Tautomerism in Organic Chemistry | Explained by IITian | Jee Mains, Advance, NEET, AIIMS & BITSAT

Tautomerism refers to the dynamic equilibrium between two compounds with same molecular formula. It is also called as desmotropism or kryptotropism or prototropy or allelotropism.

It is most often a special case of functional group isomerism. In general, the tautomers have different functional groups and exist in dynamic equilibrium with each other due to a rapid interconversion from one form to another.

It is very important to note that the tautomers are not the resonance structures of same compound.

1) Keto-enol tautomerism: The carbonyl compounds containing at least one α-hydrogen atom exhibit keto-enol tautomerism. The carbonyl group can be converted to enol form due to transfer of one of the α-hydrogen onto the oxygen atom.

Note: An alcoholic group on C=C is called enol. It is an alkene alcohol.

The % composition of keto enol tautomeric mixture depends on the relative stabilities of these two forms. In general the keto form is the low energy form and is more stable than the enol form. However the enol form is also stable in certain cases due to other stability factors.

The dynamic equilibrium between a keto form and an enol form exhibited by acetone is shown below. The tautomers are formed due to complete transfer of hydrogen. However the relatively stable keto form exists in higher percentage (about 99%).

2) The nitro-aci tautomerism: It is exhibited by nitro compounds containing atleast one α-hydrogen. In this case also, the hydrogen atom is transferred completely from one atom to another during the conversion of nitro form to aci form and vice versa.

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. The same factors that stabilize alkenes or alcohols will also stabilize the enol form. There are two strong factors and three subtle factors.

Biggies (2):

1. Aromaticity. Phenols can theoretically exist in their keto forms, but the enol form is greatly favored due to aromatic stabilization.

2. Hydrogen Bonding. Nearby hydrogen bond acceptors stabilize the enol form. When a Lewis basic group is nearby, the enol form is stabilized by internal hydrogen bonding.

Here are three more subtle effects in keto-enol tautomerism:

3. Solvent. Solvent can also play an important role in the relative stability of the enol form. For example, in benzene, the enol form of 2,4-pentanedione predominates in a 94:6 ratio over the keto form, whereas the numbers almost reverse completely in water. What’s going on? In a polar protic solvent like water, the lone pairs will be involved in hydrogen bonding with the solvent, making them less available to hydrogen bond with the enol form.

4. Conjugation . π systems are a little like Cheerios in milk: given the choice, they want to connect together than hang out in isolation. So in the molecule depicted, the more favorable tautomer will be the one on the left, where the double bond is a connected by conjugation to the phenyl.

5. Substitution. In the absence of steric factors, increasing substitution at carbon will stabilize the enol form. Enols are alkenes too – so any factors that stabilize alkenes, will stabilize enols as well. All else being equal, double bonds increase in thermodynamic stability as substitution is increased. So in the above example, the enol on the left should be the more stable one.

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