ISOMERISM 1. 60° in staggered conformation.

Compounds with the same molecular formula but different arrangements of 2. 0° in eclipsed conformation.
atoms or bonds. Types of isomerism are as follows: Conformations of Propane
1. Structural Isomerism – Isomers differ in how atoms are connected. Propane shows similar conformational behavior to ethane but with a CH3
(a) Chain Isomerism – Isomers with different carbon skeletons group. The torsional strain in the eclipsed form is higher due to CH3–H
(straight/branched). repulsion. The staggered conformation is more stable.
(b) Position Isomerism – Isomers with the same chain but functional Conformations of n-Butane
groups/multiple bonds at different positions. The conformations of n-butane are viewed around the C2–C3 bond. There are
four key conformations:
(c) Functional Isomerism – Isomers with different functional groups but same
1. Anti (Staggered): Dihedral angle is 180°, most stable.
molecular formula.
2. Gauche (Staggered): Dihedral angle is 60°, less stable.
(d) Metamerism – Isomers with same functional group but different alkyl
3. Eclipsed (CH3–H): Dihedral angle is 0°, 120°, higher energy.
groups on either side of a polyvalent atom.
4. Eclipsed (CH3–CH3): Dihedral angle is 0°, least stable.
(e) Tautomerism – A dynamic equilibrium involving proton migration and Conformations of Cycloalkanes
double bond shift. The stability of cycloalkanes depends on angle strain, torsional strain, and
- Dyad System – Tautomerism between two atoms/groups, typically involving steric strain.
α-hydrogen and electronegative atom. Baeyer’s Strain Theory assumes that all rings are planar and calculates strain
- Triad System – Tautomerism involving three atoms in conjugation enabling based on deviation from 109.5° (ideal tetrahedral angle).
proton shift. 1. Cyclopropane (60°): High strain.
- Keto-Enol Tautomerism – Equilibrium between a ketone (or aldehyde) and 2. Cyclopentane (108°): Low strain.
an enol form. Limitations of Baeyer’s Strain Theory: Assumes planarity, but most rings are
MECHANISM OF TAUTOMERISM non-planar, and does not account for torsional strain.
(i) Base-Catalyzed – A base abstracts α-hydrogen to form enolate ion which Conformations of Cyclohexane
rearranges to enol. Cyclohexane adopts non-planar conformations to relieve strain:
(ii) Acid-Catalyzed – Protonation of carbonyl oxygen followed by internal 1. Chair: Most stable, no angle or torsional strain.
proton shift forms enol. 2. Boat: Less stable due to flagpole interactions.
TAUTOMERIC MIXTURE COMPOSITION 3. Twist-boat: More stable than the boat, less stable than chair.
The more stable tautomer, usually the keto form, predominates based on 4. Half-chair: Least stable, intermediate during chair flip.
resonance, hydrogen bonding, and aromaticity. Chair flip interconverts axial and equatorial positions.
Monosubstituted Cyclohexane Derivatives
ESSENTIAL CONDITIONS FOR TAUTOMERISM
In monosubstituted cyclohexane, the substituent prefers the equatorial
Presence of α-hydrogen and possibility for conjugation/resonance
position to minimize 1,3-diaxial interactions. Bulkier groups (like tert-butyl)
stabilization.
strongly prefer the equatorial position.
TAUTOMERISM INVOLVING NITROGEN II. Configurational Isomerism
(i) Nitro–Aci Tautomerism – Interconversion between –NO₂ and –NO(OH). Geometrical Isomerism (Cis-Trans / E-Z)
(ii) Nitrile–Nitro Tautomerism – Interconversion between –C≡N and –C=NOH. Cis-trans isomerism occurs in alkenes or cyclic compounds.
(f) Ring–Chain Isomerism – Isomers differ in being cyclic (ring) or open-chain. Cis: Same side
(g) Isotopic Isomerism – Isomers differ only in the isotopic nature of atoms Trans: Opposite sides
(e.g., ¹H vs ²H). E/Z notation (Cahn–Ingold–Prelog rules):
DOUBLE BOND EQUIVALENT (DBE) / DEGREE OF UNSATURATION E: High priority groups on opposite sides.
Definition: Number of π-bonds and/or rings in a compound. Z: High priority groups on the same side.
Formula: Optical Isomerism
DBE = (2C + 2 - H + N - X) Optical isomerism occurs due to chirality (non-superimposable mirror images).
Necessary conditions for optical isomerism:
2
1. Chiral center (usually a carbon with four different groups).
Where C = carbon, H = hydrogen, N = nitrogen, X = halogens
2. No plane of symmetry (POS).
Application: Used to determine the number of rings and/or multiple bonds. 3. No center of symmetry (COS).
Stereoisomerism 4. No alternating axis of symmetry (AOS).
is a type of isomerism where compounds have the same molecular formula Elements of Symmetry
and bond connectivity but differ in the spatial arrangement of atoms. It is 1. Plane of symmetry (POS): A plane dividing a molecule into mirror halves.
divided into two broad categories: Conformational isomerism and 2. Center of symmetry (COS): A point where inversion of all parts leads to
Configurational isomerism. Conformational isomerism involves identical configuration.
interconversion through rotation around single bonds, while configurational 3. Alternating axis of symmetry (AOS): An improper rotation-reflection axis.
isomerism involves a change in connectivity or the breaking of bonds for D/L Notation
interconversion. Used in carbohydrates and amino acids, based on similarity to glyceraldehyde:
I. Conformational Isomerism D: OH on the right in Fischer projection.
Representation of Conformations L: OH on the left in Fischer projection.
1. Sawhorse Projection: A view along a C–C bond at an angle, showing the D/L notation is not related to optical rotation (+/−).
front and back carbon atoms with their substituents slanted. R/S Notation (Absolute Configuration)
2. Newman Projection: Looking straight down the C–C bond axis. The front Using Cahn–Ingold–Prelog priority rules:
carbon is a dot, and the back carbon is a circle. 1. Assign priority to 4 groups (higher atomic number = higher priority).
Conformations of Ethane 2. Place the lowest priority group behind the plane.
Ethane rotates freely about the C–C sigma bond. There are three key 3. If 1 → 2 → 3 is clockwise, the configuration is R.
conformations: 4. If 1 → 2 → 3 is counterclockwise, the configuration is S.
1. Staggered: The H atoms are as far apart as possible, making it the most Factors Affecting Conformational Stability
stable conformation. 1. Torsional strain: Caused by eclipsed bonds.
2. Eclipsed: The H atoms are aligned, making it the least stable with maximum 2. Steric hindrance: Crowding of bulky groups.
torsional strain. 3. Angle strain: Deviation from the ideal bond angle.
3. Skew: Any intermediate position. 4. Dipole interactions: Polar groups may repel or attract.
The dihedral angle is the angle between two bonds on adjacent atoms: 5. Hydrogen bonding: Can stabilize certain conformations.
JEE Advanced Tips
1. Know the energy order of conformers, especially for ethane, butane, and
cyclohexane.
2. Master Newman projections for conformational analysis.
3. Practice assigning E/Z and R/S notations without hesitation.
4. Use Fischer projections for D/L and optical activity.
5. Understand why the chair conformation of cyclohexane is more stable and
how to flip it.