Acidity of Carboxylic Acids

• Carboxylic acids are weakly acidic– One of their most important properties

120.4 Acid-Base Properties of Carboxylic Acids

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pKa Values of Some Carboxylic Acids

420.4 Acid-Base Properties of Carboxylic Acids

Effects of Substitution on Acidity

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• Conjugate bases of carboxylic acids are called carboxylate ions– More soluble than carboxylic acids

• Naming carboxylic acid salts– Name the cation– Name the anion by removing the “-ic acid” and

replacing it with “-ate”

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Basicity of Carboxylic Acids

• The carbonyl oxygen is weakly basic– plays an important role in many reactions

• Note: Carboxylate protonation is less favorable

720.4 Acid-Base Properties of Carboxylic Acids

Problems

1) You have a mixture of naphthalene and benzoic acid that you wish to separate. How might you take advantage of the acidity of one component in the mixture to accomplish the separation?

2) Without looking at a table of pKa values, rank the substances in each of the following groups in order of increasing acidity: fluoroacetic acid, 3-fluoropropanoic acid, iodoacetic acid

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Synthesis of Carboxylic Acids

1) Oxidation of primary alcohols

2) Side-chain oxidation of alkylbenzenes

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3) Grignard or organolithium with carbon dioxide

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Problem

• How would you prepare butanoic acid using two different methods?

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Carboxylic Acid Reactions

• There are four main types of reactions:1. Reactions at the carbonyl group2. Reactions at the carboxylate oxygen3. Loss of the carboxy group as CO2

(decarboxylation)4. Reactions involving the -carbon (Ch 22)

1220.7 Introduction to Carboxylic Acids Reactions

Acid-Catalyzed Esterification

• Ester:

• Carboxylic acid + alcohol + acid catalyst = Ester

• Also referred to as the Fischer esterification• Equilibrium is favorable, but not large• The alcohol needs to be present in large excess

(commonly as the solvent)

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Problem• Write out the complete mechanism for the following reaction

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Esterification via SN2 Rxn with Carboxylate Anion

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Esterification by Alkylation

• The carboxylate oxygen acts as a nucleophile

1820.8 Conversion of Carboxylic Acids into Esters

Problems

1) What reactants can you use to form the following ester using an SN2 reaction?

2) Draw the mechanism for the esterification of benzoic acid via alkylation using diazomethane.

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