ENOL CONTENT

Keto-Enol Tautomerism
H
O
C C

O
C C

H
keto

enol

For most ketones, the keto form

predominates in the equilibrium

AS A GENERAL RULE: ENOLS ARE

UNSTABLE
ol

ENOLS :
( have -OH attached to a double bond)
Think of this combination as unstable.

ene
OH

NOTE :
Phenols are not enols and they are
very stable (benzene resonance).

TAUTOMERISM
ENOL

KETO

O H

H3C C CH2

H3C C CH2
H

unstable enol

Most enols are not

favored,
O
H
H
O

enol

H3C C CH2

+
H O H

keto

TAUTOMERS :

E
N
E
R
G
Y

they rapidly change to keto.

species in
equilibrium
that differ in
the position
of a proton or
other group.

To interconvert tautomers,
a proton is transferred
from oxygen to carbon.
Mechanism, next
slide..

Tautomerism is Catalyzed by Traces of

Either Acid or Base
BASE
CATALYSIS

..

O:
H

keto

.. H-O:
..

O:
C C

C C

.. H-O: +
..

..

: O:

- ..

enolate
ion

- ..

: O:

C C

C C
enol

resonance structures

..
H-O:
H

Tautomerism is Catalyzed by Traces of

Either Acid or Base
..

ACID
CATALYSIS

..

O:

H-O-H
+
H

C C
H

keto

.. H

+O
C C

..

:O-H
H

: O:

C C

..

+
enol

H-O-H
+
H

CONVERSION OF AN ENOL TO A KETONE

( catalyzed by small amounts of acid )

ENOL

H
O H

H3C C CH2

H3C C CH2
+
H

+
H O H
H

+O

H3C C CH2
H

+O

H3C C CH2
H
H

+
H O H

O H
O

H3C C CH2
H
KETONE

Enol Percentages are Low

in Most Ordinary Ketones
O

OH

4.1 x 10-4 %

OH

CH3 C CH3

H2C

C CH3

O
H2C

CH C CH3

H2C

< 2 x 10-4 %

OH
CH C CH2

2.5 x 10-3 %

FACTORS THAT STABILIZE

THE ENOL FORM
increasing the amount in the equilibrium

MOSTLY RESONANCE
O

O
R

O
R

1.

Resonance helps stabilize the enol.

2.

Phenyl substituents R also help to stabilize

the enol by extending the resonance system.

3.

Equivalent R groups results in symmetry

which also stabilizes the enol.
(i.e., equivalent resonance contributors )

Enol Percentages in 1,3-Diketones

are Higher
O

H3C C CH2 C H

H3C C CH2 C CH3

H3C C CH2 C OC2H5

OH

H3C C C C H

OH

98 %

H3C C C C CH3

OH

80 %

H3C C C C OC2H5 8 %

SOME ADDTIONAL PROPERTIES OF ENOLS

ENOLS ARE MORE ACIDIC THAN THEIR KETO FORM

ENOLS ARE NUCLEOPHILIC / REACT RAPIDLY WITH X 2

ARE AN IMPORTANT INTERMEDIATE IN
ACID-CALTALYZED ALDOL CONDENSATIONS
MAKE COMPLEXES WITH FeCl3 (like phenols)

Discussed in class (if time).

Compound

Percent Enol
(Neat Compound)
O

CH3 C CH C H
2

H
H

C CH
3

CH2

Percent Enol
(Neat Compound)

98%

Compound

C CH
3
C
H

89%

O
C CH
3

O
CH3

CH2

C CH
3

80%

<~0.004%

73%

<~0.002%

O
CH3

CH3

O
C

0.035%

O
C OEt

CH3

0.0025%

CH2

C OEt

8%

Simple Ketones ~18 Kcal (75kJ)

or Keq 6.3 x 10-14