Organic Chemistry, 5th Edition

L. G. Wade, Jr.

Chapter 20
Carboxylic Acids

Jo Blackburn
Richland College, Dallas, TX
Dallas County Community College District
2003, Prentice Hall
 Introduction
• The functional group of carboxylic acids
consists of a C=O with -OH bonded to the
same carbon.
• 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.

Ph
Cl O
CH3CH2CH2CHCH2COOH
CH3CH2CHC OH
-phenylcaproic acid
-chlorobutyric acid
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 H
CH3CH2CHC OH C C
H COOH
2-chlorobutanoic acid
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
indicate a phthalic acid.
Br
HOOCCH2CHCH2CH2COOH
3-bromohexanedioic acid
-bromoadipic 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

COOH COOH COOH COOH COOH

NO2

NO2
OCH3 NO2
p-methoxy benzoic acid m-nitro p-nitro o-nitro
pKa = 4.46 pKa = 4.19 pKa = 3.47 pKa = 3.41 pKa = 2.16 =>
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 O
NaOH _ +
CH3 C OH 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 -chlorovalerate
potassium 3-chloropentanoate

=>
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
IR Spectroscopy

=>
Chapter 20 19
NMR Spectroscopy

=>
Chapter 20 20
 UV Spectroscopy
• Saturated carboxylic acids absorb very
weakly around 200-215 nm.
• If C=C is conjugated with C=O, molar
absorptivity = 10,000 at 200 nm.
• An additional conjugated double bond
increases the absorption wavelength to
250 nm.
=>
Chapter 20 21
Mass Spectrometry

=>
Chapter 20 22
 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.
• Alkyl benzene oxidized to benzoic acid
by hot KMnO4 or hot chromic acid.
=>
Chapter 20 23
 Grignard Synthesis
Grignard reagent + CO2 yields a
carboxylate salt.

CH3 CH3 + CH3

O C O - + H
CH3CH3CHCH2MgBr CH3CH3CHCH2COO MgBr CH3CH3CHCH2COOH

=>
Chapter 20 24
 Hydrolysis of Nitriles
Basic or acidic hydrolysis of a nitrile
produces a carboxylic acid.

Br CN + COOH
NaCN H
H2O

=>
Chapter 20 25
 Acid Derivatives
• The group bonded to the acyl carbon
determines the class of compound:
-OH, carboxylic acid
-Cl, acid chloride
-OR’, ester
-NH2, amide
• These interconvert via nucleophilic acyl
substitution. =>
Chapter 20 26
 Fischer Esterification
• Acid + alcohol yields ester + water.
• Acid catalyzed for weak nucleophile.
• All steps are reversible.
• Reaction reaches equilibrium.
O
COOH + COCH2CH3
H
+ CH3CH2OH + HOH

=>
Chapter 20 27
 Fischer Mechanism (1)
Protonation of carbonyl and attack of
alcohol, a weak nucleophile.
+ +
O H OH OH

COH COH COH

+
OH OH
H COH
COH
O
CH3CH2OH O+ H R
O

CH2CH3 CH2CH3

=>
Chapter 20 28
 Fischer Mechanism (2)
Protonation of -OH and loss of water.

+
H +
H OH OH H
+
C OH O C O
COH C OH
R
O O O
O
CH2CH3 CH2CH3 CH2CH3
CH2CH3

=>
Chapter 20 29
 Acid Chlorides
• An activated form of the carboxylic acid.
• Chloride is a good leaving group, so
undergoes acyl substitution easily.
• To synthesize acid chlorides use thionyl
chloride or oxalyl chloride with the acid.
O O
O O C Cl
C OH
+ C C + HCl + CO + CO2
Cl Cl

=>
Chapter 20 30
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 31
Amides from Acid Chlorides
• Acid chlorides react with ammonia and
amines to give amides.
• A base (NaOH or pyridine) is added to
remove HCl by-product.
O O
CCl CNHCH3
NaOH
+ CH3NH2 + NaCl + H2O

=>
Chapter 20 32
 Diazomethane
• CH2N2 reacts with carboxylic acids to
produce methyl esters quantitatively.
• Very toxic, explosive. Dissolve in ether.

O O
C OH C OCH
+ CH2N2 3 + N2

=>
Chapter 20 33
Mechanism for
Diazomethane

Chapter 20 34
=>
 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 C O- +NH CH C NHCH
+ 3 3 3
3 2
heat
+ H2O

=>
Chapter 20 35
 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 36
=>
 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 C
H
LiAl[OC(CH3)3]3H

=>
Chapter 20 37
Alkylation to Form Ketones
React 2 equivalents of an organolithium
reagent with a carboxylic acid.
O
COOH 1) 2 CH3CH2 Li C CH CH
2 3

2) H2O

=>
Chapter 20 38
End of Chapter 20

Chapter 20 39