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Tautomerism

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Last updated date: 23rd May 2024
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Tautomerism: Unveiling Molecular Transformations

Tautomers are like shape-shifters in the molecular world—they don't stick to one form. In this section, we'll explore compounds that can change into various versions of themselves without any magic. It's all about the dynamic interaction of protons and electrons.


Think of a molecule that can take on different shapes, each with a slightly rearranged set of atoms. These shape-changing structures, called tautomers, constantly switch back and forth in a fascinating dance. This isn't just for show; it has important implications in fields like biochemistry, drug discovery, and material science. Let’s find out how this molecular magic is essential for biomolecules like DNA and proteins. And it doesn't stop there; it affects the taste of food, the smell of flowers, and even how strong medicines are.


What is Tautomerism?

Tautomerism is a phenomenon where a single chemical compound tends to exist in either two or more structures of interconvertible type, which are different considering the relative position of one atomic nucleus i.e. hydrogen, in general. The two structures are known as tautomers. These types of isomer compounds only differ usually in the number of electrons and protons. They also exist in the dynamic equilibrium.


If a reaction takes place between these compounds, there is only the transfer of protons. Tautomerism is otherwise termed as desmotropism. Other names that are widely used for tautomerism are kryptomerism, allotropism or merotropy. Tautomerism is the most widely accepted term in the field of chemistry. There are several types of tautomerism, keto-enol tautomerism being the most important. In this type, one tautomer exists as a ketone while the other tautomer exists as an enol. Acetone and phenol are the two most common examples. 


Tautomerism usually happens in the presence of a catalyst.

  • Acid-Catalyst: Here, firstly, the protonation takes place, cation will be delocalized.  Then, the deprotonation will take place in the adjacent position of the cation.

  • Whereas, for base catalysts, deprotonation is the primary step. Here, rather than cation delocalization, anion delocalization takes place and finally protonation to a different position of the anion.


Characteristics of Tautomerism- 

  1. There is a movement of atoms involved which are alpha hydrogen atoms.

  2. The compounds can be separated and isolated as they are definite compounds.

  3. Tautomeric forms have two different structures.

  4. The compounds of tautomers are in equilibrium with each other.

  5. Tautomerism does not have an effect on the bond length. 

  6. Tautomerism does not decrease the energy of the molecules and hence stabilises the molecule.

  7. It occurs in planar as well as non- planar molecules.


Examples of Tautomerism

As a simple definition of Tautomerism, it is expressed as a type of isomerism, where the isomers interchange into/between one another easily to exist together in equilibrium. At the time of reaction, there occurs a proton transfer in an intramolecular fashion. Consider a tautomerism example given below.


Ketone-enol, enamine-imine,lactam-lactim are some of the examples of tautomers.


Meanwhile, some key features of Tautomerism are that this process provides more stability for the compound. In this phenomenon, there exists an exchange of a hydrogen atom between two other atoms while forming a covalent bond to either one. The reversible process is Tautomerism.


Tautomerism's Structure Needs:

  • Substances have molecules that are polar and include weakly acidic functional groups.

  • It includes moving an atom's position.

  • It doesn't impact things like bond length.

  • Usually happens in flat or non-flat molecules.


Tautomerism Types

In the 1880s, a scientist named Emil Erlenmeyer developed a rule for Tautomerism. He is one of the first people to have studied keto-enol Tautomerism. This rule states that the hydroxyl group in all alcohols is attached directly with a double-bonded carbon atom, and forms aldehydes or ketones. This happened due to the more stability of the keto form.


There are different types of Tautomerism. Among those, keto-enol Tautomerism is the most important one. Here, one structure is in enol, and the other is in ketone form. Both tautomeric forms are interconvertible to each other by the use of acid or base catalysts. This conversion process of the ketone into enol is called enolization.


The types of Tautomerism include:

  • Prototropy

This tautomerism type occurs due to the compound's acid-base behaviour. Here, the two forms differ only in the position of a proton. This structure will have the same number of charges and the empirical formula.

  • Annular Tautomerism

If a proton occupies either two or more positions of a heterocyclic system, then such a process is known as annular Tautomerism. In Tautomerism, because of the delocalization of protons, if an open structure is altered to a ring structure, then such a tautomer is known as ring-chain tautomers. An example of ring-chain tautomers is Glucose.

  • Valence Tautomerism

Valence tautomerism is a type of Tautomerism where there is a continuous formation and single and double bonds breaking in the compound without any migration of atoms or groups. It is different from the other tautomerism types and is a rapid process.


In this, there is a change in geometrical structure but no change available for mesomers or canonical resonance structure.


Tautomerism in Non-Carbonyl Compounds

Many non-carbonyl systems are available as mixtures of tautomers. A few examples are given below.


On the chemical properties of the compound, the Tautomerism can have a huge impact.


Tautomeric Form of Unsymmetrical Ketones

There is only one form of tautomer in symmetric form. But there can be two for an unsymmetrical form. Let us have a look at the example given.


Tautomerism Reaction Mechanism

Let us discuss the keto-enol tautomerization acid catalysis. It is a two-step method in an aqueous solution of acid. The carbon atom, which is closest to the functional group, is known as the alpha carbon atom. So, for this mechanism to take place, one hydrogen atom at least should be with the alpha carbon atom. It can also be known as an alpha hydrogen atom.


The resultant hydrogen atom is added to the antibonding pi-orbital of the carbonyl group parallelly. Then, this bond will undergo hyperconjugation with the C-H bond and decrease the electron density at the alpha carbon atom, where the alpha hydrogen atom will become more acidic compared to before. If the position of alpha hydrogen has not happened, the tautomerism process will be very slow. An example of this slow process is Adamatanone.


We should follow Markovnikov's rule in addition to this process. Firstly, in the mechanism, there exists a hydronium ion (H3O+), an electrophile, so the electrons exposed near the C=C bond will be donated. If the number of hydrogen atoms present in the compound is more, thereby, the addition of protons also increases.


The reaction mechanism can be given below.


Important Questions of Tautomerism

1. What is meant by the term tautomer?

2. Explain the structural requirements of a compound to possess tautomerization.

3. How is the ring-chain tautomerism obtained?

4. Give some examples of tautomerism, ring-chain tautomerism, and annular tautomerism.

5. What are the different types of tautomerism, and how are they classified? Explain.

6. How does tautomerism depend on the catalyzation process? Which is the type of such a process? Explain briefly.

7. Explain the mechanism of tautomerism in a step-by-step procedure with examples.

8. What is valence tautomerism?

9. Write the importance of the alpha carbon atom in tautomerism.

10. Explain the tautomerism related to the acid-base behavior of the molecule.

11. What is meant by annular tautomerism?

12. Protonation and deprotonation are the two essential processes in tautomerism. Justify.

13. List the applications of tautomerism in various fields.

14. Explain the stability of the keto-enol form of tautomer.


Conclusion

Tautomerism, a vital concept for JEE Main, involves isomers (same molecular formula) that differ in the position of protons and electrons. In simpler terms, molecules can exist in two forms that quickly switch between each other. This dynamic behavior impacts chemical reactions. For instance, in keto-enol tautomerism, a molecule can transform between a keto form (more common) and an enol form. Understanding tautomerism is crucial for predicting how molecules behave, influencing drug design and various chemical processes. In JEE Main, grasp the idea that molecules are dynamic, not fixed structures, to navigate questions related to tautomerism successfully.

FAQs on Tautomerism

1. How does acid show tautomerism?

Tautomerism is the special kind of functional isomerism in which migration OH H occurs in a dynamic equilibrium condition.


Acid Mechanism :


Step 1 - Acid will give H+ ion, and the Oxygen of ketone will donate its lone pair to H+ and carries a +ve charge on itself (this is a fast process)


CH3—C=0—CH3 + H+ → CH3—C=OH—CH3


Step 2 - Because Oxygen carries a +ve charge, it will attract an electron from Carbon, and a double bond between C=O will break, and it will become OH, and simultaneously Carbon will form a double bond with the neighbouring Carbon. (it's a slow and rate-determining process)


CH3—C=OH—CH3 - H+ → CH2=C-OH—CH3


Key Point - Tautomerism can be achieved in acidic and basic mediums (the major product is different for both cases) as well.


Basic Medium -  A double bond is formed between Carbon and its functional group, which has a lower number of alkyl groups.


Acidic Medium - A double bond is formed between the Carbon and its functional groups, which has more alkyl groups.


For example, consider the below reactions given.


CH3—CO—CH2—CH3 + OH-(basic) → CH2=C(OH)—CH2—CH3


CH3—CO—CH2—CH3 + H+(acidic) → CH3-C(OH)=CH—CH3

2. What is the difference between tautomerization and resonance?

Tautomerism is a real phenomenon, whereas resonance happens hypothetically. There is a movement of atoms (alpha hydrogen) involved in Tautomerism. But in resonance, the electron movement of the p orbital happens. Thus, there's no movement of atoms in the latter. While Tautomerism is represented by the double arrows (same as equilibrium), resonance is represented by one double-headed arrow.


Tautomerism happens in solutions; it means the alpha hydrogen gets removed, and another hydrogen from the water gets attached to the oxygen atom. But resonance is not restricted like Tautomerism, but only happens in solutions. Tautomerism does not have any effect on the bond length but resonance has an effect on the bond length as during resonance the single bond gets shortened while the double bond becomes longer. Tautomerism does not decrease the energy of the molecule while resonance lowers the energy of the molecule.

3. How is tautomerism different from metamerism?

Tautomerism can be defined as a phenomenon where a single chemical compound tends to exist in either two or more structures of interconvertible type, which are different considering the relative position of one atomic nucleus i.e. hydrogen, in general. On the other hand, Metamerism occurs when alkyl groups on the sides of the functional groups differ from each other. This indicates that it is an unequal distribution of carbon atoms. The main difference between tautomerism and metamerism is that tautomerism means the dynamic equilibrium between two compounds having a same molecular formula whereas metamerism refers to structural isomerism in which alkyl groups which are attached to the same functional group are different. The isomerization process of tautomers is called tautomerization whereas the isomerization of metamers is called metamerization.

4. What are the requirements for tautomerism to happen?

The compounds which undergo Tautomerism need to have a weak acidic group and also the molecules should be polar. It also requires an atom to change its position. It occurs in both types of the compounds, that is the compounds which have their atoms lying in the same plane as well as in compounds which do not have their atoms in the same plane. Tautomerism is a reaction which also needs a catalyst. The catalyst can be of two types, acidic and basic.

5. From where can I study structural isomerism and its types?

Online notes are handy for students who do not like to make notes and want to have a quick recap before the exams. The notes are also useful for those students who could not attend the classes in their schools and wish to study the missed portions. Students can download free notes from the official website of Vedantu that is Vedantu.com. The notes are available in PDF format and are written in easy and simple language. Students can access these free notes and score good marks. Vedantu also offers NCERT solutions, previous year question papers and important questions with solutions.  Students may also attend free live classes on Vedantu from the comfort of their homes.