ALCOHOLS WITH SULFURIC ACID

Acid-assisted E1
E1
Carbocation Rearrangements
DEHYDRATION OF AN ALCOHOL
An alcohol can be dehydrated by treatment with
concentrated sulfuric acid.
C H C H
3
C
H
3
C
H
3
C
+ H-O-H
H
2
SO
4
heat
C H C H
3
O
C
H
H
3
C
H
3
C
H
b-hydrogen
This is a beta-elimination reaction, similar to loss
of HCl, but requiring acid conditions, rather than
a strong base.
H O S
O
O
O H
C H C H
3
O
C H
H
H
3
C
H
3
C
H
C H C H
3
C
H
3
C
H
3
C
H
C H C H
3
C
H
3
C
H
3
C
H O S
O
O
O
+
+
C H C H
3
O
C H
H
H
3
C
H
3
C
ACID-ASSISTED E1 ELIMINATION
FOLLOWS
ZAITSEV RULE
slow
O H
H
fast
fast
-
(or alcohol or water)
LIKE E1
FROM HERE
ROLE OF THE ACID
Alcohols do not ionize because OH
-
is a strong
base (that is, OH
-
has a high energy).
R-O-H
R
+
+
O-H
-
However, if you protonate
the OH group, water leaves.
R-O-H
R
+
+
O-H
H H
+
Water is a stable, low energy, molecule.
..
..
..
..
:
:
..
..
+ H
+
NO
YES
ACID ASSISTED
R
+
R
+
OH
-
H
2
O
ROH
ROH
2
+
ionization
EXAMPLES
CH
3
OH
CH
3
CH CH CH
3
OH
CH
3
CH C CH
3
CH
3
H
3
PO
4
heat
H
2
SO
4
heat
CH C
CH
3
C H
3
C H
3
CH
3
O H
C C
CH
3
C H
3
C H
3
CH
3
H
3
PO
4
heat
CARBOCATION
REARRANGEMENTS
C H
3
C
C H
3
C H
3
C H C H
3
O H
C C
C H
3
C H
3
C H
3
C H
3
+
H
2
O
REARRANGEMENT OF A CARBOCATION
H
2
SO
4
SURPRISE!
different
skeleton !
C H
3
C
C H
3
C H
3
C H C H
3
O H
WHY NOT ?
no b-H
b-H here
C C H
3
CH
3
CH
3
CH CH
2
C H
3
C
C H
3
C H
3
C H C H
3
O H
C C
C H
3
C H
3
C H
3
C H
3
+
H
2
O
REARRANGEMENT OF A CARBOCATION
C H
3
C
C H
3
C H
3
C H C H
3
+
C C
C H
3
C H
3
C H
3
C H
3
H
+
protonation and
loss of water
OSO
3
H
loss of H
+
C C
C H
3
+
:
REARRANGEMENT
methyl shifts with
its pair of electrons
H
2
SO
4
different
skeleton !
TYPES OF CARBOCATION REARRANGEMENTS
C C
CH
3
+
+
C C
H
C C
+
1,2-methyl shift
1,2-hydride shift
1,2-phenyl shift
methyl migration
hydrogen migration
phenyl migration
groups move with their bonded electrons
methyl shift
+
CH
3
CH
3
H
+
CH
3
H
3
C
CH
3
CH
3
CH
3
H
3
C
OH
OSO
3
H
_
protonation
loss of H
2
O
loss of H
+
REARRANGEMENT - A 1,2-METHYL SHIFT
H
2
SO
4
+
CH
3
H
3
C
+
CH
3
CH
3
H
WHY DO THEY REARRANGE ?
secondary ion
tertiary ion
CARBOCATIONS
REARRANGE
TO ACHIEVE A
LOWER ENERGY
Carbocation Energies
3
o
< 2
o
< 1
o
< CH
3
+
energy
decrease
lowest highest
WHICH GROUP MIGRATES ?
C CH
H
H
3
C CH
3
+
C CH H
3
C CH
3
H
C CH CH
3
CH
3
H
C CH
H
H
3
C CH
3
+
+
+
tertiary
benzylic
The group that gives the
best carbocation will be
the one that migrates.
yes
secondary
benzylic
secondary
no
no
Competing Options
H or Me or Ph ?
BINGO !
RING EXPANSION
CH
2
OH CH
2
+
+
OMe
CH
2
+
When a carbocation is formed next to
a small strained ring (cyclopropane or
cyclobutane) the ring will often expand
to the next larger size.
MeOH
H
2
SO
4
MeOH
This allows the relief of some of the strain.
C C
CH
3
+
C C
CH
2
+
C C
CH
2
+
C C
CH
3
+
=
JUST LIKE A METHYL MIGRATION !
1
o
2
o
DO YOU HAVE A CARBOCATION?
STOP
E
X
R
E
M
E
R
E
G

N
A
D
STOP - LOOK - THINK
ALWAYS
EVALUATE FOR A
REARRANGEMENT
CAN YOU FORM A BETTER CARBOCATION ?
THE E1cb MECHANISM
THE E1cb MECHANISM
C C
H
X
C C
H
X
C C
H
X
B:
C C
C C
H
+
C C
X
C C
C C
B:
B:
proton
first
halogen
second
carbanion
This mechanism is rare since it requires special
characteristics for the substrate:
1. The proton must be easy to remove (very acidic).
This usually requires resonance stabilization in
the conjugate base.
2. The leaving group must be hesitant to leave.
This usually requires it to be a strong base,
or to have a strong bond to carbon.
O
OCH
3
H
H
acidic because the
adjacent carbonyl group
provides resonance in
the conjugate base
An Example of an E1cb Substrate
methoxide, the
leaving group, is a
strong base
strong bond
to carbon
O
O C H
3
H
H
O
O C H
3
H
O
O C H
3
H
O C H
3
O
O C H
3
N a O C H
3
C H
3
O H
+
slow
step
fast
step
conjugate base
stabilized by
resonance
WHY IT WORKS VIA E1cb
strong base =
poor leaving group
acidic hydrogen
easily removed
UNIMOLECULAR
Slow step does
not involve base
THERE IS A RANGE OF DIFFERENT
MECHANISMS FOR
b-ELIMINATION REACTIONS
SUMMARY
E1cb E2 E1 E1 E1 acid
assisted
strong strong weak
base base base
solvolysis
Zaitsev if
stereochem
allows
Zaitsev Zaitsev Zaitsev
stereospecific
anti-coplanar
alkyl halides alcohols
special
special case -
not common
acidic
neutral
carbocation rearrangements
concerted stepwise - carbocation
COMPARISON OF b-ELIMINATION MECHANISMS
requires:
acidic H and
poor leaving
group
stepwise -
carbanion
not stereospecific
K.I.S.S.
alkyl halide + strong base + heat = E2
alkyl halide + solvent + heat (solvolysis) = E1
alcohol + strong acid + heat = E1 (acid assisted)
C
O
C
H
C
X
typical situation for E1cb
H next to C=O (easy to remove)
X = strong base (difficult to break bond)
Only E1 reactions have rearrangements (carbocations)
Only E2 reactions require anti-coplanar b-hydrogens