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8.7 - Methods of Preparation of Carboxylic Acids

Interactive Audio Lesson

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Oxidation of Alcohols

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Teacher
Teacher

Today we are going to explore how primary alcohols can be oxidized to form carboxylic acids. Who can remind us what oxidation means in organic chemistry?

Student 1
Student 1

Is it when a substance loses electrons or hydrogen?

Teacher
Teacher

Exactly! So, when a primary alcohol undergoes oxidation, what do we end up with?

Student 2
Student 2

A carboxylic acid!

Teacher
Teacher

Correct! We often use potassium permanganate or dichromate solutions as oxidizing agents. Just remember: **KMnO4** for strong oxidation. Can anyone think of a practical example?

Student 3
Student 3

We can convert ethanol to acetic acid?

Teacher
Teacher

Yes! Great example. This is crucial for making vinegars and other food products!

Teacher
Teacher

In summary, oxidation of primary alcohols leads to carboxylic acids using oxidizing agents like KMnO4 or K2Cr2O7.

Oxidation of Alkylbenzenes

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Teacher
Teacher

Next, let's delve into how we can prepare aromatic carboxylic acids from alkylbenzenes. What do you think happens in this reaction?

Student 2
Student 2

The side chain gets oxidized to a -COOH group?

Teacher
Teacher

Absolutely! When we use chromic acid or KMnO4, the entire side chain can be oxidized to form a carboxylic acid. Remember, though, that tertiary groups typically don't oxidize this way. Can someone give an example?

Student 4
Student 4

Toluene can be oxidized to benzoic acid?

Teacher
Teacher

That's correct! Excellent work. Always keep in mind how the reagents function, you can think of chromic acid as a powerful oxidizer. Now for a brief summary!

Teacher
Teacher

Summary: Alkylbenzenes can be oxidized to aromatic carboxylic acids using strong oxidizing agents.

Hydrolysis of Nitriles and Amides

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Teacher
Teacher

Our next method involves the hydrolysis of nitriles. Can anyone explain what nitriles are?

Student 1
Student 1

They’re compounds containing the -CN functional group!

Teacher
Teacher

Exactly! When we hydrolyze nitriles, what do we get?

Student 3
Student 3

We can form amides first, then further hydrolyze to get carboxylic acids!

Teacher
Teacher

Well done! Remember, the use of acid or base to catalyze this process is crucial. It's a pivotal step in making many carboxylic acids. Let's wrap up this session!

Teacher
Teacher

Summary: Nitriles undergo hydrolysis to amides and then to carboxylic acids, which can be initiated by acid or basic conditions.

Reactions Involving Grignard Reagents

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Teacher
Teacher

Next, we will discuss Grignard reagents. What do you think happens when they react with carbon dioxide?

Student 4
Student 4

They should form carboxylic acids!

Teacher
Teacher

That's right! This method is quite useful because it allows us to add one carbon to the chain upon reaction with carbon dioxide. What is the significance of this process?

Student 2
Student 2

It helps in extending carbon chains for synthesis!

Teacher
Teacher

Exactly! Remember to initiate it from an alkyl halide to create the Grignard reagent first. Quick summary?

Teacher
Teacher

Summary: Grignard reagents react with carbon dioxide to produce carboxylic acids, adding one carbon atom to the structure.

Introduction & Overview

Read a summary of the section's main ideas. Choose from Basic, Medium, or Detailed.

Quick Overview

This section outlines the various methods for preparing carboxylic acids from different organic compounds.

Standard

A range of methods for synthesizing carboxylic acids is discussed, including oxidation of alcohols and aldehydes, oxidation of alkylbenzenes, hydrolysis of nitriles and amides, reactions involving Grignard reagents, as well as the hydrolysis of acyl halides and anhydrides. Each method is significant for its practical applications in organic chemistry.

Detailed

Detailed Summary of Methods of Preparation of Carboxylic Acids

Carboxylic acids, characterized by the carboxyl functional group (-COOH), can be synthesized using several methods, each important for their unique applications in organic chemistry. Understanding these methods helps in the development and production of various carboxylic acids needed in industry and laboratory settings.

1. From Primary Alcohols and Aldehydes

Primary alcohols can be readily oxidized to carboxylic acids using common oxidizing agents like potassium permanganate (KMnO4) and potassium dichromate (K2Cr2O7) in acidic, neutral, or alkaline conditions. Aldehydes also undergo oxidation to form respective carboxylic acids through milder oxidizing agents.

2. From Alkylbenzenes

Aromatic carboxylic acids can be synthetically prepared by the vigorous oxidation of alkylbenzenes using chromic acid or potassium permanganate, which oxidizes the entire side chain to the -COOH group, effectively regardless of the side chain's length. However, tertiary alkyl groups do not undergo this oxidation.

3. From Nitriles and Amides

Nitriles can be hydrolyzed to amides and subsequently to carboxylic acids by using an acid (H+) or a base (OH-) as a catalyst, depending upon the reaction conditions desired.

4. From Grignard Reagents

Grignard reagents can react with carbon dioxide (dry ice) to produce carboxylic acids. This method adds one carbon atom to the organic chain, thereby facilitating the formation of acids from alkyl halides.

5. From Acyl Halides and Anhydrides

Acid chlorides (acyl halides) hydrolyze in the presence of water to yield carboxylic acids or upon treatment with aqueous base form carboxylate ions, which when acidified yield corresponding carboxylic acids.

6. From Esters

Carboxylic acids can be produced from esters through hydrolysis, where concentrated acidic conditions yield carboxylic acids, while basic hydrolysis gives carboxylate ions.

In summary, these preparation methods emphasize the diverse strategies available to chemists for synthesizing carboxylic acids, underscoring their fundamental role in organic chemistry.

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Audio Book

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Preparation from Primary Alcohols and Aldehydes

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  1. From primary alcohols and aldehydes
    Primary alcohols are readily oxidised to carboxylic acids with common oxidising agents such as potassium permanganate (KMnO4) in neutral, acidic or alkaline media or by potassium dichromate (K2Cr2O7) and chromium trioxide (CrO3) in acidic media (Jones reagent).

Detailed Explanation

This method involves oxidizing primary alcohols, which are alcohols where the hydroxyl (–OH) group is attached to a carbon atom that is only connected to one other carbon atom. The common oxidizing agents, such as potassium permanganate (KMnO4) or chromium compounds, facilitate this transformation to produce carboxylic acids. For instance, if we start with ethanol (a primary alcohol) and oxidize it using potassium permanganate, the result will be acetic acid (ethanoic acid).

Examples & Analogies

Think of the oxidation of alcohols like the aging process of fruits. Just as a ripe banana can turn brown when exposed to air (a form of oxidation), primary alcohols become carboxylic acids when they undergo a similar process using strong chemicals. This transformation is crucial in various industries, such as making vinegar from fermented alcohol.

Preparation from Aromatic Compounds

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  1. From alkylbenzenes
    Aromatic carboxylic acids can be prepared by vigorous oxidation of alkyl benzenes with chromic acid or acidic or alkaline potassium permanganate. The entire side chain is oxidised to the carboxyl group irrespective of length of the side chain. Primary and secondary alkyl groups are oxidised in this manner while tertiary group is not affected.

Detailed Explanation

This preparation method focuses on aromatic compounds, particularly alkyl benzenes, which are compounds where a hydrocarbon chain is attached to a benzene ring. When these compounds are treated with strong oxidizers like chromic acid, the entire side chain is converted to a carboxylic acid. For example, toluene (methylbenzene) can be oxidized to benzoic acid. However, tertiary alkyl groups don’t undergo this reaction because they are resistant to oxidation.

Examples & Analogies

Imagine a tree (the benzene ring) with branches (the alkyl side chains). If you cut all the branches back to their connection to the tree trunk (the benzene), you effectively create a clean stump (the carboxylic acid). This method is significant in chemical manufacturing, especially in the production of various fragrances and dyes that contain carboxylic acids.

Preparation from Nitriles and Amides

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  1. From nitriles and amides
    Nitriles are hydrolysed to amides and then to acids in the presence of H+ or OH− as catalyst. Mild reaction conditions are used to stop the reaction at the amide stage.

Detailed Explanation

This method involves converting nitriles, which are compounds containing a –C≡N group, into carboxylic acids. First, the nitrile undergoes hydrolysis to form an amide. This process can be facilitated by either acidic (H+) or basic (OH−) conditions. If we want to produce the acid, we can continue to hydrolyze the amide, but if we desire to stop at the amide, we would use milder conditions. For example, converting benzonitrile first yields benzamide, and with continued hydrolysis, produces benzoic acid.

Examples & Analogies

Consider a garden where a seed (nitrile) can grow into a small plant (amide) and, with proper conditions, it matures into a full-fledged tree (carboxylic acid). This method is vital in organic synthesis, serving as a pathway to create many pharmaceuticals and agrochemicals.

Preparation from Grignard Reagents

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  1. From Grignard reagents
    Grignard reagents react with carbon dioxide (dry ice) to form salts of carboxylic acids which in turn give corresponding carboxylic acids after acidification with mineral acid.

Detailed Explanation

Grignard reagents, which are organomagnesium halides, react vigorously with carbon dioxide to form a carboxylate salt. Once these salts are treated with a mineral acid, they are converted into the corresponding carboxylic acids. For example, phenylmagnesium bromide (a Grignard reagent) reacts with carbon dioxide to form benzoate, which turns into benzoic acid when treated with hydrochloric acid.

Examples & Analogies

Imagine baking a cake (the Grignard reagent) where adding chocolate chips (carbon dioxide) creates a delicious chocolate cake (the carboxylic acid). This creative method is widely used in organic chemistry labs to produce complex carboxylic acids needed for various synthetic pathways.

Preparation from Acyl Halides and Anhydrides

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  1. From acyl halides and anhydrides
    Acid chlorides when hydrolysed with water give carboxylic acids or more readily hydrolysed with aqueous base to give carboxylate ions which on acidification provide corresponding carboxylic acids. Anhydrides on the other hand are hydrolysed to corresponding acid(s) with water.

Detailed Explanation

This method involves acid chlorides (a type of acyl halide) reacting with water to produce carboxylic acids directly or, if treated with a base first, yielding carboxylate ions that can also form carboxylic acids upon acidification. Anhydrides, when hydrolyzed with water, will directly yield carboxylic acids as well. For instance, if acetyl chloride (an acyl halide) is treated with water, acetic acid is formed.

Examples & Analogies

You can visualize this process like watering plants (the acid chlorides or anhydrides). Just as water transforms dry soil into nourishing mud (the acids), the hydrolysis of these compounds leads to the formation of useful carboxylic acids in our chemical garden.

Preparation from Esters

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  1. From esters
    Acidic hydrolysis of esters gives directly carboxylic acids while basic hydrolysis gives carboxylates, which on acidification give corresponding carboxylic acids.

Detailed Explanation

Esters can be converted into carboxylic acids through hydrolysis. In acidic conditions, this hydrolysis yields carboxylic acids directly. In basic hydrolysis, esters are first converted into carboxylate ions, which can then be acidified to produce the carboxylic acids. For example, treating ethyl acetate under acidic hydrolysis yields acetic acid.

Examples & Analogies

Think of sugar dissolving in water (the ester hydrolysis) to create sweet syrup (the carboxylic acid). This method is widely utilized in food and beverage industries, as it is fundamental in producing flavorful carboxylic acids from naturally occurring esters.

Definitions & Key Concepts

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

Key Concepts

  • Oxidation: A method used to convert primary alcohols to carboxylic acids using agents like KMnO4.

  • Hydrolysis: The process of breaking down nitriles and amides to form carboxylic acids.

  • Grignard Reagents: React with carbon dioxide to extend organic chains and form acids.

Examples & Real-Life Applications

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

Examples

  • Ethanol can be oxidized to acetic acid (carboxylic acid) using potassium dichromate.

  • Applying Grignard reagents on carbon dioxide can yield carboxylic acids such as propanoic acid from methyl magnesium bromide.

Memory Aids

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

🎵 Rhymes Time

  • When oxidizing alcohols, don’t forget the name, It leads to acids, they're in the game.

📖 Fascinating Stories

  • A chemist discovered that adding alcohol to an oxidizer made magic happen; it turned into a carboxylic acid - the key ingredient in flavors.

🧠 Other Memory Gems

  • O to A: Remember 'OA' for Oxidation to Acids.

🎯 Super Acronyms

CAN H - Carbon, Alcohol, Nitrile to Hydrolysis leads to acida.

Flash Cards

Review key concepts with flashcards.

Glossary of Terms

Review the Definitions for terms.

  • Term: Carboxylic Acids

    Definition:

    Organic compounds containing the carboxyl functional group (-COOH).

  • Term: Oxidation

    Definition:

    A chemical reaction that involves the loss of electrons, often resulting in an increase in oxidation state.

  • Term: Nitrile

    Definition:

    An organic compound containing a cyano group (-CN).

  • Term: Grignard Reagent

    Definition:

    An organomagnesium compound used in organic synthesis, denoted as R-MgX.

  • Term: Hydrolysis

    Definition:

    A reaction in which water is used to break down compounds.