Unit X: Haloalkanes and Haloarenes

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 Organic Chemistry
 What Is Organic Chemistry ?
The main components of organic chemistry as a discipline are:
 Structure determination—how to find out the structures of new compounds
even if they are available only in invisibly small amounts
 Theoretical organic chemistry—how to understand these structures in terms
of atoms and the electrons that bind them together
 Reaction mechanisms—how to find out how these molecules react with each
other and how to predict their reactions
 Synthesis—how to design new molecules, and then make them
 Biological chemistry—how to find out what Nature does and how the
structures of biologically active molecules are related to what they do.

 The world of perfumery

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The Organic Chemist’s Periodic Table

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 Haloalkanes and Haloarenes

 what is Haloalkanes/haloarenes ?

 The replacement of hydrogen atom(s) in an aliphatic or

aromatic hydrocarbon by halogen atom(s) results in the
formation of alkyl halide (haloalkane) and aryl halide
(haloarene), respectively.

 Examples:
 Methyl chloride, Ethyl bromide Iodoethane
 Chlorobenzene, Bromobenzene ,Iodobenzene

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 Haloalkanes and Haloarenes in Daily Life
 Haloalkanes and haloarenes play significant roles in daily life, often in ways we might not immediately
recognize. Here’s how they impact various aspects of everyday living:
Haloalkanes
 Household Products:
1. Solvents: Many household cleaning products and solvents contain haloalkanes. For example, chlorinated
solvents like trichloroethylene are used in degreasing agents.
2. Pesticides: Certain insecticides and herbicides, which are often haloalkanes, help in pest control.
 Pharmaceuticals:
1. Medicines: Various medications are derived from haloalkanes. For instance, some antibiotics and anti-
inflammatory drugs contain haloalkane structures.
 Refrigerants:
1. Cooling Systems: Haloalkanes, specifically chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons
(HCFCs), have been used as refrigerants in air conditioners and refrigerators. However, due to
environmental concerns, many of these have been phased out in favor of more eco-friendly alternatives.
 Chemical Synthesis:
1. Industrial Processes: Haloalkanes are crucial intermediates in the chemical industry for synthesizing other
compounds, including plastics and synthetic fibers.

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 Haloalkanes and Haloarenes in Daily Life

Haloarenes
1.Dyes and Pigments:
1. Colorants: Many dyes and pigments used in clothing, paints, and cosmetics contain haloarene structures.
They contribute to the vivid colors seen in these products.
2.Pharmaceuticals:
1. Medicines: Similar to haloalkanes, haloarenes are involved in the synthesis of various pharmaceuticals.
They are often used as intermediates in drug synthesis.
3.Flavors and Fragrances:
1. Aromatic Compounds: Some flavoring agents and fragrances are derived from haloarenes, which help
provide distinctive smells and tastes.
4.Electronics:
1. Materials: Haloarenes are used in the production of certain electronic components and materials,
contributing to the functionality of various electronic devices

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 Medicinal Uses of Haloalkanes and Haloarenes
 Medicinal Uses of Haloalkanes

 Antibiotics and Antimicrobials

 Chloroform: Historically used as an anesthetic, it has also been used as an antimicrobial agent. However, its use
has decreased due to safety concerns.
 Iodoform: Known for its antiseptic properties, iodoform is used in wound care and disinfectants.

 Anesthetics
 Halothane: A volatile anesthetic used in general anesthesia. It is known for its ability to provide rapid induction and
recovery.

 Anti-Inflammatory and Analgesic Agents

 Chlorpromazine: A haloalkane derivative used as an antipsychotic and for its sedative properties. It is also used to
treat nausea and vomiting.

 Anticancer Agents
 Bendamustine: An alkylating agent used in chemotherapy, particularly for treating certain types of lymphoma and
leukemia.

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 Medicinal Uses of Haloalkanes and Haloarenes
 Medicinal Uses of Haloarenes

 Antibiotics
 Chloramphenicol: An antibiotic that was one of the first broad-spectrum antibiotics. It is used to treat a variety of
bacterial infections, including typhoid fever and some forms of pneumonia.

 Anticancer Agents
 Vincristine and Vinblastine: These are alkaloids derived from the periwinkle plant (Vinca). They contain halogen
atoms and are used in chemotherapy to treat various cancers, including leukemia and lymphoma.

 Antimicrobial Agents
 Dichlorophen: An antimicrobial compound used in various disinfectants and antiseptics.

 Thyroid Treatments
 Iodine-131: A radioactive isotope used in the treatment of hyperthyroidism and thyroid cancer. It works by
targeting and destroying overactive thyroid cells.
 Antihypertensive Agents
 Hydrochlorothiazide: A thiazide diuretic used to treat hypertension and edema. It is a haloarene derivative that
helps to lower blood pressure and reduce fluid retention

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Classification of Haloalkanes and Haloarenes

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 Classification of Haloalkanes and Haloarenes
 On the Basis of Number of Halogen Atoms  Compounds Containing sp3 C—X Bond (X= F, Cl, Br, I)

 Compounds Containing sp2 C—X Bond (X= F, Cl, Br, I)

 Benzylic halides  Vinylic and Aryl halides

X
X

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 Classification of Haloalkanes and Haloarenes
 On the Basis of Number of Halogen Atoms

 Compounds Containing sp3 C—X Bond (X= F, Cl, Br, I)

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Classification of Haloalkanes and Haloarenes

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Classification of Haloalkanes and Haloarenes

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Classification of Haloalkanes and Haloarenes

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Nature of C-X Bond

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 Inductive effect
 Inductive effect
 The inductive effect is a fundamental concept in organic chemistry that describes how the electron
density in a molecule can be shifted through sigma bonds (single covalent bonds) due to the
presence of electronegative atoms or groups. This effect influences various properties of molecules,
such as acidity, basicity, and reactivity.

 Concept of Inductive Effect

 The inductive effect involves the transmission of charge through a chain of atoms in a molecule, typically along a chain of
carbon atoms, via sigma bonds. It occurs due to the electronegativity differences between atoms, which lead to a shift in
electron density along the chain.

 Factors Influencing Inductive Effect

 Electronegativity: The strength of the inductive effect is largely dependent on the electronegativity of the atom or group
involved. More electronegative atoms or groups have a stronger electron-withdrawing effect.
 Distance: The inductive effect diminishes with distance. The effect is significant within the first few bonds from the
electronegative atom or group but becomes negligible beyond that.
 Nature of Substituent: The nature and number of substituents can influence the overall inductive effect. Multiple electron-
withdrawing or donating groups can enhance or diminish the effect.

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 Inductive effect
 Types of Inductive Effects :
 Electron-Withdrawing Inductive Effect (–I Effect):
This effect occurs when an atom or group with high electronegativity pulls electron density away from adjacent atoms through
sigma bonds. For example, halogens (F, Cl, Br, I), nitro groups (–NO₂), and cyano groups (–CN) exhibit this effect. It results in a
partial positive charge on the adjacent atoms, which can make them more electrophilic.
 Electron-Donating Inductive Effect (+I Effect):
This effect is observed when an atom or group donates electron density through sigma bonds to adjacent atoms. Alkyl groups
(–CH₃, –C₂H₅) are common examples of groups that exhibit this effect. It results in a partial negative charge on the adjacent
atoms, making them less electrophilic

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 Applications of Inductive effect
Acidity and Basicity

 Acid Strength: The inductive effect helps explain why

certain acids are stronger than others. For example, in
carboxylic acids, electron-withdrawing groups (EWGs) like
–NO₂ or –Cl increase the acid's strength by stabilizing the
negative charge on the carboxylate anion. This
stabilization makes the release of H⁺ ions more favorable.

 Basicity of Amines: Electron-donating groups (EDGs) like

alkyl groups increase the basicity of amines. They donate
electron density to the nitrogen atom, making it more
nucleophilic and better at accepting protons.

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 Applications of Inductive effect
 Reactivity in Nucleophilic and Electrophilic Substitutions

 Nucleophilic Substitution: The inductive effect can affect

the reactivity of substrates in nucleophilic substitution
reactions. Electron-withdrawing groups increase the
electrophilicity of carbon atoms in molecules, making
them more susceptible to attack by nucleophiles

 In haloalkanes, the presence of electron-withdrawing groups like –NO₂ on the ring

increases the reactivity of the haloalkane towards nucleophilic substitution.

 Aniline (C₆H₅NH₂) undergoes electrophilic aromatic substitution more readily than

benzene due to the electron-donating effect of the amino group.

 Electrophilic Aromatic Substitution: Electron-donating groups activate the aromatic

ring towards electrophilic substitution reactions, while electron-withdrawing groups
deactivate it. For instance, a nitro group (-NO₂) is a strong electron-withdrawing
group that deactivates the benzene ring, making it less reactive towards
electrophiles.

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 Applications of Inductive effect
 Design of Pharmaceuticals and Agrochemicals
 Drug Design: The inductive effect is considered when designing pharmaceuticals to ensure desired reactivity, stability,
and interaction with biological targets. For example, the placement of electron-withdrawing or donating groups can fine-
tune the pKa of drugs, affecting their solubility and absorption.
 Agrochemicals: In agrochemical design, the inductive effect helps optimize the activity of herbicides and pesticides.
Modifying functional groups to adjust electron density can improve the interaction with specific biological target

 Understanding Molecular Properties

 Spectroscopy: In spectroscopic studies, the inductive

effect influences the chemical shifts in NMR and the
absorption spectra in UV-Vis spectroscopy. Changes in
electron density due to inductive effects can affect these
spectral properties.
 Polarity and Solubility: The inductive effect impacts the
overall polarity of molecules, which in turn affects their
solubility in various solvents. Electron-withdrawing groups
increase the polarity of a molecule, making it more
soluble in polar solvents.

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 Applications of Inductive effect
 Stability of Intermediates

 Carbocations and Carbanions: The inductive effect can influence the stability of intermediates in reaction mechanisms.
Electron-withdrawing groups stabilize carbocations by dispersing the positive charge through sigma bonds, while electron-
donating groups stabilize carbanions by increasing electron density.

 In summary, the inductive effect is a crucial concept that influences various aspects of molecular behavior and reactivity.
By understanding and applying the inductive effect, chemists can better design reactions, predict outcomes, and tailor
compounds for specific applications in pharmaceuticals, agrochemicals, and beyond.

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 Resonance and the Mesomeric effect
 Resonance Effect:
 The polarity induced in a molecule by the interaction of a lone pair of electrons with a pi (π) bond or the interaction of two
pi (π) bonds in nearby atoms is known as the resonance effect.

 Mesomeric effect:
 The mesomeric effect is the polarity that develops in a molecule as a result of interaction between two bonds or a bond
and a lone pair of electrons. Mesomeric effect occurs when π electrons move away from or towards a substituent group in
a conjugated orbital system. (Whereas the mesomeric effect occurs due to the functional group)

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 Resonance and the Mesomeric effect

Basic Terms Resonance Effect Mesomeric Effect

Meaning It describes the concept of interaction It is a concept that describes

between the lone electron pair and stabilization of a molecule by use of
bond electron pair of a molecule that a functional group
determines the chemical structure
Causative Agent Lone electron pair adjacent to the Presence of a functional group or
double bond conjugated system
Different Type Positive and negative resonance effect Positive and negative mesomeric
effect
Polarity Causes polarity of a molecule Has no effect as far as polarity is
concern

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 Resonance and the Mesomeric effect
 Core Difference between Resonance and Mesomeric Effect

Resonance Effect Mesomeric Effect

Resonance effect is a concept that The mesomeric effect describes the

describes the lone pair electron and bond stabilization of a molecule by use of a
pair electron of a molecule determining functional group.
the chemical structure
Resonance effect is caused by a lone Whereas the mesomeric effect occurs due
electron pair adjacent to double bond. to the functional group.
Resonance effect determine the polarity Has no influence in terms of polarity.
of a molecule unlike the mesomeric effect

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 Resonance and the Mesomeric effect
 Resonance effect :
 Resonance effect is the polarity produced in a molecule due to interaction between a lone pair of electrons and a pi
(π) bond or it is produced due to interaction of two pi (π) bond between two adjacent atoms. - Resonance effect can
be seen in molecules having conjugated double bond or in molecules having at least one lone pair of electrons and one
double bond.

 Condition for Resonance include:

 Every participating atom must be coplanar.

 Every participating atom must have the parallel p-atomic orbital (d-atomic orbital, sometimes).

 Resonance occurs in the following cases:

 A pi (π) bond conjugated with the other pi (π) bond

 A pi (π) bond conjugated with a negative charge.
 A pi (π) bond conjugated with a positive charge.
 A positive charge conjugated with a lone pair or a negative charge.
 A pi (π) bond conjugated with lone pair or free radical.

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 Resonance and the Mesomeric effect
 Resonance effect types :
 Positive Resonance Effect (+R):
 The electrons are transferred away from an atom or substituent group bound to the conjugated system in this process.
For example: -OH, -SH, -OR, -SR.

 Negative Resonance Effect (-R):

 The electrons are transferred towards the atom or substituent group associated with the conjugated system in this effect.
For example: -NO2, C=O, -COOH, -C≡N

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 Resonance and the Mesomeric effect
 State the principles of resonance:

 The rules of least charges: The resonant form with the lowest overall charge is the most significant.
 The octet principle: The resonance forms with a full octet are more significant than those lacking a full outer shell.
Stabilization of positive charges: Forms where positive charges are acting on the least electronegative atom are the
most significant.
 Stabilization of negative charges: Forms where negative charges are acting on the most electronegative atom are
the most significant.
 Covalent bonds: The most significant resonance structure has the most covalent bonds.

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 Resonance and the Mesomeric effect
 Mesomeric effect

 The polarity developed between atoms of a conjugated system by the electron transfer or pi (π) bond electron transfer.
Mesomeric effects is one of the properties of functional groups or substituents within a chemical compound. It is described
as the polarity created in the molecule due to the interaction between 2 pi (π) bonds or pi (π) bonds and lone electron
pairs found on an adjacent atom.
 There are two types of mesomeric effects:

 i) +M effect (Positive mesomeric effect) :

 When the electrons or the pi (π) electrons are transferred from

a particular group towards a conjugate system. o For the +M
effect, the group should have either a lone pair of electrons or
should have a negative charge.
 The +M effect gives negative charge to the conjugate system,
or it can be said that the electron density increases on the
conjugate system due to this. These conjugate systems show
more reactivity towards electrophiles and less reactivity
towards a nucleophile. o Group showing +M effect –NH, –NH2,
–NHR, –NR2, – O, – OH, –OR, – F, – Cl, –O–COR, – NHCOR, –
SH, – SR
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 Resonance and the Mesomeric effect
 ii) -M Effect (Negative mesomeric effect)
 When the pi (π) bond electrons are transferred from the conjugate system to a particular group thus the electron
density of the conjugate system is decreased.
 For –M effect, the group should have either a positive charge or should have a vacant orbital.
 –M effect makes the compound more reactive towards a nucleophile as it decreases the electron density in the
conjugate system.

 The group which shows –M effect:

 Significance of Mesomeric effect

 It describes the distribution of the charge in the compound, helps to decide the point at which electrophiles or
nucleophiles attack.
 Useful in describing physical characteristics such as dipole moment, bond length.

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 Comparison between Inductive effect and Resonance effect
 The inductive effect and resonance effect are both mechanisms by which substituents influence the electronic
distribution within molecules, but they operate through different principles and have distinct impacts.
 Here’s a comparison of the two:

 Mechanism of Action

Basic Terms Inductive Effect Resonance Effect:

Mechanism: The inductive effect operates through the The resonance effect involves the delocalization
transmission of electron density via σ-bonds. It of electrons through π-bonds or lone pairs of
results from the electronegativity of atoms or electrons, which can stabilize or destabilize the
groups attached to a carbon chain, which pulls or molecule by allowing the electron density to
pushes electron density along the chain. spread over a larger area.

Range It decreases rapidly with distance from the It typically affects the electronic distribution
substituent (typically diminishing significantly throughout the entire conjugated system or
within 2-3 bonds from the substituent). between specific atoms involved in the resonance.

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 Comparison between Inductive effect and Resonance effect
 Type of Effects

Basic Terms Inductive Effect Resonance Effect:

Types Positive inductive effect (electron-donating) Positive resonance effect (electron-donating)

and negative inductive effect (electron- and negative resonance effect (electron-
withdrawing). withdrawing).

Example: A fluorine atom has a strong negative The -OH group has a positive resonance effect,
inductive effect, pulling electron density away donating electron density into a conjugated
from the rest of the molecule. An alkyl group system. The -NO₂ group has a negative
has a positive inductive effect, donating resonance effect, withdrawing electron density
electron density through σ-bonds. through resonance.

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 Comparison between Inductive effect and Resonance effect
 Influence on Molecular Properties

Basic Terms Inductive Effect Resonance Effect:

Influence on Affects the acidity and basicity of molecules by Affects acidity and basicity by stabilizing or
Acidity/Basicity: altering the electron density around acidic or destabilizing the charged species through
basic sites. For example, electron-withdrawing delocalization of electron density. For example,
groups increase acidity by stabilizing the resonance stabilization of a negative charge on
negative charge on the conjugate base. a conjugate base enhances acidity.

Influence on Alters the stability of intermediates in reactions. Significantly impacts the stability of molecules
Stability: For instance, the inductive withdrawal of or ions by spreading electron density over
electron density by a substituent can stabilize a multiple atoms, leading to stabilization of
carbocation or destabilize a carbanion. structures with delocalized π-electrons.

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 Comparison between Inductive effect and Resonance effect
 Visualization

Inductive Effect: Resonance Effect:

 Typically shown by arrows indicating electron  Represented by multiple Lewis structures (resonance
withdrawal or donation through σ-bonds. structures) and the resonance hybrid, showing the
delocalization of π-electrons.

 In summary, the inductive effect operates through σ-bond interactions and affects electronic distribution over a limited
range, while the resonance effect involves π-bond interactions and can influence electronic distribution across a larger
part of a molecule or conjugated system. Both effects are crucial in understanding molecular behavior, stability, and
reactivity.

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