Organic Chemistry, 5th Edition

L. G. Wade, Jr.

Chapter 8
Reactions of Alkenes

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2003,Prentice Hall
 Reactivity of C=C
• Electrons in pi bond are loosely held.
• Electrophiles are attracted to the pi
electrons.
• Carbocation intermediate forms.
• Nucleophile adds to the carbocation.
• Net result is addition to the double bond.

=>
Chapter 8 2
 Electrophilic Addition

• Step 1: Pi electrons attack the electrophile.

E
+
C C + E C C +

• Step 2: Nucleophile attacks the carbocation.

E E Nuc
_
C C+ + Nuc: C C

=>
Chapter 8 3
Types of Additions

=>
Chapter 8 4
 Addition of HX (1)
Protonation of double bond yields the most
stable carbocation. Positive charge goes to
the carbon that was not protonated.
CH3
CH3 C CH CH3
CH3 +
H
CH3 C CH CH3 _
+ Br
H Br X CH3
CH3 C CH CH3
+
H =>
Chapter 8 5
 Addition of HX (2)
CH3 CH3
_
CH3 C CH CH3 CH3 C CH CH3 + Br
+
H
H Br

CH3 CH3
CH3 C CH CH3
+
CH3 C CH CH3 =>
H Br H
_
Br

Chapter 8 6
 Regiospecificity
• Markovnikov’s Rule: The proton of an
acid adds to the carbon in the double
bond that already has the most H’s. “Rich
get richer.”
• More general Markovnikov’s Rule: In an
electrophilic addition to an alkene, the
electrophile adds in such a way as to
form the most stable intermediate.
• HCl, HBr, and HI add to alkenes to form
Markovnikov products. =>
Chapter 8 7
 Free-Radical
Addition of HBr
• In the presence of peroxides, HBr adds
to an alkene to form the “anti-
Markovnikov” product.
• Only HBr has the right bond energy.
• HCl bond is too strong.
• HI bond tends to break heterolytically to
form ions.
=>
Chapter 8 8
 Free Radical Initiation
• Peroxide O-O bond breaks easily to
form free radicals.
heat
R O O R R O + O R

• Hydrogen is abstracted from HBr.

R O + H Br R O H + Br
=>
Chapter 8 Electrophile 9
 Propagation Steps
• Bromine adds to the double bond.
Br + C C C C
Br

• Hydrogen is abstracted from HBr.

C C + H Br C C + Br
Br
Br H

Chapter 8 Electrophile => 10

 Anti-Markovnikov ??
CH3
CH3 C CH CH3
CH3 Br
CH3 C CH CH3 + Br CH3
X CH3 C CH CH3
Br

• Tertiary radical is more stable, so that

intermediate forms faster. =>
Chapter 8 11
 Hydration of Alkenes
+ H OH
H
C C + H2O C C
alkene
alcohol

• Reverse of dehydration of alcohol

• Use very dilute solutions of H2SO4 or
H3PO4 to drive equilibrium toward
hydration.
=>
Chapter 8 12
Mechanism for Hydration
H
H
+ +
C C + H O H C C + H2O

H
+
H H O H
+
C C + H2O C C

H
+ H
H O H H O
+
C C + H2O C C + H3O =>

Chapter 8 13
 Orientation for Hydration
• Markovnikov product is formed.
H
CH3
CH3
CH3 C CH CH3 + H O+ H
CH3 C CH CH3 + H2O
+
H
CH3 H2O
CH3 C CH CH3
+O H
CH3 H H
CH3 C CH CH3 H2O

H
O H =>
Chapter 8 14
 Indirect Hydration
• Oxymercuration-Demercuration
Markovnikov product formed
Anti addition of H-OH
No rearrangements
• Hydroboration
Anti-Markovnikov product formed
Syn addition of H-OH

=>
Chapter 8 15
 Oxymercuration (1)
• Reagent is mercury(II) acetate which
dissociates slightly to form +Hg(OAc).
• +Hg(OAc) is the electrophile that attacks
the pi bond.

O O O O
_ +
CH3 C O Hg O C CH3 CH3 C O Hg O C CH3

=>
Chapter 8 16
 Oxymercuration (2)
The intermediate is a cyclic mercurinium
ion, a three-membered ring with a
positive charge.
OAc
+
Hg
+
C C Hg(OAc) C C

=>

Chapter 8 17
 Oxymercuration (3)
• Water approaches the mercurinium ion from
the side opposite the ring (anti addition).
• Water adds to the more substituted carbon to
form the Markovnikov product.

OAc OAc OAc

+ Hg
Hg Hg
C C C C C C
+
H O O
H2O H H
H2O =>
Chapter 8 18
 Demercuration
Sodium borohydride, a reducing agent,
replaces the mercury with hydrogen.
OAc
Hg H
_
4 C C + NaBH4 + 4 OH 4 C C + NaB(OH)4
_
O O
+ 4 Hg + 4 OAc
H H

=>
Chapter 8 19
 Predict the Product
Predict the product when the given alkene
reacts with aqueous mercuric acetate,
followed by reduction with sodium
borohydride.
CH3 OH
(1) Hg(OAc)2, H2O
CH3
D
(2) NaBH4
D H

anti addition =>

Chapter 8 20
 Alkoxymercuration -
Demercuration
If the nucleophile is an alcohol, ROH,
instead of water, HOH, the product is an
ether.
(1) Hg(OAc)2,
CH 3OH Hg(OAc) H
C C (2) NaBH4
C C C C
O O
H3C H3C

=>

Chapter 8 21
 Hydroboration
• Borane, BH3, adds a hydrogen to the
most substituted carbon in the double
bond.
• The alkylborane is then oxidized to the
alcohol which is the anti-Mark product.
-
(1) BH3 (2) H2O2, OH
C C C C C C
H BH2 H OH
=>
Chapter 8 22
 Borane Reagent
• Borane exists as a dimer, B2H6, in equilibrium
with its monomer.
• Borane is a toxic, flammable, explosive gas.
• Safe when complexed with tetrahydrofuran.

H
+ -
2 O + B2H6 2 O B H =>
H
THF THF . BH3
Chapter 8 23
 Mechanism
• The electron-deficient borane adds to
the least-substituted carbon.
• The other carbon acquires a positive charge.
• H adds to adjacent C on same side (syn).

=>
Chapter 8 24
 Actually, Trialkyl
CH3
H
H3C C C H
H3C H
H
3 C C + BH3
H3C H H
H B H
H C C
H H C CH3
H3C C
CH3
CH3

Borane prefers least-substituted carbon due to steric hindrance as well as

charge distribution.
=>

Chapter 8 25
 Oxidation to Alcohol
• Oxidation of the alkyl borane with basic
hydrogen peroxide produces the alcohol.
• Orientation is anti-Markovnikov.

CH3 H CH3 H
H2O2, NaOH
CH3 C C H CH3 C C H
B H2O
H H OH
=>
Chapter 8 26
 Predict the Product
Predict the product when the given alkene
reacts with borane in THF, followed by
oxidation with basic hydrogen peroxide.

CH3 (1) BH3, THF H

CH3
-
(2) H2O2, OH OH
D D
syn addition
=>
Chapter 8 27
 Hydrogenation
• Alkene + H2  Alkane
• Catalyst required, usually Pt, Pd, or Ni.
• Finely divided metal, heterogeneous
• Syn addition

Chapter 8 =>
28
 Addition of Carbenes
• Insertion of -CH2 group into a double
bond produces a cyclopropane ring.
• Three methods:
Diazomethane
Simmons-Smith: methylene iodide and
Zn(Cu)
Alpha elimination, haloform
=>
Chapter 8 29
 Diazomethane
N N CH2 N N CH2
diazomethane

H
heat or uv light
N N CH2 N2 + C
H
carbene
C H
H C
C C C
C H
H

Extremely toxic and explosive. =>

Chapter 8 30
 Simmons-Smith
Best method for preparing cyclopropanes.

CH2I2 + Zn(Cu) ICH2ZnI

a carbenoid

CH2I2
=>
Zn, CuCl

Chapter 8 31
 Alpha Elimination
• Haloform reacts with base.
• H and X taken from same carbon
+-
CHCl3 + KOH K CCl3 + H2O

Cl
C -
Cl C Cl + Cl
Cl
Cl

CHCl3 Cl

Cl
=>
KOH, H2O

Chapter 8 32
 Stereospecificity
Cis-trans isomerism maintained around
carbons that were in the double bond.

H H CHBr3 H H
C C C C
H3C CH3 NaOH, H2O H3C CH3
Br Br

=>

Chapter 8 33
 Addition of Halogens
• Cl2, Br2, and sometimes I2 add to a
double bond to form a vicinal dibromide.
• Anti addition, so reaction is
stereospecific.
Br
C C + Br2 C C =>
Br

Chapter 8 34
 Mechanism for
Halogenation
• Pi electrons attack the bromine
molecule.
• A bromide ion splits off.
• Intermediate is a cyclic bromonium ion.
Br
C C C C
+ Br Br + Br =>

Chapter 8 35
 Mechanism (2)
Halide ion approaches from side opposite
the three-membered ring.
Br
Br
C C
C C
Br Br

=>

Chapter 8 36
 Examples of
Stereospecificity

=>
Chapter 8 37
 Test for Unsaturation
• Add Br2 in CCl4 (dark, red-brown color) to
an alkene in the presence of light.
• The color quickly disappears as the
bromine adds to the double bond.
• “Decolorizing bromine” is the chemical test
for the presence of a double bond.

=>
Chapter 8 38
Formation of Halohydrin
• If a halogen is added in the presence of
water, a halohydrin is formed.
• Water is the nucleophile, instead of
halide.
• Product is Markovnikov and anti.
Br Br Br
C C C C C C + H3O
+

O O
H2O H H H =>
H2O
Chapter 8 39
 Regiospecificity
The most highly substituted carbon has
the most positive charge, so nucleophile
attacks there.

=>

Chapter 8 40
 Predict the Product
Predict the product when the given alkene
reacts with chlorine in water.

CH3
OH
Cl2, H2O CH3
D
D
Cl

=>

Chapter 8 41
 Epoxidation
• Alkene reacts with a peroxyacid to form
an epoxide (also called oxirane).
• Usual reagent is peroxybenzoic acid.

O O O
C C + R C O O H C C + R C O H

=>

Chapter 8 42
 Mechanism
One-step concerted reaction. Several
bonds break and form simultaneously.

C O R C O R
C O C
O +

C H O C O
H

=>

Chapter 8 43
 Epoxide
Stereochemistry
Since there is no opportunity for rotation
around the double-bonded carbons, cis
or trans stereochemistry is maintained.

H H Ph C O O H O
C C
H
C C
H
=>
CH3 CH3 CH3 CH3

Chapter 8 44
 Opening the
Epoxide Ring
• Acid catalyzed.
• Water attacks the protonated epoxide.
• Trans diol is formed. OH
C C
+ H O
H3O OH
O H
O
C C C C C C

H2O
O
H H2O
=>
H

Chapter 8 45
 One-Step Reaction
• To synthesize the glycol without
isolating the epoxide, use aqueous
peroxyacetic acid or peroxyformic acid.
• The reaction is stereospecific.
O
OH
CH3COOH
H
=>
OH
H

Chapter 8 46
 Syn Hydroxylation
of Alkenes
• Alkene is converted to a cis-1,2-diol,
• Two reagents:
Osmium tetroxide (expensive!), followed by
hydrogen peroxide or
Cold, dilute aqueous potassium
permanganate, followed by hydrolysis with
base

=>
Chapter 8 47
 Mechanism with OsO4
Concerted syn addition of two oxygens to
form a cyclic ester.
O O O O
C C
Os Os
C C
O O O O

H2O2 C OH
+ OsO4 =>
C OH

Chapter 8 48
 Stereospecificity
If a chiral carbon is formed, only one
stereoisomer will be produced (or a pair
of enantiomers).
CH2CH3
H CH2CH3 (1) OsO4
H C OH
C
C
(2) H2O2 H C OH =>
H CH2CH3 CH2CH3
cis-3-hexene meso-3,4-hexanediol

Chapter 8 49
 Oxidative Cleavage
• Both the pi and sigma bonds break.
• C=C becomes C=O.
• Two methods:
Warm or concentrated or acidic KMnO4.
Ozonolysis
• Used to determine the position of a
double bond in an unknown.
=>
Chapter 8 50
 Cleavage with MnO4-
• Permanganate is a strong oxidizing
agent.
• Glycol initially formed is further oxidized.
• Disubstituted carbons become ketones.
• Monosubstituted carbons become
carboxylic acids.
• Terminal =CH2 becomes CO2.
=>
Chapter 8 51
 Example
H CH3
H CH3 KMnO4
C C H3C C C CH3
CH3 CH3 (warm, conc.)
OH OH
H CH3
H3C C + C CH3
O O

=>
OH
H3C C
Chapter 8 52
O
 Ozonolysis
• Reaction with ozone forms an ozonide.
• Ozonides are not isolated, but are
treated with a mild reducing agent like
Zn or dimethyl sulfide.
• Milder oxidation than permanganate.
• Products formed are ketones or
aldehydes.
=>
Chapter 8 53
 Ozonolysis Example
O
H CH3 O3 H CH3
C C C C
CH3 CH3 O O
H3C CH3
Ozonide

H O
(CH3)2S CH3
C O O C + CH3 S CH3 =>
H3C CH3
DMSO

Chapter 8 54
End of Chapter 8

Chapter 8 55