Organic Chemistry,

L. G. Wade, Jr.

Chapter 8
Lecture
Reactions of Alkenes

lubrication

姚少凌 Chao-Ling Yao

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 8-1 Reactivity of the Carbon–
Carbon Double Bond
• The alkenes can be converted to alkyl halides,
epoxides, alcohols, aldehydes, ketones, carboxylic
acids, and other functional groups.

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 Reactivity of the Carbon–
Carbon Double Bond
• The most common reactions of double bonds transform
the pi bond into a sigma bond.
The reaction is exothermic.
The product is more stable than reactants.

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 Types of Alkene Reactions

Two molecules combine to form one product molecule.

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 8-2 Electrophilic Addition to
Alkene

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 Bonding in Alkenes
• The pi bond is delocalized above and
below the sigma bond.
The pi-bond electrons are spread farther
from the carbon nuclei.
Electrons in pi bonds are loosely held.
• The double bond acts as a nucleophile,
donating a pair of electrons to the
electrophile.
• Carbocations are intermediates in some of these reactions.
• These reactions are called electrophilic additions.

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 Electrophilic Addition

• Step 1: Pi electrons attack the electrophile.

• Step 2: Nucleophile attacks the carbocation.

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 Electrophilic Addition
Ex:
• Step 1: Protonation of the double bond forms a carbocation

• Step 2: Bromide ion attacks the carbocation.

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 Types of Additions
• Regiochemistry
orientation of
addition
which part of the
reagent adds to
which end of the
double bond.

• Stereochemistry

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 8-3 Addition of Hydrogen
Halides to Alkenes

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 Orientation of Addition:
Markovnikov’s Rule
• The addition of HBr to 2-methylbut-2-ene could lead to
either of two products.
However, only one is observed.

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 Markovnikov’s Rule

• The first step is protonation of the double bond.

 The acid proton will bond to carbon 3 in order to produce
the most stable carbocation possible.
 Stability of carbocations: 3o > 2o > 1o > +CH3
 Therefore, the proton adds to the end of the double
bond that is less substituted to give the more
substituted (stable) carbocation.
 It is said to be regioselective.
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 Markovnikov’s Rule (Continued)

• The second step is the bromide anion then adds to

the carbocation.

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 The Reaction-Energy Diagram

• The first step is rate-determining in the electrophilic

addition to an alkene.
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 Regioselectivity
• A Russian chemist, Vladmir Markovnikov, first showed
the orientation of addition of HBr to alkenes in 1869.
• Markovnikov’s rule: The addition of a proton acid to
the double bond of an alkene results in a product with
the acidic proton bonded to the carbon atom that
already holds the greater number of hydrogen atoms.
 Markovnkov orientation, Markovnikov product

• Markovnikov’s rule (extended): In an electrophilic

addition to the alkene, the electrophile adds in such a
way that it generates the most stable intermediate.

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 Example

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 More Examples

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 Free-Radical Addition of HBr
• In the presence of peroxides, HBr adds to an alkene to form
the “anti-Markovnikov” product.
Special when the reagents or solvents came from old
suppliers that had accumulated peroxides from exposure to
the air.
• Peroxides produce free radicals.
• Only HBr has just the right reactivity for each step of the
free-radical chain reaction to take place.
The peroxide effect is not seen with HCl or HI because the
reaction of an alkyl radical with HCl or HI is strongly
endothermic.
• Each step of free-radical addition is moderately exothermic,
allowing them to proceed faster than termination steps.
Consume all reactants.
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 Free-Radical Initiation
Initiation: Formation of radicals

• The peroxide bond breaks homolytically to form the

first radical:

• Hydrogen is abstracted from HBr.

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 Propagation Steps
Propagation: A radical reacts to generate another radical.
• Step 1: A Br radical adds to the double bond to generate an
alkyl radical on the more substituted C atom.

• Step 2: The alkyl radical abstracts a H atom from HBr to

generate the product and a Br radical

• The Br radical generated in Step 2 goes on to react in

Step 1, continuing the chain.
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• The peroxide effect is not seen with HCl or HI because the
reaction of an alkyl radical with HCl or HI is strongly
endothermic.

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 Example
• Bromine adds to the double bond, forming the
most stable radical possible:

• Hydrogen is abstracted from HBr:

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 Anti-Markovnikov Stereochemistry

• Stability of radical: 3o > 2o > 1o > +CH3

• In anti-Markovnikov product, H has added to the more
substituted end of the double bond.
 The end started with fewer hydrogens.

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 Stereochemistry
• Note that both mechanism for the addition of HBr to an
alkene (with or without peroxides) follow the extended
statement of Markovnikov’s rule:
The electrophile adds to the less substituted end of the
double bond to give more stable intermediate, either a
carbocation or a free radical.
In the ionic reaction, the electrophile is H+.
In the peroxide-catalyzed free-radical reaction, Br
radical is the electrophile.
The peroxide-catalyzed free-radical reaction is faster.

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 Solved Problem 8-1
Show how you would accomplish the following synthetic conversions.
(a) Convert 1-methylcyclohexene to 1-bromo-1-methylcyclohexane.
SOLUTION
This synthesis requires the addition of HBr to an alkene with Markovnikov orientation.
Ionic addition of HBr gives the correct product.

(b) Convert 1-methylcyclohexanol to 1-bromo-2-methylcyclohexane.

SOLUTION
This synthesis requires the conversion of an alcohol to an alkyl bromide with the bromine
atom at the neighboring carbon atom. This is the anti-Markovnikov product, which could
be formed by the radical-catalyzed addition of HBr to 1-methylcyclohexene.

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 Solved Problem 8-1
Continued
1-Methylcyclohexene is easily synthesized by the dehydration of 1-
methylcyclohexanol.
The most substituted alkene is the desired product.

The two-step synthesis is summarized as follows:

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 8-4 Addition of Water:
Hydration of Alkenes

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 Hydration of Alkenes
• Addition of water (with strongly acidic catalyst) to the double
bond forms an alcohol.
Hydration (addition of water)
This is the reverse of the dehydration of alcohol (Ch 7.18).
• It uses dilute solutions of H2SO4 or H3PO4 (excess water) to
drive equilibrium toward hydration.
• The addition follows Markovnikov’s rule.

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 Principle of Microscopic Reversibility
• Principle of Microscopic Reversibility
A forward reaction and a reverse reaction taking place under
the same condition (in equilibrium) must follow the same
reaction pathway in microscopic detail.
The lowest-energy transition states and intermediates are
the same.

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 Mechanism for Hydration
Step 1: Protonation of the double bond forms a carbocation.
acid-catalyzed
hydration

Step 2: Nucleophilic attack by water gives a protonated alcohol.

Step 3: Deprotonation gives the alcohol.

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 Ex: Acid-catalyzed hydration of Propene
Step 1: Protonation of the double bond forms 2o carbocation.

Step 2: Nucleophilic attack by water gives a protonated alcohol.

Step 3: Deprotonation gives the alcohol.

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 Orientation of Hydration

• The protonation follows Markovnikov’s rule: The proton

adds to the less substituted end of the double bond, so the
positive charge appears at the more substituted end (most
stable carbocation).
Like the addition of hydrogen halides, hydration is
regioselective.
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 Rearrangements Are Possible

Methyl Shift:

• A methyl shift after protonation will produce

the more stable tertiary carbocation.
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 8-5 Hydration by Oxymercuration-
Demercuration

• Many alkenes do not easily undergo hydration in

aqueous acid due to insoluble or side reactions.

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 Oxymercuration–Demercuration Reaction
• Oxymercuration-demercuration is another method for
converting alkenes to alcohols with Markovnikov orientation.
Work with many alkenes that do not easily undergo
direction hydration (addition of water to the double bond)
Milder conditions than direct hydration
No free carbocation is formed, so no rearrangements or
polymerization

Mercuric acetate
Hg(OCOCH3)2
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 1. Oxymercuration Reaction
• The reagent is mercury(II) acetate, which dissociates slightly
to form +Hg(OAc).
 +Hg(OAc) is the electrophile that adds to the pi bond.

• The intermediate is a three-membered ring called the

mercurinium ion.
• Overall, the addition of water follows Markovnikov’s rule.

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 Mechanism of Oxymercuration
Step 1: Electrophilic attack forms a mercurinium ion.

Step 2: Water open the ring to give an organomercurial alcohol.

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 2. Demercuration Reaction

• In the demercuration reaction, a hydride furnished by the

sodium borohydride (NaBH4) replaces the mercuric
acetate.
• The overall reaction gives the Markovnikov product
with the hydroxy group on the most substituted
carbon.

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 Mechanism of Demercuration
Step 1: Demercuration replaces the mercuric fragment with H to
give alcohol.

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 Ex: Oxymercuration–demercuration of propene
Step 1: Electrophilic attack forms a mercurinium ion.

Step 2: Water open the ring to give an organomercurial alcohol.

Step 3: Demercuration replaces the mercuric fragment with H to give

alcohol.

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 Stereochemistry of the Mercurinium
Ion Opening
• Water adds to the more substituted carbon to
form the Markovnikov product.
• Water approaches the mercurinium ion from the
side opposite the ring (anti addition).

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 Oxymercuration–Demercuration of
3,3,-Dimethylbut-1-ene

• The reaction does not suffer from rearrangements

because there is no carbocation intermediate.
 Better yield than direct acid-catalyzed hydration
 Suitable in Lab
 However, organomercurial compounds are highly toxic.
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 8-6 Alkoxymercuration -
Demercuration

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 Alkoxymercuration - Demercuration
Alkoxymercuration – Demercuration:
• When mercuration takes place in an alcohol solvent, the
alcohol (R-OH) serves as a nucleophile to attack the
mercurinium ion.
 Alkenes are converted to ether.

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 Alkoxymercuration - Demercuration

• Mechanism of alkoxymercuration-demercuration:
 Follow the Markovnikov orientation.

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 Solved Problem 8-2
Show the intermediates and products that result from alkoxymercuration–
demercuration of 1-methylcyclopentene, using methanol as the solvent.
SOLUTION
Mercuric acetate adds to 1-methylcyclopentene to give the cyclic mercurinium ion. This ion
has a considerable amount of positive charge on the more substituted tertiary carbon
atom. Methanol attacks this carbon from the opposite side, leading to anti addition: The
reagents (HgOAc and OCH3) have added to opposite faces of the double bond.

Reduction of the intermediate gives the Markovnikov product, 1-methoxy-1-

methylcyclopentane.

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 8-7 Hydroboration of Alkenes

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 Hydroboration of Alkenes

• Such an anti-Markovnikov hydration was impossible until H.C. Brown,

of Purdue University.
 Discovered that diborane (B2H6) adds to alkenes with anti-
Markovnikov orientation.
 The Nobel Prize in Chemistry in 1979.

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 • Diborane is a dimer composed of two molecules of borane
(BH3)
The B atom in borane has only six electrons around it, and
it’s a powerful Lewis acid.
Its tendency to acquire an additional electron pair leads it to
share two H with the other borane molecule in diborane.

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 Diborane
• Diborane (B2H6, toxic, flammable & explosive) is a dimer
of borane and is in equilibrium with a small amount of BH3.

Major Minor

• The complex of borane with tetrahydrofuran (BH3•THF)

is the most commonly used form of borane.

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 Hydroboration of Alkenes

alkylborane

• BH3 adds to the double bond of an alkene to give an

alkylborane.
• Basic hydrogen peroxide oxidizes the alkylborane to an
alcohol.

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 Mechanism of Hydroboration
• Borane is an electron-deficient compound. So, it is a
strong electrophile, capable of adding to a double bond.
• Borane adds to the double bond in a single step, with
boron adding to the less substituted carbon and
hydrogen adding to the more highly substituted carbon.
• This orientation places the partial positive charge in the
transition state on the more highly substituted carbon atom.

the same side

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 Oxidation to Alcohol

• Oxidation of the alkyl borane with basic hydrogen

peroxide produces the alcohol.
• Orientation is anti-Markovnikov.

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 Solved Problem 8-3
Show how you would convert 1-methylcyclopentanol to 2-methylcyclopentanol.
SOLUTION
Working backward, use hydroboration–oxidation to form 2-methylcyclopentanol from 1-
methylcyclopentene. The use of (1) and (2) above and below the reaction arrow indicates
individual steps in a two-step sequence.

The 2-methylcyclopentanol that results from this synthesis is the pure trans isomer. This
stereochemical result is discussed in Section 8-7C.
1-Methylcyclopentene is the most substituted alkene that results from dehydration of
1-methylcyclopentanol. Dehydration of the alcohol would give the correct alkene.

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 Stoichiometry of Hydroboration
• Three moles of alkene can react with each mole of BH3.

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 Stereochemistry of Hydroboration

• The hydroboration step adds the hydrogen and the boron

to the same side of the double bond (syn addition).
• When the boron is oxidized, the OH will keep the same
stereochemical orientation.
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 The Role of the Hydroperoxide Ion
& Oxidation of a Trialkylborane

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 Solved Problem 8-4
A norbornene molecule labeled with deuterium is subjected to hydroboration–
oxidation. Give the structures of the intermediates and products.

SOLUTION
The syn addition of BH3 across the double bond of norbornene takes place mostly
from the more accessible outside (exo) face of the double bond. Oxidation gives a
product with both the hydrogen atom and the hydroxy group in exo positions. (The
less accessible inner face of the double bond is called the endo face.)

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 8-8 Addition of Halogens to
Alkenes

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 Addition of Halogens
• Cl2, Br2, and sometimes I2 add to a double bond to
form a vicinal dihalide.
• This is an anti addition of halides.

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 Mechanism of Halogen Addition
• A halogen molecule is electrophilic.
• A nucleophile can react with a halogen, displacing a
halide ion.

Ex:

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 • In the last reaction (the previous slide), the pi electrons
of an alkene attack the bromine molecule, expelling
bromide ion.
• A halonium ion results, containing a three-membered
ring with a positive charge on the halogen atom.
 That is similar in structure to the mercurinium ion (Ch 8.5).

Positive charge, strong electrophilic

attack by a nucleophile
Ex: a halide ion

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 Mechanism: Addition of Halogens to Alkenes
Step 1: Electrophilic attack forms a halonium ion.

Step 2: The halide ion opens the halonium ion (back-side attack).

• The intermediate is a three-membered ring called the

halonium ion.
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 Ex: Addition of Br2 to propene.

Step 1: Electrophilic attack forms a bromonium ion.

Step 2: Bromide ion opens the bromonium ion.

more positive
charge C

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 Stereochemistry of Halogen Addition

• Anti stereochemistry results from the back-side attack

of the nucleophile on the bromonium ion.
• This back-side attack assures anti stereochemistry of
addition.
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 Ex:

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 Bromine Test for Unsaturation
• Add Br2 in CCl4 (dark, red-
brown color) to an alkene.
The color quickly disappears
as the bromine adds to the
double bond (left-side test
tube).

• If there is no double bond

present, the brown color will
remain (right side).
• “Decolorizing bromine” is the
chemical test for the presence
of a double bond.

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 8-9 Formation of Halohydrins

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 Mechanism of Halohydrin Formation
• A halohydrin is an alcohol with a halogen on the adjacent
carbon atom.
In the presence of water, halogens add to alkenes to form
halohydrins.
Step 1: Electrophilic attack forms a bromonium ion.

Step 2: Water opens the bromonium ion; deprotonation gives the

halohydrin.

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 Ex: Addition of Cl2 to propene in water
Step 1: Electrophilic attack forms a chloronium ion.

Step 2: Back-side attack by water opens the chloronium ion.

Step 3: Water removes a proton to give the chlorohydrin.

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 Formation of Halohydrins

• If a halogen is added in the presence of water as solvent,

a halohydrin is formed.
If that is with no solvent or with an inert solvent (Ex: CCl4
or CHCl3), a dihalide is formed.
• Water is the nucleophile.
• This is a Markovnikov addition: The bromide
(electrophile) will add to the less substituted carbon.
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 Stereochemistry of Halohydrins
• Because the mechanism involves a halonium ion,
the stereochemistry of addition is anti, as in
halogenation.

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 Orientation of Halohydrin Formation
• The more substituted carbon of the chloronium ion bears
more positive charge than the less substituted carbon.
• Attack by water occurs on the more substituted carbon to
give the Markovnikov product.

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 Solved Problem 8-5
Propose a mechanism for the reaction of 1-methylcyclopentene with bromine
water.
SOLUTION
1-Methylcyclopentene reacts with bromine to give a bromonium ion. Attack by
water could occur at either the secondary carbon or the tertiary carbon of the
bromonium ion. Attack actually occurs at the more substituted carbon, which bears
more of the positive charge. The product is formed as a racemic mixture.

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 Solved Problem 8-6
When cyclohexene is treated with bromine in saturated aqueous sodium
chloride, a mixture of trans-2-bromocyclohexanol and trans-1-bromo-2-
chlorocyclohexane results. Propose a mechanism to account for these two products.
SOLUTION
Cyclohexene reacts with bromine to give a bromonium ion, which will react with
any available nucleophile. The most abundant nucleophiles in saturated aqueous
sodium chloride solution are water and chloride ions. Attack by water gives the
bromohydrin, and attack by chloride gives the dihalide. Either of these attacks gives
anti stereochemistry.

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 8-10 Catalytic Hydrogenation
of Alkenes

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 Catalytic Hydrogenation of Alkenes

• Hydrogen (H2) can be added across the double bond in a

process known as catalytic hydrogenation.
• The reaction only takes place if a catalyst (Pt, Pd, Ni) is
used.
An example of heterogeneous catalysis (different phases)
Not homogeneous catalysis (the same phase, ex: acid-
catalyzed dehydration of an alcohol)
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 Mechanism of Catalytic Hydrogenation
• Reaction condition:
RT; atmospheric pressure; alkenes in an alcohol, an
alkane or an acetic acid; shaking or stirring.
The hydrogen and the alkene are adsorbed on the
metal surface.

• Once adsorbed, the hydrogens insert across the same

face of the double bond and the reduced product is
released from the metal.
• The reaction has a syn stereochemistry since both
hydrogens will add to the same side of the double
bond.

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 Syn Stereochemistry in
Catalytic Hydrogenation

• A solid heterogeneous catalyst adds two

hydrogen atoms to the same face of the pi bond.

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 Wilkinson’s Catalyst
• Wilkinson’s catalyst is a soluble homogenous catalyst that
catalyzes the hydrogenation of a C=C bond.
• Wilkinson’s catalyst is not chiral, but its PPh3 ligands can
be replaced by chiral ligands to give chiral catalysts that are
capable of converting optically inactive starting materials to
optically active products.
That is called asymmetric induction or enantioselective
synthesis.
PPh3 : triphenylphosphine

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 Chiral Hydrogenation Catalysts
Ex: Ryoji Noyori & William Knowles,
2001 Nobel Prize in Chemistry catalyst is chiral

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 The Need for Chiral Catalysts
• Enantioselective synthesis is particularly important in the
pharmaceutical industry, because only one enantiomer of
a chiral drug is likely to have the desired effect.
• Only the (–)-enantiomer of dopa can cross the blood–
brain barrier and be transformed into dopamine; the other
enantiomer is toxic to the patient.

*
A precursor: amino acid
 can cross
 (+) is toxic
Parkinson’s drug
 can not cross the
”blood-brain barrier”
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 8-11 Addition of Carbenes to
Alkene

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 Addition of Carbenes
• Methylene (:CH2) is the simplest of the carbenes:
uncharged, reactive intermediates.
a C atom with two bonds and two nonbonding electrons
Like borane (BH3), it is a potent electrophile (unfilled
octet).
• The insertion of the —CH2 group into a double bond
produces a cyclopropane ring.
• There are three methods:
– Diazomethane (CH3N2, UV
light or heat)
– Simmons–Smith (CH2I2 and
Zn(Cu))
– Alpha elimination of a
haloform (CHX3, NaOH, H2O)

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 Carbenes: Diazomethane Method

Problems with diazomethane:

1. Extremely toxic and explosive
2. The carbene can insert into C—H bonds.
 form many side products

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 Simmons–Smith Reaction
• Named for the two DuPont chemists who discovered it by
adding methylene iodide to the “Zinc-copper couple”.
• Preparation of the Simmons–Smith reagent:
CH2I2 + Zn(Cu)  ICH2ZnI
Simmons–Smith reagent
(a carbenoid)
• Best method for preparing cyclopropanes.

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 Alpha Elimination Reaction
• Carbenes are also formed by reactions of halogenated
compounds with bases.
At least one H and enough halogen atoms to make be acidic.
Ex: chloroform (CHCl3) or bromoform (CHBr3)

• Alpha (α) elimination:

H and halogen are lost from the same C atom.
• Beta (β) elimination:
H and halogen are lost from adjacent C atom (more common).
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 Ex: Dibromocarbene formed from CHBr3 can add to a
double bond to form a dibromocyclopropane.

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 Stereospecificity

• The cylopropanes will retain the cis or trans

stereochemistry of the alkene.

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 8-12 Epoxidation of Alkenes
• Oxidations are particularly important because many
common functional groups contain O, and alkene oxidations
are some of the best methods for introducing O into organic
molecules.
Epoxidation
dihydroxylation
oxidative cleavage of alkene double bonds.

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 Epoxidation
• An alkene reacts with a peroxyacid to form an epoxide.
An epoxide (also called oxirane) is a three-membered cyclic
ether.
Epoxides are valuable synthetic intermediates use for
converting alkenes to a variety of other function groups.
Peroxyacid is a carboxylic acid that has an extra O atom in
a –O–O– (peroxy) linkage.

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 Peroxyacids
• The epoxidation of an alkene is clearly an oxidation,
because an O atom is added.
• Peroxyacids are highly selective oxidizing.
 Some simple peroxyacids are called peracids.

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 Mechanism: Epoxidation of Alkenes
• The peroxyacid and the alkene react with each other in
a one-step (concerted) reaction to produce the
epoxide and a molecule of acid.

Ex: Epoxidation of propene by peroxyacetic acid

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 Stereochemistry of Epoxidation
• The epoxide retains whatever stereochemistry is
present in the alkene.
Because the epoxidation takes place in one step, there is no
opportunity for the alkene molecule to rotate and
change its cis or trans geometry.
• The most common peroxyacid used is MCPBA.
(meta-chloroperoxybenzoic acid)

precipitation

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 8-13 Acid-Catalyzed Opening
of Epoxides

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 Opening the Epoxide Ring
• Most epoxides are easily isolated as stable products if the
solution is not too acidic.
Any moderately strong acid protonates the epoxide.
This process is acid-catalyzed.
• Water attacks the protonated epoxide on the opposite
side of the ring (back-side attack) and forming a 1,2-diol
(called glycol).
Anti-diol is formed.

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 Mechanism: Acid-Catalyzed Opening of Epoxides
Step 1: Protonation of the epoxide activates it toward nucleophilic
attack.

Step 2: Back-side attack by the solvent (water) opens the ring.

Step 3: Deprotonation gives the diol product.

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 Ex: Acid-catalyzed hydrolysis of epoxypropane
Step 1: Protonation of the epoxide.

Step 2&3: Back-side attack by water, then deprotonation of the

product.

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 Peroxyacids for Epoxidation &
Opening the Ring
strong acid: weak acid:
epoxidation & epoxidation
opening the ring

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 8-14 Syn Hydroxylation
of Alkenes

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 Syn Hydroxylation of Alkenes
• Dihydroxylation (hydroxylation) of double bond:
Converting an alkene to a glycol requires adding a
hydroxy group to each end of the double bond.
Anti dihydroxylation: acid-catalyzed opening of epoxides
(Ch 8.13)
Syn dihydroxylation: using osmium tetroxide (OsO4) or
potassium permanganate (KMnO4)

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 Mechanism with OsO4
• The OsO4 (Osmium tetroxide or osmic acid) adds to the
double bond of an alkene in a concerted mechanism
forming an osmate ester.
 OsO4 is expensive, toxic and volatile.
• The osmate ester can be hydrolyzed (by H2O2 or
tertiary amine oxides) to produce a cis-glycol (Syn
stereochemistry) and regenerate the OsO4.

continue & repeat

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 Ex: Syn stereochemistry

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 Permanganate Dihydroxylation

• A cold, dilute solution of KMnO4 also hydroxylates

alkenes with syn stereochemistry.
 Slightly reduced yields in most case.
• The basic solution hydrolyzes the manganate ester,
liberating the glycol and producing a brown precipitate of
manganese dioxide, MnO2. Test the presence of an alkene
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 Choosing a Reagent
• How to select OsO4 or KMnO4 ?

• Osmium tetroxide is expensive, highly toxic, and volatile.

High yield; suitable for rare starting reactant.

• Potassium permanganate is safe and cheap.

Low yield; suitable for the first step of reaction or large
scale production.

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 8-15 Oxidation Cleavage of
Alkenes
• After oxidation of alkenes to glycols. Stronger conditions
can further oxidize glycols to cleave the bond that was
originally the double bond.
KMnO4 and ozone are two of the most common
reagents for such oxidative cleavages.

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 Oxidative Cleavage with KMnO4
• In a KMnO4 dihydroxylation, if the solution is warm or
acidic or too concentrated, oxidative cleavage of the
glycol may occur.
In effect, the double bond is cleaved to two carbonyl
groups (C=O).
• Disubstituted carbons become ketones.
• Monosubstituted carbons become aldehydes and are
furtherly oxidized to carboxylic acids.
• If the molecule contains a terminal =CH2 group, that
group is oxidized all the way to CO2 and water.

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 Examples

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 Ozonolysis
• Like KMnO4, ozone cleaves double bond to give ketones
and aldehydes.
However, ozonolysis is milder, and both ketones and
aldehydes can be recovered without further oxidation.

• Ozone has 142 kJ/mol of excess energy over oxygen and

it is much more reactive.
positive charge

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half a negative charge
 Mechanism of Ozonolysis
Step 1:
• The ozone adds to the double bond, forming a cyclic, five-
membered ring intermediate called primary ozonide or
molozonide, which rearranges to form the ozonide.
Cooled with dry ice (-78 oC) to minimize side reactions.
Two peroxy (-O-O-) linkages is not stable, so it rearranges
to form an ozonide.

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 Reduction of the Ozonide
Step 2:
• The ozonide is also not stable and is not isolated, but is
immediately reduced by a mild reducing agent, such
as zinc or dimethyl sulfide, to give the aldehydes
and ketones as the main products.
• When dimethyl sulfide is used, the sulfur atom gets
oxidized, forming dimethyl sulfoxide (DMSO).

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 Ex:

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 • One of the most common uses of ozonolysis has been for
determining the position of double bonds in alkenes.

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 Solved Problem 8-7
Ozonolysis–reduction of an unknown alkene gives an equimolar mixture of
cyclohexanecarbaldehyde and butan-2-one. Determine the structure of the original
alkene.

SOLUTION
We can reconstruct the alkene by removing the two oxygen atoms of the carbonyl groups
(C O) and connecting the remaining carbon atoms with a double bond. One uncertainty
remains, however: The original alkene might be either of two possible geometric
isomers.

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 Comparison of Permanganate Cleavage
and Ozonolysis
• Ozone will oxidatively cleave (break) the double bond to
produce aldehydes and ketones.
• Ozonolysis is milder than KMnO4 and will not oxidize
aldehydes further.
• A second step of the ozonolysis is the reduction of the
intermediate by zinc or dimethyl sulfide.

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 8-16 Polymerization of Alkenes
• Alkenes serve as monomers for some if the most
common polymers.
Ex: polyethylene, polypropylene, polystyrene,
poly(vinyl chloride) and many others.

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 Polymerization
• An alkene (monomer) can add to another molecule like
itself to form a chain (polymer).
• Addition polymers generally form by chain-growth
polymerization, the rapid addition of one molecule at a
time to a growing polymer chain.
• Three methods:
– Cationic, a carbocation intermediate
– Free radical
– Anionic, a carbanion intermediate (rare)

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 1. Cationic Polymerization
• An alkene is treated with an acid. Protonation of the
alkene forms a carbocation.
• Another molecule of the alkene may act as the nucleophile
and attack the carbocation to form dimer and give another
carbocation.

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Termination Step of Cationic Polymerization

• The chain growth ends when a proton is abstracted

by the weak base of the acid used to initiate the
reaction.
• The loss of a hydrogen forms an alkene and ends the
chain growth, so this is a termination step.

 Polyisobutylene (PIB, 聚異丁烯) is one of the constituents of butyl

rubber used in inner tubes and other synthetic rubber products.

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 Cationic Polymerization Using BF3 as Catalyst
• BF3 is an excellent catalyst for cationic polymerization.
• BF3 is electron-deficient and a strong Lewis acid.

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 Termination of the Polymer Chain
• The most likely ending of the BF3-catalyzed
polymerization is the loss of a proton from the carbocation
at the end of the chain.
• This side reaction terminates one chain, but it also
protonates another molecule of styrene, initiating a new
chain.

 Polystyrene (PS,聚苯乙烯) is a clear, brittle plastic that is used for

inexpensive lenses, transparent containers, and Styrofoam
insulation.
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 2. Free-Radical Polymerization
• Many alkenes undergo free-radical polymerization when
they are heated with radical initiators.
 Such as peroxide initiator at 100 oC

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 3. Anionic Polymerization
• For an alkene to gain electrons, strong electron-withdrawing
groups such as nitro, cyano, or carbonyl must be attached
to the carbons in the double bond.
Ex:
metal oxides

 Methyl α-cyanoacrylate is sold commercially as super glue.

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 8-17 Olefin Metathesis

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 Olefin Metathesis
• We can think of a double bond as two alkylidene groups
(=CHR).
• Olefin metathesis is any reaction that trades and
interchanges alkylidene groups.
Greek word: meta (change) & thesis (position)

• The 2005 Nobel Prize in Chemistry was awarded to Yves

Chauvin (French Petroleum Institute), Robert Grubbs
(Caltech), and Richard Schrock (MIT)
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 Catalysts for Olefin Metathesis
• Olefin metathesis was first observed in the 1950s, and was
used in industry to convert propylene to a mixture of but-2-
ene and ethylene.
Phillips Triolefin Process
An aluminum/molybdenum catalyst (structure was unknown)
was used.

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 Catalysts for Olefin Metathesis
• [M] = CHR
 M: metal

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 Examples for Olefin Metathesis
• Gas, leaving the solution, drive
the reaction to complete.

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 Mechanism of Olefin Metathesis
• Mechanism published by Yves Chauvin in 1971.

• The metal-alkylidene catalyst forms an intermediate four-

membered ring with an alkylidene followed by ring opening.

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