Tautomerism & Desmotropism

Tautomerism: is a phenomenon where a single chemical compound tends to exist

in two or more interconvertible structures that are different in terms of the relative
position of one atomic nucleus, which is generally hydrogen. The two structures are
called tautomers, and these types of isomer compounds usually differ only in the
number of electrons and protons. They also exist in dynamic equilibrium.

Desmo = bond & Tropos = turn

 Structure isomers " Its name is structural isomers because there is a

movement of a group, which is a proton. “The proton moves from one place
to another, resulting in a change in the structural composition. "
 " tautomers ⇌ tautomers " We can separate them easily

Example

1. keto - Enol Form

 carbonyl tautomerism
 En = double bond & ol = alcohol
 In this case, why is keto more than enol?
 Because keto is more stable than enol, the double bond in keto is between
carbon and oxygen, and the oxygen is higher in electronegativity than carbon.
The electrons in the bond will be closer to the oxygen, and the bond will be
shorter and stronger compared to enol, which is the double bond between
two carbon atoms.
2. Imine – Enamine

 Non-carbonyl tautomerism
 Imine is a functional group or organic compound containing a carbon–
nitrogen double bond (C=N). The nitrogen atom can be attached to a
hydrogen or an organic group (R)
 Why did the double bond between nitrogen and carbon change to form
between carbon and carbon? When nitrogen has three sigma bonds around
it, it will be easy to release a lone pair. When it is in a pi bond, it will be
closer to carbon. He will not release a lone pair easily. It will be easier for
Enamine to form a coordination bond and activate the compound.
 When a three sigma bond is of the same length and approximately the same
strength, it is easy to form a coordinating bond. Change its shape with a
bond of any length. The bond is not the same. Do not leave a lone pair that
can participate, not as easily as the other.

3. Lactam - Lactim
  carbonyl tautomerism
 This is a tricyclic compound. Lactone compounds are cyclic, and the atoms of
the ring can be seven or octagonal
 A cyclic compound with fewer than five atoms in the ring begins to group
together
 In the triple ring, the atoms are close to each other, so repulsion occurs
between the atoms, which stabilizes the compound.
 The bond is bent and takes the shape of a banana. Tricyclic compounds are
said to be shaped like a banana. Because they have a bond that bends, the
atoms begin to move away from each other in a straight line, so the
compound is somewhat stable.

4. Nitroso – oxime

 Non-carbonyl tautomerism
 nitroso refers to a functional group in which the nitric oxide (−N=O) group is
attached to an organic moiety
 oxime is a carbon atom and a nitrogen atom with a double bond between
them. It is connected to the nitrogen by a bond with a hydroxyl group
5. Nitrile – ketenimine
  Non-carbonyl tautomerism
 Nitriles are a class of organic compounds that contain a C≡N- functional
group called a nitrile group. There is a triple bond in the nitrile group
between carbon and nitrogen.
 Keten = double bond between two carbon atom

6. Amide – Amindol (amidic acid)

Structural requirement
Enolization = keto - Enol tautomerism

 Intramolecular H.bond
 Aromaticity
1. .

 Why did the proton emerge as 𝐶𝐻2 and not 𝐶𝐻3?

Because𝐶𝐻2 , when the H+ is lost, is a secondary carboanion, and the

carbonyl group is an electron-withdrawing group that helps stabilize the
secondary carboanion, while 𝐶𝐻3 is a primary carboanion. If instead of
an electron-withdrawing group,if there was an electron-donating group,
it would be a primary carboanion, not a sacadray carboanion..

The percentage of the enol form is very high compared to the ketone,
and the solvent present in the medium affects the percentage

Enol creates an Intramolecular H.bond between itself Intramolecular

H.bond provides stability as if the compound is do cyclization

The solvent also determines the percentage of the compound. If the

oxygen on the carbonyl atom is present in the water, it will form a
H.bond with the water Intramolecular H.bond, the ketone percentage
will be higher. If the solvent is benzene, it will be Intramolecular H.bond,
so the enol percentage is higher.

2. .

 If it has an aromatic character, a higher enol is what will be

formed
3. .
  Both C=O are present in the Syn position, and they re-partition
and the enol is transformed into a form that can act as an
Intramolecular H.bond and stabilize.
4. .

 Both C=O are in anti-mode, they do not cause crowding with each
other. In keto form, a normal form is formed, with a high
percentage.
5. .

 The enol form is not formed due to the anti-aromatic compound

 The anti-aromatic compound is less stable