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WWU -- Chemistry
WWU -- Chemistry
Addition of H-X
H
H
C
H
X
X
H
H
X
H
H
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Addition of Water
H
H
C
O
H
H+ catalyst
H
C
H
OH
OH
H+ catalyst
O
H
H
H
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MECHANISM
STEP-BY-STEP ACCOUNT OF WHAT HAPPENS
:Xstep 1
C C
C C
+
E
step 2
X
C C
E
Intermediate
intermediates are
formed during a
reaction but are
not products
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ENERGY PROFILE
two step reaction
intermediate
TS1
E
N
E
R
G
Y
TS2
-
C C
+ E
step 1
C C
+
step 2
product C C
E
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ACTIVATED COMPLEXES
X
C C
X
C C
C C
+
E
intermediate
+
C
+E
C C
CH2
CH2
CH2 CH2
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Hyperconjugation
Empty
p-orbital
H
C
H
C
H
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CARBOCATION STABILITY
HYPERCONJUGATION
..
C C
electrons in an adjacent
R
H
R
R
C R
R +
R
Most
stable
C
+
tertiary
>
CH
+
R CH R
+
secondary
>
CH2
+
R CH2
+
primary
Least
stable
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+
+
o
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Br
C
H3C
CH3
major
product
H-Br
C
H3C
CH2
CH3
H
C
H3C
minor
product
H
Br
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Markovnikovs Rule
In the ionic addition of an acid to the
carbon-carbon double bond of an alkene,
the hydrogen of the acid attaches itself to
the carbon atom which already holds the
greater number of hydrogens.
Them that has, gets!
The richer get richer!
(V. W. Markovnikov -- 1838 1904)
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Markovnikov
Markovnikov
Not
Markovnikov
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MARKOVNIKOV RULE
When adding HX to a double bond the
hydrogen of HX goes to the carbon
which already has the most hydrogens
CH2
+ HCl
CH3
Cl
REGIOSELECTIVE
REACTION
CH3
CH3
C CH2
HCl
CH3
CH3
CH3
Cl
minor
REGIOSPECIFIC
Mechanism (Markovnikov)
1)
CH CH2
slow
+
+ H
Electrophile
2)
CH-CH2 H +
_
Br
CH-CH2 H
Secondary C+
fast
Nucleophile
CH CH2 H
Br
Major product
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Mechanism (antiMarkovnikov)
1)
+
CH CH2 + H
slow
CH CH2+
Primary
carbocation
2)
CH
H
+
CH
2
_
+ Br
fast
CH CH2 Br
H
Minor!
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COMPETING PATHWAYS
rate-determining step
higher energy
intermediate
slower
faster
lower energy
intermediate
rate-determininng
(slow) step
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Markovnikov Addition to
an Alkene
CH3
CH3
C
CH2
CH3
CH3 C
CH3
CH2 H
X
major product
CH3 C
CH2 X
H
minor product
X = Cl, Br, I
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Mechanism
CH3
1)
C
CH3
CH2
H
CH
H
C
CH3
CH3
Electrophile
CH3
2)
CH2
slow
CH3
fast
C+
CH3
X
CH3
Nucleophile
CH2
H
C
CH2
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CH3
+ HCl
CH2
+ HCl
CH CH2
+ HCl
CH3
Cl
CH3
Cl
CH CH3
Cl
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CH CH2
H2SO4
(cold, concentrated)
CH CH2 H
O
OH
an alkyl hydrogen sulfate
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C C
O S O H
OSO3 H
SLOW
O
C C
+
H
C C
H
H O S O H
O
cold
FOLLOWS
MARKOVNIKOFF
RULE
OH
C C
water
room temp
H
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Addition of Water to an
Alkene
R
CH CH2
H2O
H2SO4
CH CH2 H
OH
an alcohol
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Mechanism of Hydration
1)
2)
3)
CH CH2
CH CH2 H
CH CH2 H
+ OH2
H2SO4
slow
CH CH2 H
H2O
HSO4
CH CH2 H
+ OH2
O
_
+
HSO4
CH CH2 H
OH
OH
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CH CH
Br2
CCl4
or CH2Cl2
CH CH
Br
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ADDITION OF BROMINE
Br
C C
CCl4
Br
C C
C C
+
Br
SLOW
Br
Br Br
+
Br
Br
Br
H open carbocation
Br
syn
Br
anti
would give both
cis and trans
Br
syn
anti
H
H
Br
Br
cis compound
NOT OBSERVED
H
Br
Br
H
trans compound
ACTUAL PRODUCT
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note size of
bromine
+
+
Br
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Br
Br
Br
bridging
blocks approach
from this side
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FORMATION OF ENANTIOMERS
symmetric
intermediate
Br
Br
H
Br
H
Br
ENANTIOMERS
Br
H
Br
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CH CH CH3
+
Br2
CH3
H
Br
2n possible stereoisomers
CH3
H
cis-2-butene
CH3
H
H
CH3
trans-2-butene
CH3
CH3
cis
H
trans
CH3
Br2 / CCl4
Br
CH3
Br
Br
H + H
CH3 CH3
enantiomers
Br2 / CCl4
Br
H
Br
CH3
H
CH3
Br
H
CH3
meso
cis
Br
H
H
H3C
Br
H
H
CH3
H3C
Br
Br
CH3
Br+
ADD TO
LEFT
Br
H
H3C
ADD TO
RIGHT
H
CH3
Br
H
H3C
Br
Br
ROTATE
ROTATE
Br Br
Br Br
ENANTIOMERS
H
H3C
H
CH3
CH3
H
H3C
H
H
CH3
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trans
CH3
H
H3C
Br
Br
Br
Br
CH3
H
H3C
Br+
ADD TO
LEFT
Br
H
H3C
ADD TO
RIGHT
CH3
H
Br
Br
ROTATE
H
H3C
CH3
H
ROTATE
Br Br
Br Br
MESO
Br
H
H3C
H
CH3
CH3
H3C
H
Bromination of an
Unsymmetrical Alkene
+
Br
1)
R
CH CH2
+ Br
CH
. _
: Br:
.
CH2
C
H
CH
CH2
Br
Br
Br
2)
Br
slow
C
Br
anti-addition
(stereospecific)
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Stereochemistry of
Bromination of Alkenes
Simple alkenes: Addition of bromine
or chlorine goes exclusively anti, with
the formation of a bridged ion
If a resonance-stabilized open-chain
carbocation is possible, there may be
a mixture of mechanisms, with some
molecules reacting via a bridged ion
and some molecules reacting via an
open-chain carbocation
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Stereochemistry of
Bromination of Alkenes
--Part Two
In cases where a resonance-stabilized
carbocation is possible, if the solvent
is made more polar (acetic acid or
nitromethane), the proportion of
molecules reacting via an open-chain
carbocation increases.
For simple alkenes, changing solvents
has little or no effect on
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stereochemistry.
Br2
H2O
CH
CH
+ HBr
Br
a bromohydrin
Br2 +
H2O
HOBr
+
HBr
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Mechanism
Br
R
CH2 +
CH
Br
slow
Br
CH
CH2
CH
CH2
O
H
Br
CH2
Br
CH
CH2 +
CH
Br
Br
R
Br
R
CH
CH2
O
H
H
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CH3
CH3
C
CH3
CH
CH2
HCl
CH3
CH
Cl
CH3
major
rearranged!!
H
CH2
CH3
+
CH3 C
H
CH
CH2
CH3 Cl
minor
not rearranged!!
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CH CH2
HBr
ROOR
CH CH2 Br
H
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ADDITION OF HBr
conc.
HBr
CH2
Markovnikov
Addition
CH3
Br
conc.
HBr
CH2
Oxygen
CH2Br
H
Anti-Markovnikov
Addition
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1)
light or
..
O.
..
heat
2)
..
.
O
..
Br
..
O
..
..
.O
..
..
: Br .
..
hydrogen abstraction
3)
4)
..
: Br .
..
Br
CH2 CH R
CH2 CH R
.
slow
Br
Br
CH2 CH R
.
Br
CH2 CH R
..
.
: Br
... .
hydrogen abstraction
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R
lowest
energy
R C R <
tertiary
R C H
secondary
highest
energy
methyl
()
()
( )
CH2
()
()
()
CH2
etc.
()
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CH CH R
Pt, Pd,
H2
or Ni
CH CH R
H
syn-addition
R
R
(stereospecific)
R
H2
lindlar
catalyst H
H
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Hydrogenation of Alkenes
R
CH CH R
H2
Pt, Pd,
CH CH R
or Ni
syn-addition
(stereospecific)
n H2 +
Pt(H .)2n
Pt
Pt
Pt
H.
Hydrogen Adsorbed on
Catalyst Surface
.H
Pt
H.
H.
finely-divided
particles
dispersed in
solution
.H
Pt
Pt
.H
Pt
Pt
Pt
Pt
Pt
Pt
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MECHANISM OF HYDROGENATION
.H
.H
.H
.H
.H
.H
.H
CATALYST
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MECHANISM OF HYDROGENATION
.
.
.H H H .
H
.
.
.H H H
.H H.
HYDROGEN
ADSORBS
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MECHANISM OF HYDROGENATION
R
. .
.
.
.H H H .
H
.
.
.H H H
.H H.
ALKENE
APPROACHES
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MECHANISM OF HYDROGENATION
. ..
.
.H H H .
H
.
.
.H H H
.H H.
ALKENE PICKS UP
TWO HYDROGENS
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MECHANISM OF HYDROGENATION
R
..
H
.
.
.H
.H
.H
.H
.H
ALKANE IS
FORMED
.H
.H
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CH3
CH3
H
CH3
CH3
CH3
H syn
addition
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EXAMPLES
Pt
CH3 + H2
CH3 CH CH CH3 + H2
CH3
Pt
CH2
+ H2
Pt
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C-H
H-X
H
C
H-X
anti
addition
C-H
Br2
Br
R
C
Br
C
H
anti addition
Br2
Br
Br
Br
Br
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Hydration of an Alkyne
C-H
H2O
H2SO4
HgSO4
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Hg2+
R
slow
2+ Hg
Mechanism of
Alkyne Hydration
Hg+
R
C
O
- H+
C
H
Hg+
R
C
H
H
H
acid
hydrolysis
Hg2+
H
C
R
C
H
ENOL
KETO
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Keto-Enol Tautomerism
Tautomers: Two compounds with
different structures but which exist in
equilibrium.
Most often, the two structures differ by
the position of a proton.
NOTE CAREFULLY: This is equilibrium,
not resonance!
H
R
R
H
C
H O
. :
H
ENOL
:O
..
H
KETO
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R
R
CH3
OH
C
H
O
O
C
CH3
H-C
N
C
C
H
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H
C
catalyst
H
ethylene
polyethylene
Polymerization of propene
H
CH3
C
catalyst
H
CH3
CH3
CH3
CH3
isotactic
CH3
CH3
CH3
CH3
syndiotactic
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Polymer Problems
Be sure to look at the mechanism of
free radical polymerization of
styrene (p. 733-735).
In-Text Problems 8-27, 8-28, and 829
End of chapter problems: 59, 60,
and 62
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Highlights of Chapter 8
HX addition to alkenes/ Markovnikovs
Rule
Addition of water to alkenes, H+ catalyst
Addition of halogens to alkenes/
stereochem.
Addition of X2 / H2O to alkenes
Carbocation rearrangements
Free-radical addition of HBr (Anti-Mark.)
Hydrogenation
Additions to alkynes
Addition polymers
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