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Carboxylic Acids: Nomenclature, preparation, physical properties, and

chemical reactions

Presentation · September 2020

DOI: 10.13140/RG.2.2.16402.48326

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 Carboxylic Acids

Dr. Ameer Alwash

2nd Stage

Carboxylic Acids and the Acidity of the O—H Bond

Structure and Bonding

• Carboxylic acids are compounds containing a carboxy
group (COOH).
• The structure of carboxylic acids is often abbreviated as
RCOOH or RCO2 H, but keep in mind that the central
carbon atom of the functional group is doubly bonded to
one oxygen atom and singly bonded to another.

2
Structure and Bonding
• The C—O single bond of a carboxylic acid is shorter
than the C—O bond of an alcohol.
• This can be explained by looking at the hybridization of
the respective carbon atoms.

• Because oxygen is more electronegative than either

carbon or hydrogen, the C—O and O—H bonds are polar.
3

Nomenclature—The IUPAC System

• In the IUPAC system, carboxylic acids are identified

by a suffix added to the parent name of the longest
chain with different endings being used depending
on whether the carboxy group is bonded to a chain
or a ring.
If the COOH is bonded to a chain, find the longest
chain containing the COOH, and change the “e” ending
of the parent alkane to the suffix “oic acid”.
If the COOH is bonded to a ring, name the ring and add
the words “carboxylic acid”.
Number the carbon chain or ring to put the COOH
group at C1, but omit this number from the name.
Apply all the other usual rules of nomenclature.
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 5

• Greek letters are used to designate the location of substituents

in common names.
• The carbon adjacent to the COOH is called the  carbon,
followed by the  carbon, followed by the  carbon, the  carbon
and so forth down the chain.
• The last carbon in the chain is sometimes called the  carbon.
• The  carbon in the common system is numbered C2 in the
IUPAC system.

6
• Compounds containing two carboxy groups are called
diacids. Diacids are named using the suffix –dioic acid.

• Metal salts of carboxylate anions are formed from

carboxylic acids in many reactions. To name the metal
salt of a carboxylate anion, put three parts together:

As with other acids containing more than one ionizable

hydrogen (H2SO4, H2CO3 , H3 PO4 , etc.), ionization of the
second carboxyl group occurs less readily than ionization
of the first (compare K1’s with K2’s). More energy is
required to separate a positive hydrogen ion from the
doubly charged anion than from the singly charged anion.

8
Physical Properties (M.P, B.P and solubility)
• Carboxylic acids exhibit dipole-dipole interactions
because they have polar C—O and O—H bonds.
• They also exhibit intermolecular hydrogen bonding.
• Carboxylic acids often exist as dimers held together by
two intermolecular hydrogen bonds.

Carboxylic acids salts Solubility and M.P

10
 We can separate a carboxylic acid from non-acidic
compounds by taking advantage of its solubility and their
insolubility in aqueous base; once the separation has been
accomplished, we can regenerate the acid by acidification of the
aqueous solution. If we are dealing with solids, we simply stir
the mixture with aqueous base and then filter the solution from
insoluble, non-acidic materials; addition of mineral acid to the
filtrate precipitates the carboxylic acid, which can be collected
on a filter.
If we are dealing with liquids, we shake the mixture with
aqueous base in a separatory funnel and separate the aqueous
layer from the insoluble organic layer; addition of acid to the
aqueous layer again liberates the carboxylic acid, which can
then be separated from the water. For completeness of
separation and ease of handling, we often add a water-insoluble
solvent like ether to the acidified mixture. The carboxylic acid is
extracted from the water by the ether, in which it is more soluble
(as shown in the following figure); the volatile ether is readily
removed by distillation from the comparatively high-boiling acid.
11

For example, an aldehyde prepared by the oxidation of a primary

alcohol may very well be contaminated with the carboxylic acid; this
acid can be simply washed out with dilute aqueous base. The
carboxylic acid prepared by oxidation of an alkylbenzene may very well
be contaminated with unreacted starting material; the carboxylic acid
can be taken into solution by aqueous base, separated from the
insoluble hydrocarbon, and regenerated by addition of mineral acid.
Since separations of this kind are more clear-cut and less wasteful of
material, they are preferred wherever possible over recrystallization or
distillation.

12
Industrial Sources
The most important sources of aliphatic carboxylic acids are the
animal and vegetable fats. From fats there can be obtained, in purity of
over 90%, straight-chain carboxylic acids of even carbon number
ranging from six to eighteen carbon atoms. These acids can be
converted into the corresponding alcohols, which can then be used, in
the ways we have already studied, to make a great number of other
compounds containing long, straight chain units.

13

Preparation of Carboxylic Acids

[1] Oxidation of 1° alcohols

[2] Oxidation of alkyl benzenes

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[3] Oxidative cleavage of alkynes

[4] Hydrolysis of Nitriles (longer C.A)

15

[5] Carbonation of Grignard reagent (longer C.A)

[6] Malonic ester synthesis

[7] Special methods for phenolic synthesis 16
Reactions of Carboxylic Acids

The aqueous solutions of carboxylate salts are slightly alkaline. The

basicity of an aqueous solution of a carboxylate salt is due chiefly, of
course, to the carboxylate anions, not to the comparatively few
hydroxide ions they happen to generate. We may now expand the
series of relative acidities and basicities:

17

18
19

20
 21

• Carboxylic acids are recognized through their acidity. They

dissolve in aqueous sodium hydroxide and in aqueous sodium
bicarbonate. The reaction with bicarbonate releases bubbles of
carbon dioxide.
Carboxylic Acids—Strong Organic Br Ønsted-Lowry Acids
Carboxylic acids are strong organic acids, and as such, readily
react with BrØnsted-Lowry bases to form carboxylate anions. An
acid can be deprotonated by a base that has a conjugate acid with
a higher pKa. Because the pKa values of many carboxylic acids are
~5, bases that have conjugate acids with pKa values higher than 5
are strong enough to deprotonate them.

22
• Carboxylic acids are relatively strong acids because
deprotonation forms a resonance-stabilized conjugate
base—a carboxylate anion.

• Resonance stabilization accounts for why carboxylic acids

are more acidic than other compounds with O—H bonds—
namely alcohols and phenols.

23

• Ethoxide, the conjugate base of ethanol, bears a negative

charge on the O atom, but there are no additional factors to
further stabilize the anion. Because ethoxide is less stable than
acetate, ethanol is a weaker acid than acetic acid.

• Phenoxide, the conjugate base of phenol, is more stable than

ethoxide, but less stable than acetate because acetate has two
electronegative O atoms upon which to delocalize the negative
charge, whereas phenoxide has only one.

24
 Henderson-Hasselbalch Equation
If pKa of given acid and the pH of the medium
are known, % of dissociated and undissociated
forms can be calculated using the Henderson-
Hasselbalch equation.

Henderson-Hasselbalch equation

The Inductive Effect in Aliphatic Carboxylic Acids

26
 27

Substituted Benzoic Acids

Recall that substituents on a benzene ring either donate or
withdraw electron density, depending on the balance of their
inductive and resonance effects. These same effects also
determine the acidity of substituted benzoic acids.

[1] Electron-donor groups destabilize a conjugate base, making an

acid less acidic—The conjugate base is destabilized because
electron density is being donated to a negatively charged
carboxylate anion.

28
[2] Electron-withdrawing groups stabilize a conjugate base,
making an acid more acidic. The conjugate base is stabilized
because electron density is removed from the negatively
charged carboxylate anion.

29

Preview of Oxidation and Reduction

• Carbonyl compounds are either reactants or products in

oxidation-reduction reactions.
Reduction of Carboxylic Acids and Their Derivatives
• LiAlH4 is a strong reducing agent that reacts with all
carboxylic acid derivatives.
• Diisobutylaluminum hydride ([(CH3)2CHCH2]2AlH,
abbreviated DIBAL-H, has two bulky isobutyl groups
which makes this reagent less reactive than LiAlH4.
• Lithium tri-tert-butoxyaluminum hydride,
LiAlH[OC(CH3)3]3, has three electronegative O atoms
bonded to aluminum, which makes this reagent less
nucleophilic than LiAlH4.

• Acid chlorides and esters can be reduced to either

aldehydes or 1° alcohols depending on the reagent.
• In the reduction of an acid chloride, Cl¯ comes off as the
leaving group.
• In the reduction of the ester, CH3 O¯ comes off as the
leaving group, which is then protonated by H2O to form
CH3 OH. (which one has better leaving group ability and
why?)

• Carboxylic acids are reduced to 1° alcohols with LiAlH4.

• LiAlH4 is too strong a reducing agent to stop the reaction
at the aldehyde stage, but milder reagents are not strong
enough to initiate the reaction in the first place.
1) Draw the structure corresponding to the IUPAC name.
a) 2-bromobutanoic acid b) 2,3-dimethylpentanoic acid

c) 2-secbutyl-4,4’-diethylnonanoic acid

d) 3,4-diethylcyclohexanecarboxylic acid

2) Give the IUPAC name for each compound.

O

a)
OH

b)
OH
3) Identify the starting material in each reaction.
a) O

Na2Cr2O7 OH

H2SO4, H2O

KMnO4 OH
b)
O2N

4) Which of the following bases are strong enough to

deprotonate CH3COOH?

a) F- b) (CH3)3CO- c) CH3-

5) Rank the compounds within each group in order of

decreasing acidity.
a) CH3COOH, HSCH2COOH, HOCH2COOH
b) ICH2COOH, I2CHCOOH, ICH2CH2COOH

6) Examine the 3 compounds below. Place them in

order with respect to increasing acidity.

Fluoroacetic acid, trifluoroacetic acid, iodoacetic acid

7) Rank each group of compounds in order of
decreasing acidity.
a) CO2H CO2H CO2H

Cl

CO2H
b) CO2H CO2H

O
H3CO

8) Draw the products of LiAlH4 reduction of each

compound.
a) O

OH

b) O

NH2

O
c)
N(CH3)2

9) Why is formic acid more acidic than acetic acid?

 PRACTICE PROBLEMS

1. For a solution whose pH is 6.0, what is [H+]? If [H+] is 5 x

10–7 M, what is the pH? (answer = 6.3)

2. A. For a weak acid such as the R group carboxyl group of Glu

or Asp in a protein, if the pKa of that specific residue's carboxyl
group is exactly 4.0, in an environment in which the pH = 5.0,
what would be the ratio of base to acid ( [COO–]/[COOH] )?
(Answer = 10/1)

B. For that same carboxyl group, what fraction, or what

percentage, of the total (population of all the molecules in
solution) is present in the form of the ACID (COOH) at pH 5.0?
(Answer = 9.1%)
41

Q/ Suppose that about 1:100 of the molecules of a

particular protein in solution have the imidazole group of
a specific Histidine residue in the uncharged (neutral)
form at pH 4.5. What is the pKb of that specific His
residue in that protein?

Answer (7.5)

42

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