
David Klein
Chapter 8
Alkenes: Structure and Preparation via
Elimination Reactions
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. Klein, Organic Chemistry 2e
8.2 Alkenes
• Important alkenes
Copyright © 2015 John Wiley & Sons, Inc. All rights reserved. 8-2 Klein, Organic Chemistry 2e
8.2 Alkenes
• C=C double bonds are found in a variety of compounds
including pheromones and many other classes of
compounds
8.2 Alkenes
• Why might it be helpful to know the chemical structure
of pheromones such as those below?
8.2 Alkenes
• Alkenes are also important compounds in the chemical
industry
• 70 billion pounds of propylene (propene) and 200 billion
pounds of ethylene (ethene) are both made from
cracking petroleum each year
8.2 Alkenes
8.3 Alkene Nomenclature
• Alkenes are named using the same procedure we used
in Chapter 4 to name alkanes with minor modifications
1. Identify the parent chain, which should include the C=C
double bond
2. Identify and Name the substituents
3. Assign a locant (and prefix if necessary) to each substituent.
Give the C=C double bond the lowest number possible
4. List the numbered substituents before the parent name in
alphabetical order. Ignore prefixes (except iso) when ordering
alphabetically
5. The C=C double bond locant is placed either just before the
parent name or just before the -ene suffix
1. Identify the parent chain, which should include the C=C
double bond
• The name of the parent chain should end in -ene rather
than –ane
• The parent chain should include the C=C double bond
2. Identify and Name the substituents
3. Assign a locant (and prefix if necessary) to each
substituent. Give the C=C double bond the lowest
number possible
– The locant is ONE number, NOT two. Although the double

bond bridges carbons 2 and 3, the locant is the lower of those
two numbers
4. List the numbered substituents before the parent name
in alphabetical order. Ignore prefixes (except iso) when
ordering alphabetically
5. The C=C double bond locant is placed either just before
the parent name or just before the -ene suffix
• Practice with SkillBuilder 8.1
• Name the following molecule
8.4 Alkene Isomerism
• For the pi bond to remain intact, rotation around a
double bond is prohibited
• As a result, cis and trans structures are not identical
• Is there a difference between cis-butane and trans-

butane?
• What specific type of isomers are cis and trans butene?
• In cyclic alkenes with less than 8 atoms in the ring, only
cis alkenes are stable. WHY?
• Draw the structure for trans-cyclooctene
• When applied to bicycloakenes, this rule is called

Bredt’s rule
• Apply Bredt’s rule to the compounds below
• The carbons of the C=C double bond and the atoms that
are directly attached to them must be planar to
maintain the pi bond overlap.
• A handheld model can be used to help visualize the p
orbital overlap and resulting geometry
• Cis and trans modifiers are strictly used to describe C=C
double bonds with identical groups on each carbon.
Where are the identical groups in trans-2-pentene?
• For molecules with different groups attached to the C=C

double bond, the E/Z notation is used instead of
cis/trans notation
• Assigning E or Z to a stereoisomers
1. prioritize the groups attached to the C=C double bond based
on atomic number
• Assigning E or Z to a stereoisomers
1. prioritize the groups attached to the C=C double bond based
on atomic number
2. If the top priority groups are on the same side of the C=C
double bond, it is Z (for zussamen, which means together)
3. If the top priority groups are on opposite sides of the C=C
double bond, it is E (for entgegen, which means opposite)

8.5 Alkene Stability
• Because of steric strain, cis isomers are generally less
stable than trans
• The difference in stability can be quantified by
comparing the heats of combustion
• How does heat of combustion relate to stability?
• Consider the following stability trend
• What pattern do you see?

• List the following molecules in order of increasing heat
of combustion
– 2,3,4-trimethyl-1,3-pentadiene
– 2-isopropyl-1,4-pentadiene
– 3,3-dimethyl-1,5-hexadiene
– 4,5-dimethylcyclohexene
8.6 Elimination Reactions in Detail
• In general, a H atom and a leaving group are eliminated
• To understand the mechanism of elimination, first recall

the 4 mechanistic steps we learned in chapter 7
– Nucleophilic attack
– Loss of a leaving group
– Proton transfer
– Rearrangement
• The 4 mechanistic steps we learned in chapter 7
• Which of the 4 steps MUST take place in every

elimination mechanism?
• All elimination reactions involve both loss of a leaving
group and proton transfer
• The mechanism may be a concerted (one step) process
or a step-wise process. Which process is shown below?
• All elimination reactions involve both Loss of a leaving
group and proton transfer
• The mechanism of the step-wise process:
• Could the steps happen in the reverse order?
8.7 Elimination by E2
• The E2 mechanism below matches the observed rate
law. Write a reasonable rate law for the mechanism
• How will a change in [base] or [substrate] affect the

reaction rate?
• What do the E and the 2 of the E2 notation represent?
• Practice with conceptual checkpoint 8.13
8.7 The Effect of Substrate on E2
• The kinetics of E2 and SN2 are quite similar. WHY?
• However, tertiary substrates are unreactive toward SN2
while they react readily by E2. WHY?
• 3° substrates are more reactive toward E2 than are 1°
substrates even though 1° substrates are less hindered
• The 3° substrate should proceed through a more stable

transition state (kinetically favored) and a more stable
product (thermodynamically favored). Let’s take a look
at the energy diagram – see next slide
How would both
the transition state
energy and the
product energy be
different if the
substrate were 1°?
• Notice the differences in transition state and in product
energies
8.7 Regioselectivity of E2
• If there are multiple reactive sites or regions on a
molecule, multiple products are possible
• In elimination reactions, there are often different β sites
that could be deprotonated to yield different alkenes
• What is the relationship Zaitsev product
between the alkene

products?
• Regioselectivity occurs
when one constitutional
product is formed
predominantly over the Hofmann product
other
• The identity of the base can affect the regioselesctivity
• Why does the Zaitsev product predominate when a
base that is NOT sterically hindered is used?
• Is the Zaitsev product kinetically favored,
thermodynamically favored, or both?
• Why does a sterically hindered base favor the Hofmann
product?
• Sterically hindered bases (sometimes called non-
nucleophilic) are useful in many reactions
8.7 Stereoselectivity of E2
• Consider the dehydrohalogenation (elimination of a
hydrogen and a halogen) of 3-bromopentane
• Why are both the

transition state and
product more stable
for the trans product?
8.7 Stereospecificity of E2
• What is the difference between stereoselective and
stereospecific?
• Consider dehydrohalogenation for the molecule below
• There is only one available β Hydrogen
to be eliminated
• You might imagine that it would be
possible to form both the E and Z alkene
products from this reaction. Draw both
the E and the Z products
• When the reaction is actually performed, only the E
product is observed
• Is the E formed exclusively because it is formed through

a slightly lower transition state?
• To rationalize the stereospecificty of the reaction,
consider the transition state for the reaction
• In the transition state, the C-H and C-Br bonds that are
breaking must be rotated into the same plane as the pi
bond that is forming
• Draw the transition state structure illustrating the

coplanar geometry
• There are two coplanar options for the molecule
• Why does the reaction proceed exclusively through the

Anti coplanar structure?
• To see the difference between Anti and Syn, Newman
projections and hand held models can be helpful
• Evidence suggests that a strict 180° angle is not
necessary for E2 mechanisms.
• Similar angles (175–179°) are sufficient
• The term, anti-periplanar is generally used instead of
anti-coplanar to account for slight deviations from
coplanarity
• Although the E isomer is usually more stable because it
is less sterically hindered, the requirement for an anti-
periplanar transition state can often lead to the less
stable Z isomer
• Assuming they proceed through an anti-periplanar
transition state, predict the products for the following
reactions, and label them as cis or trans
• Assuming they proceed through an anti-periplanar
transition state, predict all of the products for the
following reaction
• Will the reaction be stereospecific or stereoselective,
and what factors most affect the product distribution?
• Consider the dehydrohalogenation of a cyclohexane
• Given the anti-periplanar requirement, which of the
two possible chair conformations will allow for the
elimination to occur?
• Which of the two molecules below will NOT be able to
undergo an E2 elimination reaction? WHY?
• It might be helpful to draw their chair structures and
make a handheld model
• Draw all of the possible products if each of the
molecules below were to undergo dehydrohalogenation
8.8 Predicting Products for E2
• Consider both regioselestivity and stereoselectivity to
predict the products for the eliminations below, and
draw complete mechanisms
Cl
NaOEt NaOtBu
8.9 The E1 Mechanism
• The E1 mechanism is a 2-step process
• Similar to SN1 (chapter 7), the reaction rate for E1 is not

affected by the concentration of the base
• What does the E and the 1 stand for in the E1 notation?
8.9 The E1 Mechanism
• Given the rate law for E1, which step in the mechanism
is the rate-determining slow step?
• If the second step were the slow step, how would you
write the rate law?
• How does the substrate reactivity trend for E1 compare
to the trend we discussed in chapter 7 for SN1? WHY?
• Just like we did for SN1 in chapter 7, to explain the

reactivity trend above, we must compare the energy
diagrams for each substrate
• To compare their energies, draw the structures for each
transition state, intermediate, and product below
• Because E1 and SN1 proceed by the same first step,
their competition will generally result in a mixture of
products
• How might you promote one reaction

over the other?
• Alcohols can also
undergo elimination or
dehydration by E1, but
the –OH group is not a
stable leaving group
• In the E1 reaction below, once the water leaving group
leaves the carbocation, what base should be used to
complete the elimination?

8.9 Regioselectivity for E1
• The final step of the E1 mechanism determines the
regioselectivity
• E1 reactions generally produce the Zaitsev product
predominantly. WHY?
• Why can’t we control the regioselectivity in this

reaction like we can in and E2 reaction?
8.9 Stereoselectivity for E1
• In the last step of the mechanism, a proton is removed
from a β carbon adjacent to the sp2 hybridized
carbocation
• Draw the appropriate carbocation that forms in the
reaction below, and rationalize the product distribution
8.9 Stereoselectivity for E1
• Considering stereochemistry and regiochemistry,
predict the products if the molecule below was treated
with concentrated sulfuric acid
OH
8.10 Complete E1 Mechanisms
• Recall the similarities between SN1 and E1
• After the carbocation is formed and possibly

rearranged, the E1 proton transfer neutralizes the
charge
• Why is the first proton transfer necessary?

• Explain why the carbocation rearranges

• The maximum number of steps in an E1 mechanism is

generally four
• Consider the
energy
diagram for
the
mechanism
on the
previous
slide
• Assess each
free energy
change
• The mechanism shows the formation of the major
products
• Predict the minor elimination products as well
• In E2, the base removes the β proton as the LG leaves
• Will such a reaction require a relatively strong base?
• Will E2 dehydrations likely involve a proton transfer

prior to the elimination?
8.12 Substitution vs. Elimination
• Substitution and Elimination are always in competition
• Sometimes products are only observed from S or E
• Sometimes a mixture of products is observed
8.12 Substitution vs. Elimination
• To predict whether substitution or elimination will
predominate, consider the factors below
1. Determine the function of the reagent. Is it more likely
to act as a base, a nucleophile, or both?
– Kinetics control nucleophilicity. WHY? HOW?
– Thermodynamics control basicity. WHY? HOW?
2. Analyze the substrate and predict the expected
mechanism (SN1, SN2, E1, or E2)
3. Consider relevant regiochemical and stereochemical
requirements
8.12 Reagent Function: Nucleophilicy
1. Assessing the strength of a nucleophile
• The greater the negative charge, the more nucleophilic
it is likely to be
• The more polarizable it is, the more nucleophilic it

should be
• The less sterically hindered it is, the more

nucleophilic it should be. WHY?
8.12 Reagent Function: Basicity
1. Assessing the strength of a base
• Assess the strength of its conjugate acid quantitatively
using the pKa of its conjugate acid
• Which is a stronger base Cl- or HSO4-?
• As bases, are Cl- and HSO4- relatively strong or weak?
8.12 Reagent Function: Basicity
1. Assessing the strength of a base
• If the base is neutral, assess the strength of its
conjugate acid qualitatively using ARIO (atom,
resonance, induction, orbital)
– Compare CH3OH and CH3NH2
• If the base carries a negative formal charge,

qualitatively assess the strength of the base using ARIO
– Compare Cl- and HSO4-
8.12 Basicity vs. Nucleophilicity
• Consider each of the reagent categories

• Reagents that act as nucleophiles only are either highly
polarizable and/or they have very strong conjugate
acids
• Reagents that act as bases only have either very
low polarizability and/or they are sterically
hindered
• The stronger the reagent, the more likely it is to
promote SN2 or E2. WHY?
• The more sterically hindered reagents are more likely to
promote elimination than substitution. WHY?
• The weaker the reagent, the more likely it is to promote
SN1 or E1. WHY?
8.13 Predicting Subst. vs. Elim.
1. Analyze the function of the reagent (nucleophile and/
or base)
2. Analyze the substrate (1°, 2°, or 3°)
or base)
or base)
or base)
8.14 Predicting Products
or base)
3. Consider regiochemistry and stereochemistry
8.14 Predicting Products
3. Consider regiochemistry and stereochemistry
• Practice with
SkillBuilder 8.12
Additional Practice Problems
• Name the following molecules
Cl
Cl
• Label the molecules below as either cis or trans and
either E or Z where appropriate
F F
F F
• For the substrate, give both the kinetically favored E2
product and the thermodynamically favored E2 product.
Explain what conditions can be used to favor each.
Br
• Since tertiary substrates react more readily than
secondary or primary in both E1 and E2 mechanisms,
what factor(s) usually controls which mechanism will
dominate and why?
• Consider both regioselestivity and stereoselectivity to
predict the major product for the elimination below
Br NaOEt
• Predict the major product if the alcohol below were
treated with concentrated sulfuric acid. Be aware of the
possible rearrangements.
conc
H2SO4
OH
Cl
• Predict the major NaOEt
product for the
following reactions
considering
competing NaSH
substitution and
Cl
elimination pathways.
NaOH
Cl

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Organic Chemistry

• The parent chain should include the C=C double bond

– The locant is ONE number, NOT two. Although the double

• Practice with SkillBuilder 8.1

• Is there a difference between cis-butane and trans-

• What specific type of isomers are cis and trans butene?

• Draw the structure for trans-cyclooctene

• When applied to bicycloakenes, this rule is called

• For molecules with different groups attached to the C=C

• Practice with SkillBuilder 8.2

• How does heat of combustion relate to stability?

• What pattern do you see?

• To understand the mechanism of elimination, first recall

• Which of the 4 steps MUST take place in every

• Could the steps happen in the reverse order?

• Practice with SkillBuilder 8.4

• How will a change in [base] or [substrate] affect the

• The 3° substrate should proceed through a more stable

• Practice with conceptual checkpoint 8.14

between the alkene

• Practice with SkillBuilder 8.5

• Why are both the

• Is the E formed exclusively because it is formed through

• Draw the transition state structure illustrating the

• Why does the reaction proceed exclusively through the

• Practice with SkillBuilder 8.6

• Practice with conceptual checkpoint 8.20

• Practice with SkillBuilder 8.7

• Similar to SN1 (chapter 7), the reaction rate for E1 is not

• What does the E and the 1 stand for in the E1 notation?

• Just like we did for SN1 in chapter 7, to explain the

• How might you promote one reaction

• Practice with conceptual checkpoint 8.27

• Why can’t we control the regioselectivity in this

• Practice with conceptual checkpoint 8.31

• After the carbocation is formed and possibly

• Why is the first proton transfer necessary?

• Explain why the carbocation rearranges

• The maximum number of steps in an E1 mechanism is

• Practice with SkillBuilder 8.9

• Will E2 dehydrations likely involve a proton transfer

• Sometimes a mixture of products is observed

• The more polarizable it is, the more nucleophilic it

• The less sterically hindered it is, the more

• Which is a stronger base Cl- or HSO4-?

• As bases, are Cl- and HSO4- relatively strong or weak?

• If the base carries a negative formal charge,

• Consider each of the reagent categories

• Practice with SkillBuilder 8.10

• Practice with SkillBuilder 8.11

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