Have you played this game?

9/10/2020 Dr. Erum Akbar 1

ORGANIC CHEMISTRY
CHEM-201

TAUTOMERISM
LESSON 7

Dr Erum Akbar Hussain

Associate Professor
Chemistry Department, LCWU
 A reaction which involves simple proton transfer in an
intramolecular fashion is called a tautomerism.

Tautomers are isomers of a compound which differ only in

the position of the protons and electrons

They are constitutional isomers of two compounds that

readily interconvert between one another.

9/10/2020 Dr. Erum Akbar 3

 ketone – enol:
H−O−C=C O=C−C−H

enamine – imine:

H−N−C=C N=C−C−H

amide – imidic acid:

H−N−C=O N=C−O−H

Molecules having Tautomerism

9/10/2020 Dr. Erum Akbar 4
Carbonyl tautomerism
9/10/2020 Dr. Erum Akbar 5
Acid/alkali catalyzed Mechanism
9/10/2020 Dr. Erum Akbar 6
Acetone keto enol conversion
9/10/2020 Dr. Erum Akbar 7
 The reason for the equilibrium lying to the left is due
to bond energies. The keto form has a C–H, C–C, and
C=O bond whereas the enol has a C=C, C–O an O–H
bond.

The sum of the first three is about 359 kcal/mol (1500

kJ/mol) and the second three is 347 kcal/mol (1452 kJ/mol).
The keto form is therefore more thermodynamically stable by
12 kcal/mol (48 kJ/mol).

Although the keto form is most stable for aldehydes

and ketones in most situations, there are several
factors that will shift the equilibrium toward
the enol form.

Predicting Direction of Equilibrium

9/10/2020 Dr. Erum Akbar 8
 Tautomers are stabilized by solvent

 Hydrogen bonding

 Conjugation

Factors stabilizing Tautomers

9/10/2020 Dr. Erum Akbar 9

Examples Guanine & Uracil
9/10/2020 Dr. Erum Akbar 10