Chapter 12
Carboxylic Acids
Introduction
• Carbonyl (-C=O) and hydroxyl (-OH) on the
same carbon is carboxyl group.
• Carboxyl group is usually written -COOH.
• Aliphatic acids have an alkyl group bonded to
-COOH.
• Aromatic acids have an aryl group.
• Fatty acids are long-chain aliphatic acids.
Chapter 20
2
Common Names
• Many aliphatic acids have historical names.
• Positions of substituents on the chain are
labeled with Greek letters.
Chapter 20
3
IUPAC Names
• Remove -e from alkane (or alkene) name, add -oic
acid.
• The carbon of the carboxyl group is #1.
Cl O
Ph
CH3CH2CHC OH
H
2-chlorobutanoic acid
H
C C
COOH
trans-3-phenyl-2-propenoic acid (cinnamic
acid)
Chapter 20
4
Naming Cyclic Acids
• Cycloalkanes bonded to -COOH are named as
cycloalkanecarboxylic acids.
• Aromatic acids are named as benzoic acids.
COOH
COOH
CH(CH3)2
OH
2-isopropylcyclopentanecarboxylic acid
o-hydroxybenzoic acid
(salicylic acid)
Chapter 20
5
Dicarboxylic Acids
• Aliphatic diacids are usually called by their
common names (to be memorized).
• For IUPAC name, number the chain from the
end closest to a substituent.
• Two carboxyl groups on a benzene ring
COOH
indicate a phthalic acid.
Br
HOOCCH2CHCH2CH2COOH
3-bromohexanedioic acid
-bromoadipic acid
COOH
1,3-benzenedicarboxylic acid
m-phthalic acid
Chapter 20
6
Structure of Carboxyl
• Carbon is sp2 hybridized.
• Bond angles are close to 120.
• O-H eclipsed with C=O, to get overlap of 
orbital with orbital of lone pair on oxygen.
Chapter 20
7
Boiling Points
Higher boiling points than similar alcohols,
due to dimer formation.
Acetic acid, b.p. 118C
Chapter 20
8
Melting Points
• Aliphatic acids with more than 8 carbons
are solids at room temperature.
• Double bonds (especially cis) lower the
melting point. Note these 18-C acids:
– Stearic acid (saturated): 72C
– Oleic acid (one cis double bond): 16C
– Linoleic acid (two cis double bonds): -5C
Chapter 20
9
Solubility
• Water solubility decreases with the length of the
carbon chain.
• Up to 4 carbons, acid is miscible in water.
• More soluble in alcohol.
• Also soluble in relatively nonpolar solvents like
chloroform because it dissolves as a dimer.
Chapter 20
10
Acidity
Chapter 20
11
Resonance Stabilization
Chapter 20
12
Substituent Effects on Acidity
Chapter 20
13
Salts of Carboxylic Acids
• Sodium hydroxide removes a proton to form the
salt.
• Adding a strong acid, like HCl, regenerates the
carboxylic acid.
O
CH3
C OH
NaOH
O
CH3
_ +
C O Na
HCl
Chapter 20
14
Naming Acid Salts
• Name the cation.
• Then name the anion by replacing the
-ic acid with -ate.
Cl
-
CH3CH2CHCH2COO K
+
potassium 3-chloropentanoate
potassium -chlorovalerate
Chapter 20
15
Properties of Acid Salts
• Usually solids with no odor.
• Carboxylate salts of Na+, K+, Li+, and NH4+
are soluble in water.
• Soap is the soluble sodium salt of a long
chain fatty acid.
• Salts can be formed by the reaction of an
acid with NaHCO3, releasing CO2.
Chapter 20
16
Purifying an Acid
Chapter 20
17
Some Important Acids
• Acetic acid is in vinegar and other foods,
used industrially as solvent, catalyst, and
reagent for synthesis.
• Fatty acids from fats and oils.
• Benzoic acid in drugs, preservatives.
• Adipic acid used to make nylon 66.
• Phthalic acid used to make polyesters.
Chapter 20
18
Synthesis Review
• Oxidation of primary alcohols and
aldehydes with chromic acid.
• Cleavage of an alkene with hot KMnO4
produces a carboxylic acid if there is a
hydrogen on the double-bonded carbon.
• Cleavage of an alkyne with ozone or hot
permanganate.
Chapter 20
19
Fischer Esterification
•
•
•
•
Acid + alcohol yields ester + water.
Acid catalyzed for weak nucleophile.
All steps are reversible.
Reaction reaches equilibrium.
O
COOH
+
H
+ CH3CH2OH
Chapter 20
COCH2CH3
+ HOH
20
Amides from Acids
• Amine (base) removes a proton from the
carboxylic acid to form a salt.
• Heating the salt above 100C drives off
steam and forms the amide.
O
O
O
C OH CH NH
+
3
2
C O- +NH CH
3
3
C NHCH
3
heat
Chapter 20
+ H2O
21
Reduction to 1 Alcohols
• Use strong reducing agent, LiAlH4.
• Borane, BH3 in THF, reduces carboxylic acid to
alcohol, but does not reduce ketone.
Chapter 20
22
Reduction to Aldehyde
• Difficult to stop reduction at aldehyde.
• Use a more reactive form of the acid (an acid
chloride) and a weaker reducing agent, lithium
aluminum tri(t-butoxy)hydride.
O
O
CCl
LiAl[OC(CH3)3]3H
C
Chapter 20
H
23
Esters from Acid Chlorides
• Acid chlorides react with alcohols to give
esters in good yield.
• Mechanism is nucleophilic addition of the
alcohol to the carbonyl as chloride ion
leaves, then deprotonation.
O
O
CCl
COCH3
+ CH3OH
+ HCl
Chapter 20
24
End of Chapter 12
Chapter 20
25