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Stereochemistry Reading Time: 12 min 2 Nomenclature Systems

Geometrical Isomerism in Alkenes: The CIS-TRANS and E-Z Nomenclature

Master the art of distinguishing between different spatial arrangements in alkenes and predict geometrical isomers with confidence.

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Nomenclature Systems
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Why Geometrical Isomerism Matters

Geometrical isomerism arises due to restricted rotation around double bonds in alkenes. These isomers have the same molecular formula but different spatial arrangements, leading to distinct physical and chemical properties.

🎯 JEE Importance

Geometrical isomerism questions appear in every JEE paper, testing your understanding of stereochemistry, priority rules, and isomer prediction. Mastering this topic can secure 2-4 easy marks.

1. Conditions for Geometrical Isomerism

Essential Requirements

Restricted Rotation

Double bond prevents free rotation, locking groups in position

Different Groups

Each carbon of double bond must have two different substituents

Examples

Shows Geometrical Isomerism

CH₃-CH=CH-CH₃

Different groups on both carbons

No Geometrical Isomerism

CH₂=CH-CH₃

Same groups on one carbon

2. CIS-TRANS Nomenclature System

The Traditional Approach

CIS-TRANS system works when each carbon of the double bond has at least one identical group.

CIS Configuration

Definition: Similar groups are on the same side of the double bond

CIS-2-Butene

CH₃
C=C
CH₃

Both CH₃ groups on same side

Higher boiling point

TRANS Configuration

Definition: Similar groups are on the opposite sides of the double bond

TRANS-2-Butene

CH₃
C=C
H
H
C=C
CH₃

CH₃ groups on opposite sides

Lower boiling point

💡 Physical Property Differences

  • CIS isomers have higher boiling points (more polar)
  • TRANS isomers have lower melting points (better packing)
  • CIS isomers are less stable due to steric hindrance
  • TRANS isomers are more thermodynamically stable

3. E-Z Nomenclature System (IUPAC)

The Comprehensive Approach

E-Z system works for all alkenes using Cahn-Ingold-Prelog priority rules to assign configurations.

Cahn-Ingold-Prelog Priority Rules

Rule 1: Atomic Number

Higher atomic number gets higher priority

Br (35) > Cl (17) > S (16) > O (8) > N (7) > C (6) > H (1)

Rule 2: Isotopes

Higher mass number gets higher priority

D (²H) > H (¹H), T (³H) > D > H

Rule 3: Sequential Comparison

If first atoms are same, compare second atoms

-CH₂CH₃ > -CH₃ (C,C,H vs C,H,H)

Rule 4: Multiple Bonds

Treat multiple bonds as duplicate atoms

-CH=O treated as C(O,O), -C≡N as C(N,N,N)

Assigning E/Z Configuration

Step 1: Assign priorities to groups on each carbon using CIP rules

Step 2: Check positions of high priority groups

Step 3: Assign configuration:

E Configuration (Entgegen)

High priority groups OPPOSITE

1 → High
C=C
2 ← Low
2 ← Low
C=C
1 → High

Z Configuration (Zusammen)

High priority groups TOGETHER

1 → High
C=C
1 → High
2 ← Low
C=C
2 ← Low

Example: 1-Bromo-1,2-dichloroethene

Step 1: Assign priorities

Left carbon: Br (35) > Cl (17) → Priority: Br > Cl

Right carbon: Cl (17) > H (1) → Priority: Cl > H

Step 2: Check positions

Br (1)
C=C
Cl (2)
Cl (1)
C=C
H (2)

High priority groups are TOGETHER → Z configuration

Correct name: (Z)-1-bromo-1,2-dichloroethene

4. Predicting Number of Geometrical Isomers

Systematic Approach

For Simple Alkenes: C=C

Formula: 2ⁿ where n = number of carbons with two different groups

Alkene Type Formula n value Isomers
abC=Cab 2 4 (2 pairs of enantiomers)
abC=Cac 1 2 (CIS & TRANS)
abC=Ccd 2 4 (EE, EZ, ZE, ZZ)

For Polyenes

Independent double bonds: Multiply possibilities for each double bond

Cumulated dienes: Consider overall molecule symmetry

Conjugated dienes: s-CIS and s-TRANS conformers possible

Practice: Predict isomers for CH₃-CH=CH-CH=CH-CH₃

Step 1: Identify double bonds

Two double bonds: C₂=C₃ and C₄=C₅

Step 2: Analyze each double bond

C₂=C₃: CH₃, H on C₂ and H, CH on C₃ → Shows geometrical isomerism

C₄=C₅: CH, H on C₄ and H, CH₃ on C₅ → Shows geometrical isomerism

Step 3: Calculate total isomers

Each double bond can have E or Z configuration

Total possibilities = 2 × 2 = 4 geometrical isomers

Possible isomers: EE, EZ, ZE, ZZ

5. Practice Problems

Test Your Understanding

Problem 1: Assign E/Z configuration to Br-CH=CH-Cl

Hint: Compare atomic numbers of substituents

Problem 2: How many geometrical isomers for CH₃-CH₂-CH=CH-CH₃?

Hint: Check if both carbons have different substituents

Problem 3: Assign configuration to HOOC-CH=CH-COOH

Hint: -COOH has higher priority than -H

Problem 4: Predict isomers for CH₃-CH=CH-CH=CH-COOH

Hint: Consider both double bonds independently

Need Help?

Draw the molecules, assign priorities using CIP rules, and determine relative positions of high priority groups.

📋 Quick Reference Guide

CIP Priority Order

  • I > Br > Cl > S > P > F > O > N > C > H
  • -CH₂OH > -C≡CH > -CH=CH₂ > -CH₂CH₃
  • -COOH > -CHO > -CH₂OH > -C₆H₅
  • R > H (always)

Memory Aids

  • E = Enemy (opposite sides)
  • Z = Zame Zide (same side)
  • CIS = Same side (like siblings)
  • TRANS = Across (like transformers)

Common Mistakes to Avoid

Wrong: Using CIS-TRANS when no identical groups
Wrong: Forgetting to check both carbons of double bond
Wrong: Not following CIP rules sequentially
Wrong: Confusing E/Z with optical isomerism

🎯 JEE Exam Strategy

Quick Identification

First check if geometrical isomerism is possible

🔍
Systematic Approach

Always use CIP rules step-by-step for E/Z assignment

Verification

Verify your answer by checking both double bond carbons

📝
Drawing Helps

Draw the molecule to visualize group positions

Ready to Master More Stereochemistry?

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