11/1/2010

1
Chapter 6
Addition Reactions of
Alk Alkenes
The characteristic reaction of alkenes is
addition to the double bond.
Reverse of elimination, AB represents:
HH; hydrogenation reaction
HOH; hydration reaction
HX; hydrohalogenation reaction
Reactions of Alkenes
; y g
XX; halogenation reaction
Also epoxidation, formation of a 3-membered
ring with an O
+ AB
C C A
C C B
+ HH
o
o o
H C C
H H
H H
H
t
C C
H
H
H
H
Hydrogenation of Ethylene
exothermic AH= 136 kJ/mol
catalyzed by finely divided Pt, Pd, Rh, Ni
Example
H
2
, Pt
CH
2
H
3
C
H
3
C
(73%)
CH
3
H
H
3
C
H
3
C
What three alkenes yield 2-methylbutane on
catalytic hydrogenation?
Problem 6.1
H
2
, Pt
can be used to measure relative stability of
isomeric alkenes
correlation with structure is same as when heats
of combustion are measured
Heats of Hydrogenation
11/1/2010
2
H
H
H
C C
A
B
X
Y
Mechanism of Catalytic Hydrogenation
Interaction with the metal catalyst is critical
Hydrogen bonds to the surface of the metal
H
H
H
Mechanism of Catalytic Hydrogenation
Alkene uses its t electrons to bond to the surface
of the metal; the other carbon bonds to H
H H
A
B
X
Y
H H
H
C C
H
Mechanism of Catalytic Hydrogenation
H
H
H
C C
A
B
X
Y
H
H
H
H
Heats of Hydrogenation of Isomers
CH
3
CH
2
CH
2
CH
3
119
115
Ethylene 136
Monosubstituted 125-126
cis-Disubstituted 117-119
Heats of Hydrogenation (kJ/mol)
trans-Disubstituted 114-115
Terminally disubstituted 116-117
Trisubstituted 112
Tetrasubstituted 110
Match each alkene of Problem 6.1 with its correct
heat of hydrogenation.
126 kJ/mol
highest heat of
hydrogenation;
least stable isomer
Problem 6.2
118 kJ/mol
112 kJ/mol
lowest heat of
hydrogenation;
most stable isomer
11/1/2010
3
Stereochemistry of Alkene Hydrogenation
There are two spatial stereochemical aspects of
alkene hydrogenation:
syn addition of both H atoms to double bond
hydrogenation is stereoselective, corresponding to
addition to less crowded face of double bond
A reaction in which a single starting material A reaction in which a single starting material
can give two or more stereoisomeric products
but yields one of them in greater amounts than
the other (or even to the exclusion of the other)
is said to be stereoselective.
syn addition
anti addition
syn Addition versus anti Addition
Example of syn-Addition
H
2
, Pt
CO
2
CH
3
CO
2
CH
3
CO
2
CH
3
CO
2
CH
3
H
(100%)
CO
2
CH
3
H
A single starting material can give two or more
stereoisomeric products, but gives one of them
in greater amounts than any other.
Stereoselective reaction
H
3
C
CH
3
H
3
C
H
H cat
Both products correspond to
syn addition of H
2
.
Example of A Stereoselective Reaction
H
2
, cat
CH
3
H
3
C
H
3
C
H
H
H
H
3
C
CH
3
H
3
C
H
H
H
But only this one
is formed.
H
3
C
CH
3
H
3
C
H
Top face of double
bond blocked by
Example of A
Stereoselective
Reaction
H
2
, cat
bond blocked by
this methyl group
H
2
adds to
bottom face of
double bond.
H
CH
3
H
3
C
H
3
C
H
H
11/1/2010
4
General Equation for Electrophilic
Addition
The t electrons of the alkene can be used to
form bonds in a reaction it is a nucleophile.
Alkenes can add on species that are
electrophiles
An hydrogen halide (acid) is an electrophilic
+ EY
o+ o
C C E Y C C
y g ( ) p
species the t electrons can be used to bond to
H
+
A Hydrogen Halide is an Electrophile
(EY is HX in the reaction below)
+ HX
o+ o
C C H X C C
CH
3
CH
2
CH
2
CH
3
H H
CHCl
3
, -30C
C C
HBr
Electrophilic addition of
hydrogen halides to alkenes
proceeds by rate-determining
formation of a carbocation
intermediate.
Electrons flow from the t
Mechanism
Electrons flow from the t
system of the alkene (electron
rich) toward the positively
polarized proton of the
hydrogen halide.
Mechanism
..
..
:
X :

H C C
+
X H
C C
..
..
:
H C C
..
..
X :
Markovnikovs Rule:
When an unsymmetrically substituted alkene
reacts with a hydrogen halide, the hydrogen
adds to the carbon that has the greater number
f h d b i d h h l dd
Regioselectivity of Hydrogen Halide
Addition
of hydrogen substituents, and the halogen adds
to the carbon that has the fewer hydrogen
substituents.
Markovnikov's Rule
acetic acid
Br
CH
3
CH
2
CHCH
2
H CH
2
CH
3
CH
2
CH
HBr
(80%)
CH H
CH
3
CH C
C C
HBr
CH
3 H
CH
2
H CH
3
C
Br
(90%)
C C
acetic acid
CH
3
H
(100%)
HCl
CH
3
CH
3
Cl
0C
11/1/2010
5
CH
3
CH
2
CH
2
CH
2
+
primary carbocation is less stable: not formed
Mechanistic Basis for Markovnikov's Rule
Protonation of double bond occurs in the direction
that gives more stable of two possible
carbocations.
Br
CH
3
CH
2
CHCH
3
CH
2
CH
3
CH
2
CH
HBr
CH
3
CH
2
CHCH
3
+ Br

+
primary carbocation is less stable: not formed
(CH
3
)
2
CHCH
2
+
primary carbocation is less stable: not formed
Mechanistic Basis for Markovnikov's Rule
(CH
3
)
2
CCH
3
+ Br

+
HBr
(
3
)
2 3
CH
3
CH
3
CH
3
C
Br
C C
CH
3
CH
3
H
H
Mechanistic Basis for Markovnikov's Rule
H
H
CH
3
H
+
H
secondary carbocation
is less stable: not
formed
HCl
H
CH
3
CH
3
Cl
CH
3
+
Cl

HCl, 0C
CH
3
CHCH(CH
3
)
2
+
H
2
C CHCH(CH
3
)
2
+
CH CHC(CH )
H
Carbocation Rearrangements Can Occur
CH
3
CHCH(CH
3
)
2
CH
3
CHC(CH
3
)
2
CH
3
CHCH(CH
3
)
2
Cl
(40%)
CH
3
CH
2
C(CH
3
)
2
Cl
(60%)
CH
3
CHCH
3
OSO
2
OH
CH
3
CH CH
2
HOSO
2
OH
Isopropyl
h d lf t
Addition of H
2
SO
4
to Alkenes
follows Markovnikov's rule
yields an alkyl hydrogen sulfate
hydrogen sulfate
slow
+ CH
3
CH CH
2
H
..
SO
2
OH
..
O
+ ..

Mechanism
CH
3
CH CH
3
+
SO
2
OH
..
: O
fast
CH
3
CHCH
3
OSO
2
OH
..
:
11/1/2010
6
Alkyl Hydrogen Sulfates Undergo
Hydrolysis in Hot Water, Form Alcohols
HOH
CH
3
CHCH
3
O SO
2
OH heat
HO SO OH + CH CHCH
+
HOSO
2
OH + CH
3
CHCH
3
O H
1. H
2
SO
4
2. H
2
O, heat
(75%)
OH
not all alkenes yield alkyl hydrogen sulfates
on reaction with sulfuric acid
these do: H
2
C=CH
2
, RCH=CH
2
, RCH=CHR'
these don't: R
2
C=CH
2
, R
2
C=CHR, R
2
C=CR
2
Reaction Selectivity
The presence of one H on each carbon is
critical to the addition of H
2
SO
4
.
Does that mean the other alkenes cannot be
hydrated to alcohols?
Acid-Catalyzed Hydration of Alkenes
HOH C C
+
OH C C H
reaction is acid catalyzed; typical hydration
medium is 50% H
2
SO
4
-50% H
2
O
(90%)
50% H
2
SO
4
50% H
2
O
H
3
C
H
3
C CH
3
H
C C
OH
C CH
2
CH
3
CH
3
CH
3
Regioselectivity follows Markovnikovs rule
Follows Markovnikov's Rule
50% H
2
SO
4
50% H
2
O
(80%)
OH
CH
3
CH
2
involves a carbocation intermediate
is the reverse of acid-catalyzed dehydration of
+ H
2
O
H
+
H
3
C
H
3
C
C CH
2
OH
C CH
3
CH
3
CH
3
is the reverse of acid catalyzed dehydration of
alcohols to alkenes
Step (1) Protonation of double bond
H
3
C
C CH
2
+ O
+
H
H
:
Mechanism
H
3
C H
slow
+
H
3
C
H
3
C
C CH
3
H
+ O
H
: :
Step (2) Capture of carbocation by water
+
H
3
C
H
3
C
C CH
3
H
+ O
H
: :
fast
Mechanism
H
3
C H
+
H
O
H
: C
CH
3
CH
3
CH
3
11/1/2010
7
Step (3) Deprotonation of oxonium ion
+
H
O
H
: C
CH
3
CH
CH
3 O
H
: :
H
+
Mechanism
H
CH
3
H
fast
O
+
H
H
H
: +
H
O: C
CH
3
CH
3
CH
3
..
ethylene CH
2
=CH
2
1.0
propene CH
3
CH=CH
2
1.6 x 10
6
2-methylpropene (CH
3
)
2
C=CH
2
2.5 x 10
11
The more stable the carbocation the faster it is
Relative Rates Acid Catalyzed Hydration
The more stable the carbocation, the faster it is
formed, and the faster the reaction rate.
+ H
2
O
H
+
H
3
C
H
3
C
C CH
2
OH
C CH
3
CH
3
CH
3
Principle of Microscopic Reversibility
In an equilibrium process, the same intermediates
and transition states are encountered in the
forward direction and the reverse, but in the
opposite order.
Lets examine the kinetics and thermodynamics
Hydration-Dehydration Equilibrium
How do we control the position of the
equilibrium and maximize the product?
Le Chateliers Principle
A system at equilibrium adjusts so to minimize
any stress applied to it.
For hydration-dehydration, the key stress is water.
Adding water pushes the equilibrium toward
product (alcohol); removing water pushes toward
reactant (alkene) reactant (alkene)
At constant T and P, reactions proceed to
decrease free energy (AG, spontaneous reaction)
The sign of G is always positive, but AG can be
positive or negative.
AG = G
product
G
reactant
; spontaneous when AG <
0
Le Chateliers Principle
For a reversible reaction: aA + bB cC + dD
The relationship between AG and AG
o
is:
At equilibrium, AG = 0 and the following becomes
true:
Substituting K
eq
into the previous equation gives:
AG
o
= - RT lnK
eq
Reactions for AG
o
positive are endergonic and for
AG
o
negative are exergonic.
11/1/2010
8
Synthesis: Suppose you wanted to prepare
1-decanol from 1-decene?
Hydroboration Oxidation of Alkenes
Needed: a method for hydration of alkenes
with a regioselectivity opposite to
Markovnikov's rule.
OH
Two-step reaction sequence called hydroboration-
oxidation converts alkenes to alcohols with a
regiochemistry opposite to Markovnikov's rule.
Synthesis
1 h droboration 1. hydroboration
2. oxidation
OH
Hydroboration Step
+ HBH
2
C C H BH
2
C C
Hydroboration can be viewed as the addition of
borane (BH
3
) to the double bond.
But BH
3
is not the reagent actually used.
Hydroboration Step
Hydroboration reagents:
H
2
B
H
H
BH
2
Diborane (B
2
H
6
)
normally used in an
ether-like solvent
called diglyme g y
Borane-tetrahydrofuran
complex (H
3
B-THF)
+O
BH
3

Oxidation Step
H
2
O
2
, HO

H BH
2
C C H OH C C
Organoborane formed in the hydroboration
step is oxidized with hydrogen peroxide.
Examples
1. B
2
H
6
, diglyme
2. H
2
O
2
, HO

(93%)
OH
( %)
1. B
2
H
6
, diglyme
2. H
2
O
2
, HO

(82%)
OH
11/1/2010
9
hydration of alkenes
regioselectivity opposite to Markovnikov's rule
no rearrangement
stereospecific syn addition
Features of Hydroboration-Oxidation
(98%)
H
3
C
H
3
C
CH
3
H
C C
1. H
3
B-THF
2. H
2
O
2
, HO

H
C C CH
3
CH
3
CH
3
H OH
H and OH become attached to same face
of double bond
syn Addition
1. B
2
H
6
, diglyme
CH
3
CH
3
H
only product is trans-2-methylcyclopentanol
(86%) yield
2. H
2
O
2
, NaOH
H H
HO
Mechanism: 1-Methylcyclopentene + BH
3
syn addition of H and B to
double bond
B adds to less substituted carbon
Organoborane
Intermediate
Add hydrogen peroxide; OH
replaces B on same side
Trans-2-methylcyclohexanol
+ X
2
X X C C C C
Addition of Halogens to Alkenes
Electrophilic addition to double bond forms a ect op c add t o to doub e bo d o s a
vicinal dihalide.
limited to Cl
2
and Br
2
F
2
addition proceeds with explosive violence.
I
2
addition is endothermic: vicinal diiodides
dissociate to an alkene and I
2
.
Examples
CHCl
3
0C
CHCH(CH
3
)
2
CH
3
CH
Br
2
CH
3
CHCHCH(CH
3
)
2
(100%)
Br Br
The stereochemistry of halogen addition is anti.
H
trans-1,2-Dibromocyclopentane
80% yield; only product
Br
2
H
H
Br
Br
H
H
A halonium ion is the key intermediate in the
halogenation of alkenes
Br
2
is not polar, but it is polarizable.
two steps
(1) formation of bromonium ion
Mechanism is electrophilic addition
(1) formation of bromonium ion
(2) nucleophilic attack on bromonium ion by
bromide
11/1/2010
10
ethylene H
2
C=CH
2
1
propene CH
3
CH=CH
2
61
2-methylpropene (CH ) C=CH 5400
Relative Rates of Bromination
2-methylpropene (CH
3
)
2
C=CH
2
5400
2,3-dimethyl-2-butene (CH
3
)
2
C=C(CH
3
)
2
920,000
More highly substituted double bonds react faster.
Alkyl groups on the double bond make it more
electron rich.
H
2
C CH
2 BrCH
2
CH
2
Br + Br
2
?
+
C C
+
..
: :
Br

Mechanism?
C C
Br : :
..
: :
..
Br
No obvious explanation for anti addition
provided by this mechanism.
H
2
C CH
2
BrCH
2
CH
2
Br + Br
2
+
C C
..
: :
Br

Mechanism
Cyclic bromonium ion
+
C C
Br : :
+
: :
..
Br Mutual polarization of
Br
Br
Electrons flow from
Br
Br
o
o+ o+
Formation of
Bromonium Ion
Mutual polarization of
electron distributions
of Br
2
and alkene
Electrons flow from
alkene toward Br
2
.
t electrons of alkene
displace Br

from Br.
Br

Br
+
Stereochemistry of Anti Addition
+

Br : :
..
..
Br
..
..
..
Br
Br
..
:
..
..
: :
Attack of Br

from side
opposite CBr bond of
bromonium ion gives anti
addition.
Cyclopentene +Br
2
B i i
trans-Stereochemistry

Bromonium ion

Bromide ion attacks the bromonium ion

from side opposite carbon-bromine
bond; anti addition trans-1,2-dibromo-
cyclopentane is the only product
trans-Stereochemistry
in vicinal dibromide
11/1/2010
11
Anti Addition of Bromine to 2-Butene
Br
2
R
S R
S
meso
Anti addition to trans 2 butene gives the meso
Br
2
R
R
50%
+
S
S
50%
Anti addition to trans-2-butene gives the meso
compound; cis-2-butene gives a racemic mixture
+ X
2
X X C C C C
Alkenes react with X
2
to form vicinal dihalides.
Alkenes react with X
2
in water to give vicinal
Vicinal Halohydrins from Alkenes
+ H
2
O
OH
+ HX
+ X
2
X C C
C C
2
g
halohydrins.
Examples
H
2
C CH
2
BrCH
2
CH
2
OH + Br
2
H
2
O
(70%)
Cl
2
H OH
H
trans-2-chlorocyclopentanol
anti addition: only product
H
2
O
H
H
OH
Cl
H
Mechanism
+
Br
..
..
:
..
O
Br
..
:
..
..
O
+
Bromonium ion is the intermediate
Water is nucleophile that attacks
bromonium ion.
Cyclopentene
+ Cl
2
Chloronium
ion
Water attacks
chloronium ion
from side opposite
carbon-chlorine
bond.
trans-Stereochemistry
in oxonium ion
(77%)
H
3
C
C CH
2
H
3
C
CH
3
OH
C CH
2
Br CH
3
Br
2
H
2
O
Regioselectivity
Markovnikov's rule is applied to halohydrin
formation: the halogen adds to the carbon
having the greater number of hydrogens.
11/1/2010
12
H
O
H
o+
..
H
O H
o+
..
H
3
C
CH
2
H
3
C
o+
C
H
3
C
CH
2
H
3
C
C
o+
Explanation
Transition state for attack of water on
bromonium ion has carbocation character;
more stable transition state (left) has positive
charge on more highly substituted carbon.
Br : :
o+
Br
: :
o+
acetic acid
Br
CH
3
CH
2
CHCH
3
CH
2
CH
3
CH
2
CH
HBr
(80%)
Markovnikov's Rule
Can HBr addition take place such that Br is
bonded to C1 in this molecule? Yes bonded to C1 in this molecule? Yes.
When HBr is added to an alkene in the presence
of peroxides, an anti-Markovnikov addition is
observed called the peroxide effect
The reaction occurs via the free radical
mechanism
C C C C
CH
2
CH
3
CH
2
CH
HBr
Addition of HBr to 1-Butene
CH
3
CH
2
CH
2
CH
2
Br
only product in
absence of peroxides
only product when
peroxides added to
reaction mixture
Br
CH
3
CH
2
CHCH
3
C C C C
CH
2
CH
3
CH
2
CH
HBr
addition opposite
to Markovnikov's
rule occurs with
Addition of HBr to 1-Butene
CH
3
CH
2
CH
2
CH
2
Br
only product when
peroxides added to
reaction mixture
rule occurs with
HBr (not HCl or HI)
Addition of HBr with a regiochemistry opposite to
+ HBr
hv
CH
2
(60%)
CH
2
Br
H
Photochemical Addition of HBr
Markovnikov's rule can also occur when initiated
with light with or without added peroxides.
Addition of HBr opposite to Markovnikov's rule
proceeds by a free-radical chain mechanism.
Initiation steps:
Mechanism
..
..
O R R O
..
..
O
.
R
..
..
..
..
O R
.
+
+
O
.
R
..
..
+ O R
..
..
H
.
Br
..
..
:
..
Br H
..
:
11/1/2010
13
Propagation steps:
Mechanism
.
..
CH
3
CH
2
CH CH
2
Br:
..
+
CH
3
CH
2
CH CH
2
..
.
Br
..
:
..
..
+ ..
..
.
CH
3
CH
2
CH CH
2
Br:
..
..
H Br:
..
..
CH
3
CH
2
CH
2
CH
2
Br:
.
Br:
H
2
C CH
2
H
2
C CHCH
3
Epoxides
are examples of heterocyclic compounds
three-membered rings that contain oxygen
ethylene oxide propylene oxide
O O
H
3
C
Epoxide Nomenclature
Substitutive nomenclature: named as epoxy-
substituted alkanes.
epoxy precedes name of alkane
1,2-epoxypropane 2-methyl-2,3-epoxybutane
H
2
C CHCH
3
O
CHCH
3
O
C
3
C
H
3
C
1
2 3 4
O
RCOOH
Epoxidation of Alkenes
peroxy
acid
C C +
O
+ CH
3
COOH
(52%)
+ CH
3
COH
O
O
Stereochemistry of Epoxidation
C C +
syn addition
RCOOH
O
C C
O
+
O
RCOH
syn addition
Problem 6.23 Give the structure of the alkene,
including stereochemistry, that you would choose
as the starting material in a preparation of
synthetic disparlure (6.22, nomenclature).
peroxy acid
O H H
H H
disparlure
(cis-2-Methyl-7,8-epoxyoctadecane)
11/1/2010
14
ethylene H
2
C=CH
2
1
propene CH
3
CH=CH
2
22
2-methylpropene (CH
3
)
2
C=CH
2
484
2 th l 2 b t (CH ) C CHCH 6526
Relative Rates of Epoxidation
2-methyl-2-butene (CH
3
)
2
C=CHCH
3
6526
More highly substituted double bonds react faster.
Alkyl groups on the double bond make it more
electron rich.
Mechanism of Epoxidation
The peroxy acid reacts with the alkene to form a
bicyclic ring intermediate.
The ring dissociates to the epoxide.
Additon is syn; alkene stereochemistry is retained.
syn addition to trans-2-butene gives racemic
Epoxidation of 2-Butene
RCO
3
H
R
R
S
S
50%
+
50%
syn addition to trans 2 butene gives racemic
mixture; cis-2-butene gives the meso diastereomer
R
S
R
S
RCO
3
H
meso
Ozonolysis has both synthetic and analytical
applications.
Used for synthesis of aldehydes and ketones
Used for identification of substituents on the
double bond of an alkene
First step is the reaction of the alkene with ozone.
Ozonolysis of Alkenes
First step is the reaction of the alkene with ozone.
The product is an ozonide.
+ O
3 C
C
O
O O
C C
Second step is reduction of the ozonide.
Two aldehydes, two ketones, or an aldehyde
and a ketone are formed.
Ozonolysis of Alkenes
+ O
3
C
C
O
C C
C O C O
+ H
2
O, Zn
O O
The ozonide can also be reduced with dimethyl
sulfide.
1. O
3
CH
3
CH
2
CH
3
H
C C
CH
2
CH
3
Example
1. O
3
2. H
2
O, Zn
(38%) (57%)
CH
2
CH
3
C O
CH
2
CH
3
C O
CH
3
H
+
11/1/2010
15
Polymerization of Alkenes
Alkenes react with alkenes to form polymers by
three mechanisms:
cationic polymerization
free-radical polymerization
coordination polymerization
H
2
SO
4
monomer
(C
4
H
8
)
Dimerization of 2-methylpropene
(CH
3
)
2
C CH
2
Cationic Polymerization
H
2
SO
4
+
two dimers
(C
8
H
16
)
CH
3
CCH
CH
3
CH
3
C(CH
3
)
2
CH
3
CCH
2
C
CH
3
CH
3
CH
2
CH
3
Step (1) Protonation of double bond
H
3
C
H
3
C
C CH
2
+ O
+
H
H
H
:
l
Mechanism of Dimerization
H
3
C H
slow
+
H
3
C
H
3
C
C CH
3
H
+ O
H
: :
+
CH
3
H
2
C C
CH
3
CH
3
C
CH
3
+
CH
3
Mechanism of Dimerization
CH
3
CCH
2
C
CH
3
CH
3
CH
3
CH
3
+
The carbocation formed
can lose a proton to form
a dimer or react with
another molecule of
alkene to form a polymer
Mechanism of Dimerization
CH
3
CCH
CH
3
CH
3
C(CH
3
)
2
CH
3
CCH
2
C
CH
3
CH
3
CH
2
CH
3
Two constitutional
CH
3
CCH
2
C
CH
3
CH
3
CH
3
CH
3
+
Two constitutional
isomers are the
products
200 C
2000 atm
O
2
peroxides
H
2
C CH
2
CH CH CH CH CH CH CH
Free-Radical Polymerization of Ethylene
polyethylene
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
Peroxides are used for free radical reactions as
initiators;
they readily form hydroxy or alkoxy radicals
11/1/2010
16
..
RO:

..
RO
..
H
2
C CH
2
H
2
C CH
2

CH H C
Mechanism
CH
2
H
2
C
H
2
C CH
2
H
2
C CH
2

..
RO:
The process continues
H
2
C CHCH
3
Free-Radical Polymerization of
Propene
polypropylene
CH CH CH CH CH CH CH
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3

..
RO
..
H
2
C CHCH
3
H
2
C CHCH
3

..
RO:
CHCH H C
Mechanism
CHCH
3
H
2
C
H
2
C CHCH
3
H
2
C CHCH
3

..
RO:
As noted before, the process
continues
Likewise...
H
2
C=CHCl polyvinyl chloride
H
2
C=CHC
6
H
5
polystyrene
F
2
C=CF
2
Teflon