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Reactions of Alkenes
6-1
Table of Contents
Reactions of Alkenes
6-3
Characteristic Reactions
Descriptive Name(s )
Reaction
C C
HCl
( H X)
C C
+ H2 O
C C
C C
H
C C
Cl( X)
H
C C
OH
( X) Br
C C
Br( X)
Br2
( X2 )
Br2
( X2 )
H2 O
HO
C C
Br( X)
Hydrochlorination
(hydrohalogenation)
Hydration
Bromination
(halogenation)
Halohydrin formation
(Bromohydrin
formation)
6-4
Characteristic Reactions
C C
+ Hg(OAc) 2
C C
BH3
C C
OsO4
C C
H2
H2 O
HgOAc
Oxymercuration
C C
HO
C C
H BH2
Hydrob
y
oration
C C
HO OH
D iol formation
(oxidation)
C C
H H
Hydrogenation
(reduction )
Reaction Mechanisms
6-6
G 0 = H 0 TS0
Exergonic reaction:
reaction: A reaction in which the Gibbs free
energy of the products is lower than that of the
reactants; the position of equilibrium for an exergonic
reaction favors products
products.
Endergonic reaction:
reaction: A reaction in which the Gibbs free
energy of the products is higher than that of the
reactants;
t t the
th position
iti off equilibrium
ilib i
ffor an endergonic
d
i
reaction favors starting materials.
6-7
H 0 < 0
S0 > 0
G 0 > 0; th e
position of equilib riu m
favors reactants
At h igh er temperatures
w hen TS0 > H0 an d
G 0 < 0, th e position of
equ ilibrium favors
products
p
G 0 < 0; th e
position of equilib riu m
favors products
6-8
Energy Diagrams
Heat of reaction,
reaction : The difference in enthalpy
between reactants and products.
Exothermic reaction:
reaction: A reaction in which the enthalpy of
th products
the
d t is
i llower th
than th
thatt off the
th reactants;
t t a
reaction in which heat is released.
Endothermic reaction:
reaction: A reaction in which the enthalpy
py
of the products is higher than that of the reactants; a
reaction in which heat is absorbed.
6-9
Energy Diagrams
Energy diagram:
diagram: A graph showing the changes in
energy
gy that occur during
g a chemical reaction.
Reaction coordinate:
coordinate: A measure in the change in
positions of atoms during a reactions progression.
6-10
Activation Energy
Transition state:
state:
An unstable species of maximum energy formed during
th course off a reaction.
the
ti
A maximum on an energy diagram.
Activation Energy,
Energy G: The difference in Gibbs
free energy between reactants and a transition
state.
If G is large, few collisions occur with sufficient energy
to reach the transition state; reaction is slow.
If G is small
small, many collisions occur with sufficient
energy to reach the transition state; reaction is fast.
6-11
Energy Diagram
An energy diagram for a one-step reaction with no
intermediate.
6-12
Energy Diagram
6-13
Electron pushing
6-15
Electron Pushing
6-16
6-17
6-18
6-19
6-20
6-21
6-22
Electrophilic Additions
Electrophilic Addition: A common type of reaction with
alkenes in which an electrophilic species adds to a
b d
bond.
Hydrohalogenation using HCl, HBr, HI
Hydration using H2O in the presence of H2SO4
Halogenation using Cl2, Br2
Halohydrination
y
using
g HOCl,, HOBr
Oxymercuration using Hg(OAc)2, H2O followed by
reduction
A characteristic pattern of the mechanism of each
reaction is making a bond between a nucleophile
( bond)) and an electrophile
p
(the
(
reagent).
g )
6-23
Addition of HX
CH3 CH= CH 2 + H Br
Propene
Br
Addition is regioselective
Regioselective reaction:
reaction: An addition or substitution
reaction in which one product is formed in preference to
all others that might be formed.
Markovnikov
Markovnikovs
s rule:
rule: In the addition of HX or H2O to an
alkene, H adds to the carbon of the double bond having
the greater number of hydrogens.
6-24
HBr + 2-Butene
A two-step mechanism
Step 1: Make a new bond between a nucleophile ( bond) and an
electrophileadd a proton.
6-25
Carbocations
Carbocations
6-27
Carbocation Stability
relative stability
H
H
C+
H
Methyl
cation
(meth yl)
CH3
H
C+
H
Ethyl
cation
(1)
CH3
CH3
C+
H
Isopropyl
cation
(2)
CH3
CH3
C+
CH3
t ert-Bu tyl
cation
(3)
6-28
Carbocation Stability
We can account for the relative stability of carbocations
if we assume that alkyl groups bonded to a positively
charged
h
d carbon
b are electron
l t
releasing
l
i and
d th
thereby
b
delocalize the positive charge of the cation.
electron releasing ability of alkyl
We account for this electron-releasing
groups by (1) the inductive effect, and (2)
hyperconjugation.
6-29
6-30
Hyperconjugation
Involves partial overlap
of the -bonding orbital
off an adjacent
dj
tC
C-H
H or C
CC bond with the vacant
2p orbital of the cationic
carbon.
The result is
delocalization of the
positive charge.
6-31
HBr + 2-Butene
6-32
Addition of H2O
Addition of water is called hydration.
Acid-catalyzed hydration of an alkene is regioselective;
hydrogen adds preferentially to the less substituted
carbon of the double bond (to the carbon bearing the
greater number of hydrogens).
HOH adds in accordance with Markovnikovs rule.
CH3 CH=CH2 + H2 O
Propene
CH3
CH3 C=CH2 + H2 O
2-Methylprop
y p p ene
H2 SO4
OH H
CH3 CH-CH2
2-Propanol
CH3
CH3 C-CH2
HO H
2-Methyl-2-propanol
y
p p
H2 SO4
6-33
slow, rate
slow
determining
CH 3 CHCH 3
:O H
A 2 carbocation
intermediate
CH 3 CHCH 3 +
fast
O+
fast
CH3 CHCH 3 + H O H
: OH
H
:
O:
O+
H
H
An oxonium ion
:
CH3 CHCH 3
CH3 CHCH 3
6-34
Carbocation Rearrangements
6-35
Carbocation Rearrangements
In addition of HCl to an alkene.
Cl
+ HCl
3,3-D imethylbu te
tenee
1-bu
Cl
In acid-catalyzed
acid catalyzed hydration of an alkene
alkene.
+ H2 O
3
3-Methyl-1-buten
1
e
H2 SO4
OH
2 M th l 2 b t oll
2-Methyl-2-butan
6-36
Carbocation Rearrangements
The driving force is rearrangement of a less stable
carbocation to a more stable one.
CH 3
CH 3 C- CHCH 3 + : Cl :
:
Cl :
CH 3
CH 3 CCH= CH 2 + H
H
3-Methyl-1-butene
slow, rate
determining
H
A 2 carbocation
intermediate
fast
CH 3
CH 3 CC CHCH 3
+
H
A 3 carbocation
6-37
Carbocation Rearrangements
Reaction of the more stable carbocation (an
electrophile) with chloride ion (a nucleophile) completes
th reaction.
the
ti
If possible, a carbocation will always rearrange to a
more stable one.
CH3
fast
CH3
2 Chl
2-Chloro-2-methylbutane
2
th lb t
6-38
Br2
CH2 Cl2
CH3 CH-CHCH3
2,3-D ib romob utane
Cyclohexene
Br2
CH2 Cl 2
Br
+
Br
Br
trans- 1,2-Dibromocyclohexane
(a racemic mixture)
6-40
6-41
B2
Br
Br
Br
Br
(1S,2S)-1,2-D ibromocyclohexan
l h
e
Br
Br
B
Br
Br
(1R,2R)-1,2-D ibromocyclohexane
6-42
HO
O Cl
C
CH3 CH- CH2
+ HCl
1-Chloro-2-propanol
(a chlorohydrin)
6-43
OH
Br
1-Methylcyclopentene
OH
+ HBr
Br
H
H
2-Bromo-1-methylcyclopentanol
( a racemic mixture )
6-45
H O:
H
R
H
R
:Br :
C
H
H
:Br :
Br
C
H
R
Br
H
H
+ H3 O+
C
H
O H
H
6-46
6-47
6-48
Oxymercuration/Reduction
Mercu ry(II)
acetate
O
+ CH3 COH
HgOAc
An organ omercury
comp ou
o nd
A cetic
acid
reduction
OH
OH
NaBH4
HgOAc
H
2-Pen tanol
O
+ CH COH + Hg
3
Acetic acid
6-49
Oxymercuration/Reduction
An important feature of oxymercuration/reduction is that
it occurs without rearrangement, unlike acid-catalyzed
additions
dditi
off water
t to
t alkenes.
lk
1 . Hg(OAc) 2 , H2 O
2 . NaBH
N BH4
OH
3,3-D imeth yl-2-b utanol
Cyclopentene
Hg
g ( OAc ) 2
H2 O
N aBH4
OH
Hg OA c
(Anti addition of
OH and HgOAc)
OH
H
H
Cyclopentanol
6-50
Oxymercuration/Reduction. Mechanism
Step 1: Break a bond to give stable molecules or
ions.
+
AcO- Hg
AcO
Hg- OAc
AcO Hg + AcO
AcO(an electrophile)
6-51
Oxymercuration/Reduction
Step 3: Make a new bond between a nucleophile
(H2O) and an electrophile at the more substituted
b tto open th
b d ring.
i
carbon
the th
three-membered
6-52
Oxymercuration/Reduction
Anti stereoselective
Formation of a bridged
g mercurinium ion intermediate
and anti attack of the nucleophile to open the threemembered ring.
R i
Regioselective
l ti
The more substituted carbon of the mercurinium ion
intermediate has the greater degree of partial positive
character.
Computer modeling indicates that the C-Hg bond to the
more substituted carbon of the bridged intermediate is
longer than the one to the less substituted carbon.
ring-opening
opening transition state is reached more easily
The ring
by attack at the more substituted carbon.
6-53
Hydroboration/Oxidation
CH2 CH3
+ 3 CH2 = CH2
H
Borane
CH2 CH3
Triethylborane
(a trialkylborane)
CH3 CH2 B
B2 H6
D iborane
Hydroboration/Oxidation
Borane forms a stable complex with ethers such as
THF.
The reagent is used most often as a commercially
available solution of BH3 in THF.
2
: O:
+ B2 H6
Tetrahydrofuran
((THF))
+ :O BH3
BH3 TH F
6-55
Hydroboration/Oxidation
Hydroboration is both
regioselective
g
((boron bonds to the less hindered
carbon)
and syn stereoselective.
+
H
CH3
1-Methylcyclopentene
BH3
H3 C
BR2
H
(Syn addition of BH 3 )
(R = 2-methylcyclopentyl)
6-56
Hydroboration/Oxidation. Mechanism
Concerted regioselective and syn stereoselective
addition of B and H to the carbon-carbon double bond.
A
Approach
h iis thi
this way b
because B iis llarger th
than H
H.
H B
H
CH3 CH2 CH2 CH= CH2
Hydroboration/Oxidation. Mechanism
6-58
Hydroboration/Oxidation. Mechanism
Step 2: Rearrangement of an R group with its pair of
bonding electrons to an adjacent oxygen atom.
R
R B O O H
R
R
R B O
O-H
6-59
Oxidation/Reduction
6-60
Oxidation/Reduction
Balanced half-reactions for the hydration, oxidation and
reduction of propene.
OH
CH 3 CH= CH2 + H2 O
Propene
CH3 CHCH3
2-Propanol
HO OH
CH 3 CH= CH2 + 2 H2 O
Propene
CH3 CH= CH2 + 2 H+ + 2 e Propene
CH 3 CHCH 2 + 2 H + + 2 e 1,2-Propanediol
CH3 CH2 CH3
Propane
6-61
O O
Os
O O
A cyclic osmate
OH
N aHSO 3
H2 O
OH
cis -1,2-Cyclopentanediol
(a cis glycol)
O
OsO
O4 is
i used
d iin catalytic
t l ti amounts
t with
ith another
th oxidizing
idi i
agent to reoxidize its reduced forms of osmium and,
thus, recycle OsO4. Two commonly used oxidizing
agents
t are
CH3
HOOH
Hyd rogen
peroxid e
CH3 COOH
CH3
t ert -Bu tyl h yd roperoxide
(t -BuOOH)
6-62
Os
Os
O
O
O
2 H 2O
OH
Os
OH
HO
OH
6-63
Oxidation with O3
O
1 . O3
CH3 CCH3
2 . ( CH3 ) 2 S
Propanone
(a ketone)
O
+ HCCH 2 CH3
Propanal
(an aldehyde)
6-64
Syn-addition
:O
CH3
H
H3C
H3C
CH3
H
6-65
O3
C
C
( CH3 ) 2 S
CH3 CH
CH3
O O
Acetaldehyde
An ozonide
H3 C
Step 2:
O
O
O
C
molozonide
rearrangement
O
C
C
O
O
6-66
H
H3C
O
C
C
O
CH3
H3C
S
H3C
CH3
CH3
O
H
:O :
+
CH3
H3C
6-67
Reduction of Alkenes
Pd
25C, 3 atm
Cyclohexane
6-68
Reduction of Alkenes
Reduction of Alkenes
Even though addition occurs with syn stereoselectivity,
some product may appear to result from trans addition.
CH 3
CH3
H 2 / Pt
CH 3
CH3
70% tto 85%
cis- 1,2-Dimethylcyclohexane
1,2-Dimethylcyclohexene
CH3
CH3
30% to15%
t 15%
trans -1,2-Dimethylcyclohexane
((racemic))
H2 / Pt
H
CH3
H
Pt
H CH3
CH3
CH3
1,6-D imeth ylcyclohexene
6-70
H0 of Hydrogenation
Eth yle ne
S tru ctural
Formu la
CH2 =CH2
Prop en e
CH3 CH=CH2
N ame
H
[[k J ((k cal)/m
) ol]]
-137 (-32.8)
-126 (-30.1)
1-Bu te ne
-127 (-30.3)
-120 (-28.6)
t rans -2-Bu te ne
-115 (-27.6)
-113 (-26.9)
-111 (-26.6)
6-71
H0 of Hydrogenation
H0 for
f a trans-alkene
t
lk
iis llower th
than th
thatt off an
isomeric cis-alkene.
A trans-alkene
trans alkene is more stable than an isomeric ciscis
alkene.
6-72
Reaction Stereochemistry
As we will
A
ill see, th
the stereochemistry
t
h i t off th
the product
d t
for some reactions depends on the
stereochemistry of the starting material; that is,
is
some reactions are stereospecific
stereospecific..
6-73
Reaction Stereochemistry
Br2
CH2 Cl2
Br Br
CH3 CH-CHCH3
2,3-D
2,3
D ib romob utane
Bromination of cis-2-Butene
Step 1: Make a bond between a nucleophile ( bond)
and an electrophile.
6-75
Bromination of cis-2-Butene
Step 2: Make a new bond between a nucleophile and
an electrophile.
6-76
Bromination of trans-2-Butene
Step 1: make a new bond between a nucleophile (
bond) and an electrophile.
6-77
Bromination of trans-2-Butene
Step 2: Make a new bond between a nucleophile and
an electrophile.
6-78
Bromination of 2-Butene
Stereospecific reaction:
reaction: A reaction in which the
stereochemistry of the product depends on the
stereochemistryy of the starting
g material.
6-79
Oxidation of 2-Butene
OsO4 oxidation of cis-2-butene gives meso-2,3butanediol.
H
H
H3 C
C
H
H3 C
CH3
cis-2-Butene
( hi l)
(achiral)
OsO4
CH3
HO
OH
(2S 3R) 2 3 Butanediol
(2S,3R)-2,3-Butanediol
ROOH
id entical;
a meso
compoun d
OH
HO
2
H
H
CH3
H3 C
((2R,3S)-2,3-Butanediol
, ) ,
6-80
Oxidation of 2-Butene
H
2
C
H
CH3
H3 C
H
trans-2-Buten e
(achiral)
OsO4
CH3
H
HO
OH
(2S,3S)-2,3-Butaned iol
ROOH
OH
HO
2
a pair of
enantiomers;
a racemic
mixture
CH3
H
H
H3 C
(2R,3R)-2,3-Butaned iol
Reaction Stereochemistry
Reaction Stereochemistry
Br
Br
redraw as
a chair
con formation
Br
Br
6-83
H
Br
H
H
Br
Br
Br
Br
Br
6-84
Problem 6.34
6-85
Problem 6.34
6-86
Problem 6.34
6-87
Problem 6.34
6-88
Reactions
of Alkenes
End Chapter 6
6-89