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8.9.4 - Substitution Reactions in the Hydrocarbon Part

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Halogenation of Carboxylic Acids

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Teacher
Teacher

Today, we will explore the exciting world of halogenation of carboxylic acids. Specifically, we'll focus on how carboxylic acids with an alpha-hydrogen can react with halogens.

Student 1
Student 1

What exactly happens during this reaction, and why is it important?

Teacher
Teacher

Great question! When we treat a carboxylic acid with chlorine or bromine in the presence of red phosphorus, a halogen substitutes the alpha-hydrogen, forming alpha-halocarboxylic acids. This is called the Hell-Volhard-Zelinsky reaction.

Student 2
Student 2

Why is red phosphorus used specifically?

Teacher
Teacher

Red phosphorus serves as a catalyst that facilitates this reaction by creating a polar environment conducive to halogenation. Remember, this reaction modifies acidity and enhances reactivity.

Student 3
Student 3

Can you summarize the importance of this reaction?

Teacher
Teacher

Certainly! Halogenation modifies the properties of carboxylic acids, making them more versatile in organic synthesis.

Electrophilic Substitution in Aromatic Carboxylic Acids

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Teacher
Teacher

Now, let’s shift gears to electrophilic substitution reactions involving aromatic carboxylic acids. Who can tell me what that entails?

Student 4
Student 4

Is it where an electrophile replaces a hydrogen atom on the aromatic ring?

Teacher
Teacher

Exactly! However, carboxylic acids are unique in that they act as deactivating and meta-directing groups. This means they slow down the reaction rate compared to other substituents.

Student 1
Student 1

Why do they deactivate the ring?

Teacher
Teacher

The carboxyl group has a strong electronegative oxygen that pulls electron density away from the aromatic ring, making it less reactive to incoming electrophiles.

Student 3
Student 3

Does this mean we can’t use Friedel-Crafts reactions with them?

Teacher
Teacher

You’re on the right track! Friedel-Crafts reactions are not suitable for carboxylic acids because the catalyst will bond to the carboxyl group, which hinders the reaction.

Student 2
Student 2

Can you recap the significance of these reactions?

Teacher
Teacher

Sure! Understanding how carboxylic acids undergo electrophilic substitutions helps chemists predict reaction pathways in benzene derivatives and design new synthetic routes.

Introduction & Overview

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Quick Overview

This section focuses on the substitution reactions involving carboxylic acids, detailing halogenation and electrophilic substitution.

Standard

The section provides insight into the substitution reactions of carboxylic acids, detailing processes such as halogenation at the alpha position and electrophilic substitution involving aromatic carboxylic acids, emphasizing the reactivity differences of the functional groups involved.

Detailed

Substitution Reactions in the Hydrocarbon Part

This section emphasizes two significant types of substitution reactions pertaining to carboxylic acids, specifically halogenation and aromatic electrophilic substitution.

1. Halogenation

Carboxylic acids with an alpha-hydrogen can undergo halogenation, where chlorine or bromine reacts in the presence of red phosphorus, leading to the formation of alpha-halocarboxylic acids. This process is formally recognized as the Hell-Volhard-Zelinsky reaction. The significance lies in modifying the acidity and reactivity of the carboxylic acid by adding halogen atoms at critical positions that affect biological and chemical properties.

2. Ring Substitution

Aromatic carboxylic acids are involved in electrophilic substitution reactions, where they act as deactivating and meta-directing groups during the substitution process. Notably, these acids do not participate in Friedel-Crafts reactions due to the nature of the carboxylic group, which renders the aromatic ring less reactive by forming a complex with the catalyst (usually aluminum chloride). This highlights how substituents can significantly influence the reactivity pattern of aromatic compounds.

In conclusion, understanding substitution reactions helps evaluate the chemical behavior of carboxylic acids and their derivatives in synthetic applications and organic reactions.

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Electrophilic Substitution in Aromatic Carboxylic Acids

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Aromatic carboxylic acids undergo electrophilic substitution reactions in which the carboxyl group acts as a deactivating and meta-directing group. They however, do not undergo Friedel-Crafts reaction (because the carboxyl group is deactivating and the catalyst aluminium chloride (Lewis acid) gets bonded to the carboxyl group).

Detailed Explanation

Aromatic carboxylic acids can participate in electrophilic substitution reactions, where an electrophile replaces a hydrogen atom on the benzene ring. However, the carboxyl group (-COOH) is electron-withdrawing, making the ring less reactive towards electrophiles. This property means that when reactions do occur, new substituents will attach in a meta position relative to the carboxyl group. The presence of the carboxyl group also prevents the Friedel-Crafts reactions from occurring, which typically require a reactive aromatic system and a good electrophile.

Examples & Analogies

Imagine a family dinner with a strict parent (the carboxyl group) who sets the rules about who can come to dinner (the electrophiles coming in to substitute on the benzene ring). Because the parent is strict, they only allow certain friends (the substituents) to sit at the table in specific places (meta position). The parent won't let anyone else come in that disrupts the family dynamics (the Friedel-Crafts reaction is stopped because the strict parent won’t allow it).

Definitions & Key Concepts

Learn essential terms and foundational ideas that form the basis of the topic.

Key Concepts

  • Halogenation modifies the acidity and reactivity of carboxylic acids.

  • The Hell-Volhard-Zelinsky reaction enables the introduction of halogens at the alpha position.

  • Electrophilic substitution reactions reveal how substituents like carboxylic acids influence aromatic compound behavior.

Examples & Real-Life Applications

See how the concepts apply in real-world scenarios to understand their practical implications.

Examples

  • When chloroacetic acid is formed via halogenation of acetic acid, it exhibits increased acidity compared to acetic acid.

  • In the example of benzoic acid undergoing nitration, the reaction favors the meta position due to the presence of the carboxyl group.

Memory Aids

Use mnemonics, acronyms, or visual cues to help remember key information more easily.

🎵 Rhymes Time

  • In the ring of aromatic light, the carboxyl group will steer out of sight, meta they go, in the substitution fight.

📖 Fascinating Stories

  • Imagine a carboxylic acid on a mission to change its scenery. It cloaks itself in halogens through a clever disguise while wandering the aromatic landscape, taking the path less traveled by directing a new electrophile to the meta position.

🧠 Other Memory Gems

  • HAP (Halogenation, Alpha, Position) can help you remember that halogens are placed at the alpha position in carboxylic acid reactions.

🎯 Super Acronyms

CARB (Carboxylic Acid Reactivity Basics) can remind you about the characteristics of carboxylic acid reactions, including their behavior in electrophilic substitutions.

Flash Cards

Review key concepts with flashcards.

Glossary of Terms

Review the Definitions for terms.

  • Term: Halogenation

    Definition:

    A reaction where halogens are introduced into a compound, in this case, carboxylic acids.

  • Term: Electrophilic Substitution

    Definition:

    A reaction in which an electrophile replaces a hydrogen atom in an aromatic compound.

  • Term: HellVolhardZelinsky Reaction

    Definition:

    A method for the halogenation of carboxylic acids at the alpha position in the presence of phosphorus.

  • Term: Metadirecting group

    Definition:

    A substituent that directs incoming electrophiles to the meta position of an aromatic ring.