CHAPTER 17

CARBOXYLIC ACIDS

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Chapter Outline
•  (17.1) Structure
•  (17.2) Nomenclature
•  (17.3) Physical properties
•  (17.4) Acidity
•  (17.5) Preparation of carboxylic acids
•  (17.6) Reduction
•  (17.7) Esterification
•  (17.8) Conversion to acid chlorides
•  (17.9) Decarboxylation

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Structure of Carboxylic Acids
•  Functional group: Contains a carbonyl group and a
hydroxyl group (-CO2H or -COOH)

•  General formulas
•  Aliphatic carboxylic acid – RCOOH
•  Aromatic carboxylic acid – ArCOOH
•  α,β-Unsaturated carboxylic acids – RCH2=CH2COOH

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Nomenclature of Carboxylic Acids: IUPAC System

•  Final -e is dropped from the name of the parent alkane,

and the suffix -oic acid is added
•  Chain is numbered beginning with the carbon of the
carboxyl group
•  Common names formic acid and acetic acid are retained

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Nomenclature of Carboxylic Acids: IUPAC System

•  If the compound contains a C=C bond or a C≡C bond,

change the infix from -an- to -en- or -yn-

•  Carboxyl group takes precedence over most other

functional groups

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Nomenclature of Carboxylic Acids: IUPAC System

•  Dicarboxylic acids are named by adding the suffix

-dioic acid to the name of the carbon chain that contains
both carboxyl groups

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Nomenclature of Carboxylic Acids: IUPAC System

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Nomenclature of Carboxylic Acids: IUPAC System

•  Benzoic acid: Simplest aromatic carboxylic acid

•  Naming derivatives of benzoic acid
•  Numbers are used to show the location of substituents relative
to the carboxyl group

•  Naming aromatic dicarboxylic acids

•  The words dicarboxylic acid are added to benzene
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Nomenclature of Carboxylic Acids: Common Names

•  When common names are used, the Greek letters α, β, γ, δ, and

so forth are used as prefixes to locate substituents

•  Presence of a ketone carbonyl in a substituted carboxylic acid is

indicated by the prefix keto- (Acetyl group: CH3CO- or Ac-)

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Table 17.1 - Several Aliphatic Carboxylic Acids: Their
Common Names and Derivations

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Example 17.1 - Naming Carboxylic Acids
•  Write the IUPAC name for each carboxylic acid

•  Solution
a.  (Z)-9-Octadecenoic acid (oleic acid)
b.  ​trans-2-Hydroxycyclohexanecarboxylic acid
c.  (R)-2-Hydroxypropanoic acid [(R)-lactic acid]
d.  Chloroacetic acid (IUPAC name: Chloroethanoic acid)

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Example
•  What is the IUPAC name for the following carboxylic
acid?

1.  Benzoic acid

2.  1-Cyclohexenoic acid
3.  2-Cyclohexenoic acid
4.  1-Cyclohexenecarboxylic acid
5.  2-Cyclohexenecarboxylic acid

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Example
•  What is the IUPAC name for the following carboxylic
acid?

1.  3-Bromo-4-methylbenzoic acid

2.  4-Methyl-3-bromobenzoic acid
3.  Phthalic acid (IUPAC: Benzene-1,2-dicarboxylic acid)
4.  4-Carboxy-2-bromotoluene
5.  5-Carboxy-2-methyl-1-bromobenzene

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Example
•  What is the IUPAC name for the following carboxylic
acid?

1.  2-Propylhexanoic acid

2.  4-Propylhexanoic acid
3.  2-Butylpentanoic acid
4.  4-Carboxyoctane
5.  5-Carboxyoctane

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Example
•  The structure for oleic acid is shown below
•  What is the IUPAC name of this compound?

1.  ​cis-Octadecenoic acid

2.  (Z)-octadec-9-enoic acid
3.  (Z)-octadecyl-9-en-1-oic acid
4.  (Z)-octadecen-9-oic acid
5.  (Z)-9-octadecylenoic acid

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Example
•  Which of the following is not an acyl derivative?

1. 2. 3.

4. 5.

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Physical Properties of Carboxylic Acids
•  Carboxylic acids are associated by hydrogen bonding
into dimers in liquid and solid states

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Physical Properties of Carboxylic Acids
•  Carboxylic acids have higher boiling points than other
types of organic compounds of comparable molecular
weight
•  Result from their polarity and their ability to form very strong
intermolecular hydrogen bonds

•  More soluble in water than alcohols, ethers, aldehydes,

and ketones of comparable molecular weight
•  Result of forming hydrogen bonds with water molecules
through both their C=O and OH groups

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Table 17.2 - Boiling Points and Solubilities in Water of Selected Carboxylic
Acids, Alcohols, and Aldehydes of Comparable Molecular Weight

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Physical Properties of Carboxylic Acids
•  Solubility in water decreases as molecular weight
increases
•  Hydrophilic carboxyl group increases water solubility
•  Hydrophobic hydrocarbon chain decreases water solubility

•  Liquid carboxylic acids from propanoic acid to

decanoic acid have extremely foul odors

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Example
•  Why do carboxylic acids boil at higher temperatures
than most molecules of the same molecular weight?

1.  They have more oxygen atoms than most other molecules
2.  They can participate in hydrogen bonding
3.  They are polar molecules
4.  They have more oxygen atoms than most other molecules,
and they can participate in hydrogen bonding
5.  They can participate in hydrogen bonding and they are
polar molecules

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Acidity - Acid Ionization Constants
•  Carboxylic acids are weak acids
•  Values of Ka for most unsubstituted aliphatic and aromatic
carboxylic acids fall within the range of 10−4 to 10−5
•  Greater acidity of carboxylic acids relative to alcohols
because of:
•  Delocalization of the negative charge of the carboxylate anion
through resonance
•  Electron-withdrawing inductive effect of the carbonyl group

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Acidity - Acid Ionization Constants
•  Electron-withdrawing ability of electronegative chlorine atoms
stabilizes the anionic charge by electron withdrawal through σ-bonds
•  Strength of the inductive effect is proportional to the number of
chlorine atoms present

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Acidity - Acid Ionization Constants
•  The form of carboxylic acid present in an aqueous
solution depends on the pH of the solution

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Acidity - Reaction with Bases
•  Carboxylic acids, whether soluble or insoluble in water,
react with NaOH, KOH, and other strong bases to give
water-soluble salts

•  Form water-soluble salts with ammonia and amines

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Acidity - Reaction with Bases
•  React with sodium bicarbonate and sodium carbonate to
form water-soluble sodium salts and carbonic acid

•  Carbonic acid breaks down to carbon dioxide and water

•  Acid-base properties of carboxylic acids allow an easy

separation of carboxylic acids from water-insoluble
nonacidic compounds (next page)
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Figure 17.1 - Flowchart for the Separation of Benzoic
Acid from Benzyl Alcohol (PhCO2H from PhCH2OH)

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Example 17.3 - Salts of Carboxylic Acids
•  Complete each acid-base reaction and name the
carboxylic salt formed

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Example 17.3 - Solution
•  Each carboxylic acid is converted to its sodium salt
•  In (b), carbonic acid is formed: It decomposes to carbon
dioxide and water

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Example
•  Rank the following molecules in acidity from least
acidic to most acidic

1.  A, C, B
2.  B, A, C
3.  C, B, A
4.  B, C, A
5.  C, A, B

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Example
•  Rank the following molecules in acidity from most
acidic to least acidic

1.  A, C, B, D
2.  C, B, D, A
3.  B, C, A, D
4.  A, B, C, D
5.  C, B, A, D

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Example
•  Chloroacetic acid is a stronger acid than acetic acid
•  Which is the best explanation?

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Example
1.  More resonance structures can be drawn for chloroacetic
acid than for acetic acid
2.  More resonance structures can be drawn for chloroacetate
ion than for acetate ion
3.  Because of its high electronegativity, chlorine is able to
donate electrons to the chloroacetate ion by the inductive
effect, thereby stabilizing this ion
4.  Because of its high electronegativity, chlorine is able to
withdraw electrons from the chloroacetate ion by the
inductive effect, thereby stabilizing this ion
5.  Chlorine is larger than hydrogen and can better hold a
negative charge

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Example
•  p-Chlorobenzoic acid is more acidic than p-
methylbenzoic acid

1.  True
2.  False

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Preparation of Carboxylic Acids
•  Carboxylation of Grignard reagents
•  Overall conversion of an alkyl/aryl halide to a carboxylic acid
•  (1) Involves treating a Grignard reagent with carbon dioxide
to obtain the magnesium salt of a carboxylic acid
•  (2) Protonation of the magnesium salt with aqueous acid
gives a carboxylic acid

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Example
•  What sequence of reagents will accomplish the
following transformation?

1. 4.

2. 5.

3.

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Example – Nitrile Hydrolysis (Ch.18)
•  Determine the product of the following sequence of
reactions

1. 2. 3.

4. 5.

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Reduction of Carboxylic Acids
•  Carboxyl group is very resistant to reduction
•  Not affected by catalytic hydrogenation under conditions that
easily reduce (1) aldehydes and ketones to alcohols and (2)
alkenes and alkynes to alkanes
•  Lithium aluminum hydride reduces a carboxyl group
to a 1° alcohol: Reduction is carried out in diethyl ether
or tetrahydrofuran (Et2O or THF)

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Reduction of Carboxylic Acids
•  Balanced equations for treatment of a carboxylic acid with
LiAlH4 to form a tetraalkoxy aluminate ion, followed by its
hydrolysis in water

•  Selective reduction of other functional groups: Carboxyl groups

are NOT affected by (1) catalytic hydrogenation under conditions
that reduce aldehydes, ketones, alkenes, and alkynes, (2) NaBH4
=> one can selectively reduce these functional groups to
alcohols or alkanes in the presence of carboxyl groups

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Reduction of Carboxylic Acids
•  Selective catalytic hydrogenation

•  Selective reduction with NaBH4: aldehyde or ketone carbonyl

groups can be reduced selectively in the presence of a carboxyl
group using the less reactive NaBH4

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Fischer Esterification
•  Esters can be prepared by treating a carboxylic acid
with an alcohol in the presence of an acid catalyst,
commonly H2SO4, ArSO3H, or gaseous HCl
•  Preparation of an ester in this manner is called Fischer
esterification

•  Acid-catalyzed esterification is reversible

•  Quantities of both carboxylic acid and alcohol remaining at
equilibrium are appreciable
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Fischer Esterification
•  Involves nucleophilic acyl substitution
•  By careful control of reaction conditions, it is possible
to prepare esters in high yield
•  (1) If the alcohol is inexpensive relative to the
carboxylic acid, it can be used in excess to drive the
equilibrium to the right
•  (2) Water can be removed by azeotropic distillation
and a Dean-Stark trap (Figure 16.1)

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Example 17.4 - Fischer Esterification

•  Complete the equation for each Fischer esterification

reaction

•  Solution

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Synthesis of Methyl Esters Using Diazomethane

•  Diazomethane (CH2N2)
•  Potentially explosive, toxic yellow gas
•  Best represented as a hybrid of two resonance contributing
structures

•  Treating a carboxylic acid with diazomethane in ether

solution converts the carboxylic acid to its methyl ester

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Synthesis of Methyl Esters Using Diazomethane

•  Esterification occurs in two steps

•  Step 1: Deprotonation: Proton transfer to diazomethane gives
a carboxylate anion and methyldiazonium cation

•  Step 2: Bond formation between a nucleophile and an

electrophile: Nucleophilic displacement of N2 gives the
methyl ester (key step)

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Conversion to Acid Chlorides
•  Acyl halides (acid halides): Functional group
containing a carbonyl group bonded to a halogen atom
•  Among the acyl halides (X = F, Cl, Br), acid chlorides are
frequently used in the laboratory and in industrial organic
chemistry because of their lower cost and ready availability

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Conversion to Acid Chlorides
•  Acid chlorides are most often prepared by treating a
carboxylic acid with thionyl chloride (SOCl2)

•  Mechanism for this reaction is divided into two steps

•  Step 1: Reaction with SOCl2 transforms OH, a poor leaving
group, into a chlorosulfite group, a good leaving group (key
step)

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Conversion to Acid Chlorides
•  Step 2: Nucleophilic attack of chloride ion gives a tetrahedral
carbonyl addition intermediate, which collapses to give the
acid chloride, SO2, and the chloride ion

O O

R C O S Cl + Cl
-

-
O O O

R C O S Cl R-C-Cl + SO2 + Cl
-

Cl

A tetrahedral carbonyl
addition intermediate

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Example 17.5 - Making Acid Chlorides
•  Complete the equation for each reaction

•  Solution

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Example – Reaction Sequence (incl. Ch.18)
•  Determine the product of the following sequence of
reactions

1. 4.

2. 5.

3.
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Decarboxylation (more in Ch.19)
•  Most carboxylic acids, if heated to a very high temperature,
undergo thermal decarboxylation (loss of CO2 from a carboxyl
group)

•  Typical acids are quite resistant to moderate heat and melt or

even boil without decarboxylation
•  Exceptions: Carboxylic acids that have a carbonyl group β to the
carboxyl group: undergo decarboxylation readily on mild heating

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Decarboxylation: β-Ketoacids
•  Thermal decarboxylation of a β-ketoacid involves rearrangement
of six electrons in a cyclic six-membered transition state

•  Example: Only one carboxyl group in oxalosuccinic acid, an intermediate

in the tricarboxylic acid (TCA) cycle, has a carbonyl in the β-position to it

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Decarboxylation: Malonic Acids
•  Thermal decarboxylation of malonic acid and substituted
malonic acids: decarboxylation occurs if there is any carbonyl
group at the β-position

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Decarboxylation: Malonic Acids
•  Decarboxylation of malonic acids involves rearrangement of six
electrons in a cyclic six-membered transition state
•  Step 1: Redistribution of six electrons in a cyclic six-
membered transition state gives carbon dioxide and the enol
form of a carboxyl group (key step)
•  Step 2: Keto-enol tautomerism of the enol gives the more
stable keto form of the carboxyl group

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Example 17.6 - Decarboxylation Reactions
•  Each of these carboxylic acids undergoes thermal
decarboxylation
•  Draw a structural formula for the enol intermediate and final
product formed in each reaction

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Example 17.6 - Solution
•  Carboxylic acids

•  Enol intermediates and products

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Problem 17.24 – Benzil/Benzylic Acid
Rearrangement
•  The reaction of an α-diketone with concentrated NaOH
or KOH gives the salt of an α-hydroxyacid
•  This reaction is given the general name benzil-benzylic acid
rearrangement
•  Propose a mechanism for this reaction

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Problem 17.24 – Benzil/Benzylic Acid
Rearrangement
•  Step 1: Addition of hydroxide ion to one of the carbonyl groups
forms a tetrahedral carbonyl addition intermediate: Make a bond
between a nucleophile and an electrophile (key step)

•  Step 2: Collapse of the intermediate with simultaneous

regeneration of the carbonyl group and migration of a phenyl
group gives benzylic acid

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Problem 17.24 – Benzil/Benzylic Acid
Rearrangement
•  Step 3: Proton transfer: Take a proton away, or more simply,
transfer a proton to form the benzylate anion

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