CHEMICAL BONDING (ORGANIC CHEMISTRY):

1. Covalent Bonding

Definition: Covalent bonds form when two atoms share electrons mutually
to complete their outer electron shells (octet rule).

Characteristics:

Nonmetals (e.g., carbon, oxygen, nitrogen) typically form covalent bonds.

Bonds can be single, double, or triple, depending on the number of

electron pairs shared.

By: Dr Luqman
Example:

Methane (CH₄): Carbon shares its four electrons with four hydrogen atoms,
completing their valence shells.

C + 4H2 ----------------- CH4 (Methane)

Bond Polarity:

Nonpolar Covalent Bond: Electrons are shared equally.

Example: H₂ (Hydrogen molecule).

Polar Covalent Bond: Electrons are shared unequally.

Example: H₂O (Water) where oxygen pulls more electron density from
hydrogen.
 2. Ionic Bonding

Definition: Ionic bonds form when one atom donates an electron to another,
creating oppositely charged ions that attract each other.

Characteristics:

Typically occurs between metals and nonmetals (e.g., NaCl).

The metal loses electrons (forms a cation), and the nonmetal gains electrons
(forms an anion).

Example:

Sodium Chloride (NaCl): Sodium (Na) donates an electron to chlorine (Cl),

forming Na⁺ and Cl⁻ ions.
Na + Cl ----------------NaCl

By: Dr Luqman
3. Metallic Bonding

Definition: Metallic bonds occur between metal atoms, where electrons are
free to move through a lattice of positive ions.

Characteristics:

Results in properties like electrical conductivity and malleability in metals.

The "sea of electrons" allows electrons to move freely, enabling conductivity.

Example:

Copper (Cu): Copper atoms bond by sharing their electrons freely, which
allows electricity to flow.

Metallic bonding is typically seen in pure metals, like copper, and doesn't
involve specific reactions.
 4. Types of Covalent Bonds in Organic Molecules

Sigma (σ) Bonds: The first bond formed between two

atoms, where electron density is shared directly
between the nuclei.

Pi (π) Bonds: Second Bond Formed after sigma bonds in

double or triple bonds structures, involving sideways
overlap of p-orbitals.

By: Dr Luqman
 5. Bond Strength and Length

Single Bonds: Longest and weakest bonds (e.g., C-C in ethane).

Example: Ethane (C₂H₆): The single bond between two carbon

atoms is relatively weak.

By: Dr Luqman

Double Bonds: Shorter and stronger than single bonds (e.g., C=C in
ethene).

Example: Ethene (C₂H₄): The double bond between two carbon atoms
is stronger than a single bond.

Ethene is also called Ethylene

 Triple Bonds: Shortest and strongest bonds (e.g., C≡C in ethyne).

Example: Ethyne (C₂H₂): The triple bond between two carbon atoms
is the strongest bond.

6. Coordinate Covalent Bond (Dative Bond)

Definition: A coordinate covalent bond is a type of covalent bond in

which both electrons shared in the bond come from the same atom. This
typically happens when a lone pair of electrons from one atom is shared
with another atom that has an empty orbital.

Characteristics:

One atom donates both electrons to form the bond, while the other atom
accepts them.

It is similar to a regular covalent bond but differs in the source of the

shared electrons.
Ammonia (NH₃) and Boron Trifluoride (BF₃): In the reaction between
ammonia (NH₃) and boron trifluoride (BF₃), ammonia donates a lone
pair of electrons to boron to form a coordinate covalent bond.

By: Dr Luqman
 7. Hydrogen Bond

Definition: A hydrogen bond is a weak attraction between a

hydrogen atom that is bonded to a very electronegative atom (like
oxygen, nitrogen, or fluorine) and another electronegative atom
with a lone pair of electrons.

Characteristics:

It is not a true bond, but a weak attraction between molecules.

It happens when hydrogen is bonded to highly electronegative

atoms like oxygen or nitrogen.

By: Dr Luqman
Example:

Water (H₂O): In water, the hydrogen atoms of one water molecule

are attracted to the oxygen atom of another water molecule,
forming hydrogen bonds.
 Hybridization Concept

Hybridization refers to the concept of atomic orbitals mixing to form

new, hybrid orbitals that are better suited for bonding. This concept
helps explain the shapes, bond angles, and reactivity of molecules.
There are several types of hybridization based on the number of
atomic orbitals involved:
By: Dr Luqman
1. Sp Hybridization:

Occurs when one s orbital and one p orbital combine, forming two
sp hybrid orbitals.

The two sp orbitals are oriented in a straight line, 180° apart.

This is common in molecules with a triple bond (e.g., acetylene,

C₂H₂).

Example: CO2 shows Sp Hybridization in picture below:

 This diagram explains the sp hybridization of carbon in CO₂ (carbon dioxide).

1. Structure of CO₂:

CO₂ has a linear geometry with a bond angle of 180°.

Carbon forms two double bonds with two oxygen atoms.

By: Dr Luqman
2. Hybridization of Carbon:

The central carbon atom in CO₂ is sp hybridized:

One S orbital and one P orbital from carbon combine to form two sp hybrid orbitals.

These sp orbitals are oriented linearly, 180° apart, and each forms a sigma (σ) bond with
the oxygen atoms.

The remaining two orbitals in carbon remain unhybridized.

3. π Bonds in CO₂:

Each unhybridized orbital from carbon overlaps with an unhybridized orbital from oxygen
to form two π bonds (one with each oxygen atom).

4. Hybridization of Oxygen:

Each oxygen atom is sp² hybridized:

Three sp² orbitals form, two of which hold lone pairs, and the third forms a σ bond with
carbon.

The unhybridized orbital on oxygen forms the π bond with carbon.

5. Result:

Carbon forms two σ bonds (using sp orbitals) and two π bonds (using unhybridized
orbitals).

The molecule has a linear shape due to sp hybridization.

This diagram shows that Oxygen is Sp2 hybridized & Carbon is sp
hybridized. So we will say this is Sp Hybridization.
 SP2 Hybridization:

Introduction: Mixing of 1 S orbital and 2 P orbitals to form 3 sp²

hybrid orbitals, leaving 1 unhybridized orbital.

Geometry: Trigonal planar, bond angle 120°.

Example:

Ethene (C₂H₄):

Each carbon forms 3 σ bonds (2 with H, 1 with C) using sp² orbitals.

Unhybridized orbitals overlap to form a π bond (double bond).

By: Dr Luqman
 STEPS IN SP2 HYBRIDIZATION:

1. Promotion of Electrons.

An electron from the lower-energy 2s orbital is promoted to an empty or partially

filled 2p orbital to allow for more bonding. For example:

Carbon has an electronic configuration: 1s² 2s² 2p².

After electron is promoted, resulting in: 1s² 2s¹ 2p³.

2. Mixing of orbitals

One 2s orbital and two 2p orbitals mix to form three new, equivalent sp² hybrid orbitals.

The third 2p orbital remains unhybridized.

 3. Formation of Hybrid Orbitals

The three sp² hybrid orbitals are:

Equivalent in energy and shape.

Oriented in a trigonal planar arrangement at 120° to minimize electron repulsion.

The unhybridized 2p orbital lies perpendicular to the plane of the sp² orbitals.

4. Overlap of Orbitals for Bonding

The sp² hybrid orbitals overlap with orbitals of other atoms to form sigma (σ) bonds.

The unhybridized 2p orbital forms a pi (π) bond by sideways overlap with another unhybridized p orbital on
a neighboring atom.

Example: Ethene (C₂H₄)

Each carbon atom undergoes sp² hybridization.

The sp² orbitals form σ bonds with:

Two hydrogen atoms.

The other carbon atom.

The unhybridized p orbitals from each carbon atom overlap to form the π bond, resulting in a double bond
between the carbons.

Visualization

3 sp² orbitals → Planar triangular arrangement.

1 unhybridized p orbital → Perpendicular to the plane.

 SP3 HYBRIDIZATION:

Introduction: Mixing of 1 S orbital and 3 P orbitals to form 4 sp³

hybrid orbitals of equal energy.

Geometry: Tetrahedral, bond angle 109.5°.

Example: By: Dr Luqman

Methane (CH₄):

In methane Carbon forms 4 σ bonds with hydrogen using sp³ orbitals.

Tetrahedral shape ensures bond angles of 109.5°.

C
 Steps in sp³ Hybridization:

1. Ground State Electronic Configuration:

Only two unpaired electrons are available in 2px & 2py for bonding in this state, which
is insufficient for forming four bonds.

2. Promotion of Electron:

One electron from the 2S orbital is promoted to 2Pz. So the empty orbital is filled now.

New configuration: .

Now, there are four unpaired electrons, allowing carbon to form four bonds.

3. Hybridization:

The 2S orbital and all three 2P orbitals (i.e. 2Px, 2Py, 2Pz ) combine to form four sp³
hybrid orbitals.

Each sp³ orbital has 25% S-character and 75% P character.

These orbitals are identical in shape and energy and are arranged in a tetrahedral
geometry.
 4. Bond Formation:

Each sp³ hybrid orbital overlaps with an orbital of another atom to form a sigma
(σ) bond.

Example in methane (CH₄):

Each sp³ orbital of carbon overlaps with the orbital of a hydrogen atom to form
four equivalent σ bonds.

The result is a tetrahedral molecule with bond angles of 109.5°.

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 Conjugation in Organic Chemistry

Conjugation means the overlap of p-orbitals in a molecule,

allowing for the delocalization of π-electrons across adjacent
atoms in a same molecule. This delocalization provides stability
to the molecule and often gives it unique chemical and physical
properties, such as color and reactivity. Delocalization means
jumping of electrons from one site to another site in a molecule.

By: Dr Luqman

Conditions for Conjugation

1. Alternating Single and Double Bonds: Conjugation occurs

when a molecule has alternating single and double bonds in a
chain or ring (e.g., in benzene or butadiene).

Pi Electrons

2. p-Orbital Overlap: Conjugation requires that the participating

atoms have unhybridized p-orbitals. This enables the electrons
to delocalize.

3. Planarity: The involved atoms must be in the same plane to

maximize p-orbital overlap.
 By: Dr Luqman

How Conjugation Works

Conjugation involves the delocalization of π-electrons

across the system of connected p-orbitals. Instead of
being localized in one specific bond, these electrons are
shared across the conjugated system. This leads to the
formation of molecular orbitals that extend over multiple
atoms, lowering the overall energy of the system.
 Example of Conjugation: 1,3-Butadiene

1,3-Butadiene is a classic example of a conjugated system. Its

structure is as follows:

CH2=CH-CH=CH2

Double Bonds: The molecule has alternating single and double

bonds.

p-Orbitals: The two double bonds contain π-electrons in

overlapping p-orbitals.

Delocalization: The π-electrons can delocalize across all four

carbon atoms due to the continuous overlap of p-orbitals.

By: Dr Luqman

Resonance Structures of 1,3-Butadiene

The delocalization of electrons in 1,3-butadiene can be

depicted through resonance structures:

1. Structure 1: CH2=CH-CH=CH2

2. Structure 2: CH2⁻-CH=CH⁺-CH2

These resonance forms illustrate the electron delocalization,

which increases the stability of the molecule.
 Example 2: Benzene Conjugation

By: Dr Luqman

Benzene (C₆H₆)

Structure:
Benzene consists of six carbon atoms in a ring with alternating single and double bonds:

Conjugation:

Each carbon atom in benzene has a p-orbital. These p-orbitals overlap to form a continuous ring of
delocalized π-electrons above and below the plane of the ring.

The π-electrons are spread evenly across all six carbon atoms, making benzene highly stable.

Effect:

This delocalization leads to resonance and gives benzene its characteristic stability and
aromaticity.
 Resonance in Organic Chemistry

Resonance is a concept used to describe the delocalization of electrons in

molecules that cannot be represented by a single Lewis structure.
Instead, multiple resonance structures are drawn, which are different
valid Lewis structures for the same molecule. The actual structure of the
molecule is a resonance hybrid, which is a weighted average of all
resonance structures.

Characteristics of Resonance:

1. Electron Delocalization: Resonance occurs when electrons, especially

π-electrons or lone pairs, are shared between two or more adjacent
atoms, leading to delocalization.

2. Multiple Valid Lewis Structures: Resonance structures are alternative

ways to represent the same molecule, differing only in the positions of π-
electrons or lone pairs.

3. Resonance Hybrid: The actual molecule does not switch between

resonance structures. Instead, it exists as a resonance hybrid that
combines features of all the structures, often with lower energy and
greater stability.

4. Planarity: Resonance typically occurs in planar molecules where p-

orbitals can overlap effectively.

5. Equal Connectivity: All resonance structures must have the same

arrangement of atoms (only the electron distribution differs).
 Rules for Writing Resonance Structures

1. Same Number of Electrons: All resonance structures must have the same total
number of electrons.

2. Position of Atoms Remains Fixed: Only the electrons move; atoms do not
change their positions.

3. Valid Lewis Structures: Each resonance structure must obey the rules of
valency and the octet rule, where applicable.

By: Dr Luqman

4. Major vs. Minor Contributors:

The most stable resonance structure (with minimal formal charges, full octets,
and negative charges on electronegative atoms) contributes more to the
resonance hybrid.

Less stable structures contribute less but still influence the molecule's
properties.

How Resonance Works

Electrons in π-bonds or lone pairs move between adjacent atoms, creating

partial bonds and charges. The delocalized electrons reduce electron repulsion
and increase stability. Resonance is particularly common in conjugated systems,
where alternating single and double bonds allow for delocalization.
 Examples of Resonance

1. Benzene (C₆H₆)

Resonance Structures: Benzene has two equivalent resonance structures

where the positions of the double bonds alternate.

O O
/ \ / \
| | -> | |
\ / \ /

O O

Resonance Hybrid: The actual structure is a hybrid where all six C–C bonds
are equal in length (intermediate between single and double bonds).

Effect: Resonance gives benzene its exceptional stability (aromaticity) and

unique chemical properties.

By: Dr Luqman

2. Carbonate Ion (CO₃²⁻)

Structure: The carbonate ion has three resonance structures:

Resonance Hybrid: The actual structure has all three C–O bonds with equal
bond lengths, and the negative charge is evenly distributed across the three
oxygen atoms.

Effect: Resonance increases the stability of the carbonate ion.

 Importance of Resonance

1. Stability: Resonance stabilizes molecules by delocalizing electrons,

lowering the overall energy.

2. Reactivity: Delocalized electrons influence the reactivity of molecules in

reactions, such as electrophilic aromatic substitution in benzene.

3. Acidity and Basicity: Resonance can affect the strength of acids and
bases. For example, the carboxylate ion (RCOO⁻) is stabilized by resonance,
making carboxylic acids stronger acids.
By: Dr Luqman

4. Spectroscopy: Resonance affects molecular properties such as UV-Vis

absorption and NMR chemical shifts, which are used to analyze molecules.

Limitations of Resonance

Resonance is a theoretical concept, and individual resonance structures do

not physically exist.

Drawing resonance structures may not fully represent the true electronic
distribution, as it is based on approximations.
 Hyperconjugation:

Hyperconjugation is a stabilizing interaction that occurs when

electrons in a sigma (σ) bond, typically C–H or C–C, interact with an
adjacent empty or partially filled p-orbital, π-orbital, or antibonding
orbital. This interaction results in the delocalization of electrons,
enhancing the stability of the molecule.

Key Features of Hyperconjugation

1. Delocalization of Electrons: Unlike resonance, which involves π-

electrons or lone pairs, hyperconjugation involves σ-electrons.

2. Adjacent Bonds: The effect occurs when a σ-bond is adjacent to:

A carbocation (empty p-orbital),

A double bond (π-system), By: Dr Luqman

A radical (partially filled p-orbital).

3. Bonding Interaction: The σ-electrons partially overlap with the

empty or partially filled orbital, distributing the electron density and
increasing stability.

4. No Lone Pairs Required: This distinguishes hyperconjugation from

resonance.
 Types of Hyperconjugation

1. Sigma-π Hyperconjugation: Delocalization between a σ-bond and an

adjacent π-system.

2. Sigma-p Hyperconjugation: Delocalization between a σ-bond and an

adjacent empty or partially filled p-orbital (e.g., carbocations or radicals).

Mechanism of Hyperconjugation

In hyperconjugation, the electrons in a σ-bond interact with an adjacent

orbital. For example:

In carbocations, the empty p-orbital of the positively charged carbon overlaps

with the σ-electrons of the adjacent C–H bonds. This spreads the positive
charge across multiple atoms, reducing the energy of the system.

In alkenes, the σ-electrons of a C–H bond interact with the π-system,

enhancing stability by spreading out electron density.

By: Dr Luqman

Hyperconjugation does not occur in CarboAnions!

Example 1: Sigma - P orbital Hyperconjugation in ethyl carbocation

One Carbon which has + charge because its P orbital is empty

OR CH3 - CH2+

By: Dr Luqman

We can also write above structure as:

Ethyl Carbocation
In Carbocation (C+) there are 3 bonds of carbon atom but If one hydrogen donates it's
electrons to Carbocation empty P orbital then + charge will be disappear because
carbon bonds will be again formed as 4 bonds

By: Dr Luqman

Any hydrogen can be released by donating it's electrons to Carbocation to stabilize it!
 S2

S1

S3

So Total 3 No bond Resonance structure (S1 - S3) can be formed due to

hyperconjugation in ethyl Carbocation.
it is called no bond Resonance because the bond of any one hydrogen is
break to give electrons to Carbocation (C+) to complete it's 4 Bonds and
stabilized Carbocation by removing+ charge on it.

Total No of No Bond Resonance Structure: 3

Total Alpha Carbons = 1

Total Alpha Hydrogens = 3

 To Find the alpha carbon and alpha hydrogens in an ethyl carbocation
(CH₃-CH₂⁺), follow these steps:

1. Identify the positively charged carbon (carbocation):

In CH₃-CH₂⁺, the second carbon (C2) is the carbocation (positively

charged).

By: Dr Luqman

2. Alpha carbon:

The alpha carbon is any carbon atom directly attached to the

carbocation.

In this case, the carbon in CH3 is the alpha carbon because it is directly
bonded to the carbocation (C2).

3. Alpha hydrogens:

Alpha hydrogens are the hydrogens attached to the alpha carbon.

The CH₃ group (C1) has three hydrogens directly attached to it. These are
the alpha hydrogens.

Carbocation

3- Alpha Hydrogen

Alpha Carbon
3 ALPHA HYDROGEN
 2. Sigma - Pi Hyperconjugation:

1. The molecule has a double bond (CH₂=CH-) and a C–H bond next to it.

2. The electrons in the C–H bond (sigma bond) can shift and interact with the
π-electrons of the double bond.

3. This causes the double bond to move to the next carbon pair, and the
hydrogen becomes slightly detached, creating a partial positive charge (H⁺) on
the first carbon.

4. The shifting of electrons stabilizes the molecule by spreading the charge

across the atoms.

This is called hyperconjugation because the sigma bond interacts with the pi
system to share electron density and increase stability.
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 AROMATICITY (ORGANIC CHEMISTRY)

The special stability of certain cyclic molecules due to the way their
electrons are shared. These molecules, called aromatic compounds,
have a unique structure where electrons in double bonds (π-
electrons) are spread out over the entire ring, making the molecule
more stable than expected.

By: Dr Luqman

Requirements for Aromaticity:

1. Cyclic Structure: The molecule must form a ring.

2. Planarity: The atoms in the ring must lie in the same plane.

3. Conjugation: The π-electrons must be delocalized, meaning they

are spread over several atoms.

4. Hückel's Rule: The number of π-electrons must be 4n+2, where n is

any whole number (0, 1, 2, 3, etc.)

Example:

Benzene (C₆H₆) is the classic aromatic compound with 6 π-electrons

because in case of benzene n=1 so huckle formula: 4(1)+2=6.
 Non-Aromatic Compounds

These are molecules that do not meet the criteria for aromaticity. This could be because:

1. Not cyclic: The molecule does not form a closed ring.

2. Not planar: The atoms are not arranged in a flat plane, so π-electrons can't overlap
effectively.

3. No conjugation: The molecule doesn't have alternating single and double bonds or a
delocalized system of π-electrons.

By: Dr Luqman

Example:

Cyclohexane (C₆H₁₂): A six-membered ring with only single bonds between the carbon
atoms, so there is no delocalized π-electron system.

Anti-Aromatic Compounds

These are molecules that meet the criteria for being aromatic, meaning they are:

1. Cyclic: The molecule forms a ring.

2. Planar: The atoms are arranged in a flat plane.

3. Conjugated: The molecule has alternating single and double bonds, or a system that
allows for delocalization of π-electrons.

But still they're not aromatic because they have wrong number of Pi-Electrons (4n). They
do not follow huckle formula & causing instability.

Example:

Cyclobutadiene (C₄H₄): A four-membered ring with alternating single and double bonds
and 4 π-electrons. It is unstable and highly reactive due to its anti-aromatic nature.
 To find "n" using Hückel's rule, follow these simple steps:

1. Count the π-electrons:

Each double bond has 2 π-electrons.

Count all π-electrons from double bonds or lone pairs that are part of the
conjugated system.

2. Use Hückel's formula:

4n+2 = no of Pi Electrons. By: Dr Luqman

3. Solve for n:

Rearrange the above formula:

n = no of Pi Electrons - 2
4

Example: Benzene (C₆H₆)

1. Count the π-electrons:

Benzene has 6 π-electrons (3 double bonds, 2 electrons on double bond).

2. Apply the formula:

n = 6 pi electrons - 2
4

So: n = 4/4 = 1 Answer .

It means for benzene, n = 1.

If the number of π-electrons doesn’t fit in 4n+2 then , the compound is not aromatic.
 INDUCTIVE EFFECT:

The inductive effect is a way that atoms or groups in a molecule can pull or
push electrons through sigma bonds either away or towards the Molecule.
OR the shifting of electron from less electronegative to more electronegative
atom is called inductive effect.

Following is the Explaination: By: Dr Luqman

1. Electronegativity:

Atoms that are more electronegative (like oxygen or chlorine) attract

electrons towards themselves. This creates a partial negative charge where
they are, and a partial positive charge on the other end of the molecule.

2. Electron-donating vs. electron-withdrawing:

Electron-donating groups (like alkyl groups: -CH₃, -C₂H₅) push electrons

towards the rest of the molecule.

Electron-withdrawing groups (like -NO₂, -Cl) pull electrons away from the
molecule.

3. Effect on reactivity:

When a molecule has groups that withdraw electrons, it becomes more likely
to attract things that have electrons (like nucleophiles).

When a molecule has groups that donate electrons, it becomes more likely to
attract things that are electron-deficient (like electrophiles).
 In HF (Hydrogen Fluoride), fluorine exhibits a -I (negative inductive)
effect. Due to its high electronegativity, fluorine withdraws electron
density from hydrogen, making the H atom more positive and the F
atom more negative. This contributes to the polarity and acidity of HF.

So: Fluorine = Negative Inductive Effect

Hydrogen = Positive Inductive Effect

By: Dr Luqman
 Factors Affecting Inductive Effect:

1. Distance:

As the distance from the electron-withdrawing group increases, the

inductive effect decreases.

Example: C–C–C–C–Cl → The inductive effect is strongest at C1 and

decreases for C2, C3, and C4.

By: Dr Luqman

2. Degree of Carbon:

Tertiary carbons experience a stronger inductive effect than secondary

or primary carbons. Carbon attached to 2C is called secondary carbon
& carbon attached to 3C is called tertiary carbon.

Inductive effect order: Tertiary > Secondary > Primary.

 3. Electronegativity of Substituent:

Higher electronegativity of the substituent increases the

inductive effect (e.g., –F > –Cl > –Br > –I).
Fluorine is more electronegative than chlorine.

4. Number of Substituents:

Multiple electron-withdrawing groups increase the inductive

effect.

By: Dr Luqman

5. Type of Substituent:

Electron-withdrawing groups (e.g., –NO₂, –CN) show a stronger

negative inductive effect, whereas electron-donating groups
(e.g., –CH₃, –OCH₃) may exhibit a positive inductive effect.

6. No. Of carbon:

More number of carbon increases the inductive Effect.

 Example 1: Electron-Withdrawing Group (-NO₂)

Consider the molecule nitrobenzene (C₆H₅NO₂).

The nitro group (-NO₂) is an electron-withdrawing group. It pulls

electron density away from the benzene ring through the sigma
bonds.

As a result, the ring becomes electron-deficient, making it more

likely to undergo electrophilic reactions (because electrophiles
are attracted to areas with low electron density).

By: Dr Luqman

Example 2: Electron-Donating Group (-CH₃)

Now, consider methylbenzene (C₆H₅CH₃), also known as toluene.

The methyl group (-CH₃) is an electron-donating group. It pushes

electron density toward the benzene ring.

This makes the ring more electron-rich and more reactive in

electrophilic substitution reactions, as it attracts electrophiles.
A list of electron-donating and electron-withdrawing groups:

Electron-Donating Groups (EDGs):

1. Alkyl groups (-CH₃, -C₂H₅, etc.)

2. -OH (Hydroxyl group)

3. -OCH₃ (Methoxy group)

4. -NH₂ (Amino group)

5. -NH₃⁺ (Ammonium group)

By: Dr Luqman
6. -R (General alkyl or aryl groups)

7. -C₆H₅ (Phenyl group, sometimes)

Electron-Withdrawing Groups (EWGs):

1. -NO₂ (Nitro group)

2. -CN (Cyano group)

3. -COOH (Carboxyl group)

4. -CHO (Aldehyde group)

5. -COR (Acyl group)

6. -COOR (Ester group)

7. -SO₃H (Sulfonic acid group)

8. -CF₃ (Trifluoromethyl group)

9. -Cl, -Br, -I (Halogens)

10. -N₃ (Azide group)

 ELECTROMERIC EFFECT :

Instantaneous Dipole means there will be a (+) charge

on carbon and a (-) charge on adjacent carbon.

By: Dr Luqman
 Symmetrical Examples:

1. Alkene (CH₂=CH₂) reacting with H⁺

Electrons from the π-bond shift to one carbon, forming a

carbocation (+) and a carbanion (−).

By: Dr Luqman

2. Alkyne (CH≡CH) reacting with H⁺

π-electrons shift, generating a positively charged carbon (+)

and negatively charged carbon (−).
 Unsymmetrical Examples:

1. Carbonyl group (C=O) reacting with H⁺:

Electrons from the π-bond shift towards oxygen because O is more

electronegative and attracts electrons towards itself, creating a
positive carbon and a negative oxygen.

2. Nitrile (C≡N) reacting with H⁺:

π-electrons shift towards nitrogen because nitrogen is more

electronegative, forming a positively charged carbon (+) and a
negatively charged nitrogen (−).

By: Dr Luqman

Key Points:

Symmetrical shifts occur in alkenes and alkynes.

Unsymmetrical shifts occur in polarized bonds like C=O or C≡N.

 3. When CH₃–CH=CH₂ (propene) interacts with H⁺

The π-electrons from the double bond shift towards one of

the carbons, creating a carbocation at the most stable
position.

In this case, the positive charge forms on the middle carbon

(CH) due to hyperconjugation and inductive effects from
the CH₃ group.

This leads to the structure:

CH₃–C⁺–CH₃ (a secondary carbocation).

By: Dr Luqman
 By: Dr Luqman

Example: In a carbonyl group

Example: In a carbonyl group (C=O), (C=O), when CN⁻ attacks, the π-
when H⁺ attacks, the π-electrons electrons shift towards oxygen to
shift towards the oxygen atom. stabilize the negative charge.
Result: Carbon becomes positively Result: Carbon becomes
charged (C⁺), and oxygen becomes negatively charged (C⁻), and
negatively charged (O⁻). oxygen becomes negatively
charged (O⁻).
Difference Between Symmetrical and Unsymmetrical Structures in Organic Chemistry:

1. Symmetrical Structures:

Molecules or bonds are identical on both sides of a central atom or axis.

Example: Alkenes like CH₂=CH₂ (ethene) have equal electron distribution.

Reactions often involve homolytic cleavage (equal sharing of electrons).

By: Dr Luqman

2. Unsymmetrical Structures:

Molecules or bonds are not identical on both sides, leading to polarity.

Example: Carbonyl groups like C=O or C≡N have uneven electron distribution.

Reactions often involve heterolytic cleavage (unequal sharing of electrons).

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 STERIC EFFECT (ORGANIC CHEMISTRY)

STERIC EFFECT :
It is the impact of the size and position of atoms or
groups in a molecule on its behavior and reactivity.

By: Dr Luqman

Types of Steric Effects:

1. Steric Hindrance:

The repulsion between two groups present on a carbon atom if

the distance between two is less than Vander Waals radius.

Example: the distance between two Alkyl Groups in CiS-2-BUTENE is

less than Vander Waals radius so these 2 groups will repel each
other which is called Steric hindrance.
Question: Why Cis-2-butene is less stable than trans-2-butene?

Trans-2-butene is more stable than cis-2-butene because the

methyl groups in the trans 2 butene are on opposite sides,
reducing steric repulsion. This results in lower energy and
greater stability compared to the cis 2 butene, where the
methyl groups are closer and experience steric strain.

By: Dr Luqman

ENERRGY
STERIC HINDRANCE
=
STABILITY

Increased Steric hindrance will decrease stability but increase energy.

 By: Dr Luqman

2. Steric Strain:

Atoms forced too close together repel each other, increasing the
molecule’s energy.

Example: Cyclohexane's boat conformation has strain due to

hydrogens being too close.

3. Steric Protection:

Bulky groups shield reactive parts of a molecule, preventing side

reactions.

Example: Large ligands in catalysts can protect them from

deactivation.
 By: Dr Luqman
1. Methyl Carbon:

Reaction: Fast SN2 reaction.

Explanation: Methyl carbon has no attached alkyl groups (just

three hydrogens). This absence of steric hindrance allows the
nucleophile to easily attack the electrophilic carbon from the
backside, leading to a smooth displacement of the leaving group.

2. Primary Carbon:

Reaction: Slow SN2 reaction.

Explanation: A primary carbon has one alkyl group attached. This

introduces slight steric hindrance but still allows the nucleophile
to perform a backside attack. The reaction is slower compared to
methyl carbon due to this small steric effect.
 3. Secondary Carbon:

Reaction: Very slow SN2 reaction.

Explanation: Secondary carbons have two alkyl groups attached,

causing significant steric hindrance around the electrophilic
carbon. The nucleophile finds it difficult to approach and attack,
making the reaction very slow.

By: Dr Luqman
4. Tertiary Carbon:

Reaction: SN2 does not occur; SN1 is favored.

Explanation: Tertiary carbons have three bulky alkyl groups

attached, creating extreme steric hindrance. The nucleophile
cannot access the backside of the electrophilic carbon, making
SN2 impossible. However, tertiary carbons are prone to
undergoing SN1 reactions because the bulky groups stabilize the
carbocation intermediate formed during the reaction.
 TAUTOMERISM:

When a single compound exists in two or more readily interconvertible

structures (called tautomers) that differ in the position of a Hydrogen
(protons) and, consequently, the placement of a double bond. These
tautomers exist in dynamic equilibrium and can interconvert through
a chemical process, often catalyzed by acids or bases.

By: Dr Luqman

Key Features of Tautomerism:

1. Structural Difference: Tautomers differ in the position of:

A hydrogen atom (proton).

A double bond.

2. Dynamic Equilibrium: Tautomers exist in equilibrium, but the ratio

of one form to another depends on factors like solvent, temperature,
and pH.

3. No Change in Molecular Formula: The molecular formula of the

tautomers remains the same; only the connectivity of atoms changes.
 Step 1: Protonation of the Carbonyl Group

The carbonyl oxygen (C=O) attracts a proton (H⁺) from the acid (H₃O⁺).

This creates an oxonium ion (a positively charged oxygen atom) which makes the carbonyl
carbon more reactive.

Step 2: Deprotonation of the α-Hydrogen

A water molecule (H₂O) removes the hydrogen atom (H) from the α-carbon (the carbon
next to the C=O).

When this happens, the electrons from the broken C-H bond form a new double bond
between the α-carbon and the carbonyl carbon.

Simultaneously, the electrons in the C=O bond move to the oxygen, forming the enol form
(C=C-OH).

The catalyst (H₃O⁺) is regenerated, keeping the process ongoing.

 Step 1: Deprotonation of the α-Hydrogen

The base (OH⁻) removes the hydrogen atom from the α-carbon,
creating an intermediate called the enolate ion.

The enolate ion is stabilized by resonance, meaning the negative

charge can shift between the oxygen atom and the α-carbon.

Step 2: Protonation of the Enolate Ion

The enolate ion's negatively charged oxygen atom grabs a hydrogen

atom (H⁺) from water (H₂O).

This results in the formation of the enol form (C=C-OH), while the
base (OH⁻) is regenerated.
 Key Differences Between Acid and Base Mechanisms

Acid-Catalyzed: Starts with protonation (adding H⁺) to the carbonyl

oxygen.

Base-Catalyzed: Starts with deprotonation (removing H⁺) from the

α-carbon.

By: Dr Luqman

Final Notes

The keto form is usually more stable than the enol form, so the
equilibrium lies mostly toward the keto side.

This interconversion is important in reactions like aldol

condensation and is influenced by the environment (acidic or basic).

How to identify Alpha Hydrogen or Alpha Carbon?

It is already discussed in hyperconjugation PDF.

ask admin for that PDF.
 Importance of Keto-Enol Tautomerism

1. Reactivity in Organic Reactions:

The enol form is often more reactive and participates in
reactions like aldol condensation or Claisen condensation.

2. Stability and Equilibrium:

While the keto form is usually more stable, the enol form can
sometimes be stabilized, for example, through hydrogen
bonding or resonance.

3. Biological Systems:
In biology, nucleic acid bases (like adenine and guanine) exist in
tautomeric forms, affecting DNA base pairing

Factors Affecting Tautomerism:

Acid/Base Strength: Strong acids or bases can catalyze the

tautomeric shift.

Solvent: Polar solvents can stabilize the enolate intermediate in

base-catalyzed tautomerism.

Temperature: Higher temperatures may favor the enol form due

to the increased energy, though keto is still usually more stable.
 NOMENCLATURE OF ORGANIC COMPOUNDS
Nomenclature of organic compounds is a system for naming organic
chemical compounds based on their structure. The most widely
accepted naming system is the IUPAC (International Union of Pure and
Applied Chemistry) nomenclature. This system allows for the
systematic and consistent naming of organic compounds.

By: Dr Luqman

Basic Principles of IUPAC Nomenclature

1. Identify the Parent Chain:

The parent chain is the longest continuous chain of carbon atoms in

the molecule. This chain determines the base name of the compound.

The chain must contain the highest-priority functional group, if any.

Number the chain from the end nearest to the highest-priority

functional group or substituent.

2. Naming the Compound:

The name of the compound consists of three parts:

Prefix: Indicates the substituents or functional groups attached to the

parent chain.

Infix: Indicates the presence and position of double or triple bonds (if
applicable).

Suffix: Indicates the type of functional group present (e.g., -ol for
alcohol, -al for aldehyde, -one for ketone).
 Steps in Nomenclature of Organic Compounds

1. Find the Parent Hydrocarbon Chain:

Identify the longest continuous chain of carbon atoms.

Name it based on the number of carbon atoms it contains:

1 carbon: Meth-

2 carbons: Eth-
By: Dr Luqman
3 carbons: Prop-

4 carbons: But-

5 carbons: Pent-

6 carbons: Hex-

7 carbons: Hept-

8 carbons: Oct-

9 carbons: Non-

10 carbons: Dec-

2. Number the Chain:

Number the carbon atoms in the parent chain, starting from the end
nearest to any substituents or functional groups. This ensures the
lowest possible numbers for the substituents.
 3. Name the Substituents:

Substituents are groups attached to the parent chain.

Common substituents include alkyl groups (e.g., methyl, ethyl),

halogens (e.g., chloro, bromo), and functional groups (e.g.,
hydroxyl -OH, amino -NH₂).

Name the substituents and indicate their position by the

number assigned to the carbon in the parent chain.

By: Dr Luqman

4. Assign the Suffix for Functional Groups:

The functional group has their own suffix listed below in red
color:

For example:

Alcohol: -ol (e.g., ethanol, CH₃CH₂OH)

Aldehyde: -al (e.g., formaldehyde, CH₂O)

Ketone: -one (e.g., acetone, CH₃COCH₃)

Carboxylic Acid: -oic acid (e.g., acetic acid, CH₃COOH)

Amines: -amine (e.g., aniline, C₆H₅NH₂)

 Examples of Organic Compound Nomenclature
1. Methane (CH₄):

Simple hydrocarbon with 1 carbon atom (meth-) and no functional group.

2. Ethene (C₂H₄):

Two carbon atoms (eth-) with a double bond (ene).

By: Dr Luqman
3. 2-Methylpropane (C₄H₁₀):

Parent chain: propane (C₃ chain).

Methyl group (-CH₃) attached to the second carbon.

4. Butan-2-ol (C₄H₁₀O):

Parent chain: butane (C₄ chain) with an alcohol group (-OH) on the second carbon.

5. 3-Bromo-2-chloropropane (C₃H₆ClBr):

Parent chain: propane (C₃ chain).

Chlorine (Cl) attached to carbon 2 and bromine (Br) attached to carbon 3.

6. Pentanoic Acid (C₅H₁₀O₂):

Parent chain: pentane (C₅ chain) with a carboxylic acid group (-COOH) on the first
carbon.
 How To Name a complex organic compound:
1. Identify the Parent Chain:

Find the longest carbon chain. The base name depends on the number of
carbon atoms (e.g., pentane for a 5-carbon chain).

By: Dr Luqman
2. Identify the Functional Group:

Identify the highest-priority functional group (e.g., -COOH for carboxylic

acids). The suffix will reflect this (e.g., -oic acid).

3. Number the Chain:

Number the chain starting from the functional group to give it the lowest
possible number.

4. Name and Number Substituents:

Identify substituents (e.g., methyl (CH₃)) and their positions. Add these as
prefixes with numbers (e.g., 3-methyl).

5. Combine the Information:

Combine the parent chain name, substituent prefixes, and functional group
suffix (e.g., 3-methylpentanoic acid).
 Example:

CH₃-CH₂-CH₂-CH(C₆H₅)-COOH

Parent chain: pentanoic acid

Substituent: phenyl (C₆H₅) on carbon 4.

Final name: 4-Phenylpentanoic acid.

By: Dr Luqman
EFFECT OF STRUCTURE ON REACTIVITY OF COMPOUNDS:

1. Functional Groups: Dictate the types of reactions a compound can undergo. For
example, carboxylic acids react with bases, and alkenes undergo addition
reactions.

2. Bond Strength and Length: Weaker bonds (like C=C in alkenes) are more reactive.
Shorter bonds are harder to break.

3. Inductive Effects: Electron-Withdrawing Groups (EWGs) make compounds more

electrophilic, increasing reactivity toward nucleophiles. Electron-Donating Groups
(EDGs) make compounds more nucleophilic.

4. Resonance Effects: Delocalization of electrons stabilizes structures, making

them more electrophilic (e.g., carbonyl compounds) and reactive toward
nucleophiles.

5. Steric Effects: Bulkier groups near reactive sites hinder reactions. Smaller, less
hindered compounds are more reactive.

6. Hybridization: Sp hybridized carbons (e.g., alkynes) are more reactive than sp²
(e.g., alkenes) and sp³ carbons (e.g., alkanes) due to greater electron density.

7. Molecular Geometry: Cis-trans isomerism affects reactivity; cis isomers are often
more reactive than trans. Strained rings (e.g., epoxides) are highly reactive due to
angle strain.

Summary:

Reactivity is due to functional groups, bond strength, electronic effects, steric

hindrance, hybridization, and geometry. Strained molecules and specific electron
effects (donating or withdrawing) enhance reactivity, while steric hindrance or
resonance can stabilize or reduce it.
This PDF IS MADE BY: Dr.Muhammad Luqman!

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