UNIT (9) CARBOXYLIC ACIDS, ESTERS, AMINES, AND AMIDES
9.1 Carboxylic Acids
The functional group in carboxylic acids is called the carboxyl group. A carboxyl group
is a carbonyl group (C = O) with a hydroxyl group (-OH) attached to the carbonyl carbon
atom.
O
Representation of a carboxyl group
O
Carboxylic acid: R
C
C
OH
or
COOH
or
CO2H
OH
(R = H, or aliphatic or aromatic hydrocarbon)
9.2 Naming Carboxylic Acids
The names of carboxylic acids end in “-oic acid,” indicating the presence of the carboxyl
group, ie: propanoic acid, butanoic acid, pentanoic acid, etc. When naming carboxylic
acids, the “–e” is dropped from the alkane containing the carboxyl group and replaced
with “-oic acid”. The chain is numbered from the carboxylic acid group which is always
located on the first carbon. The location of the functional group is not included in the
name.
Examples:
CH 3 - COOH
ethanoic acid
CH 3 - CH2 - CH2 - COOH
butanoic acid
CH 3 - CH2 - COOH
propanoic acid
COOH
CH3
CH 3 - CH - CH2 - COOH
4
3
2
1
3-methylbutanoic acid
benzoic acid
Some members of this class are widely known by their common names. Common names
of acids you should know:
HCOOH
Formic acid
CH 3COOH
Acetic acid
A solution of acetic acid and water is known as vinegar.
9-1
Worked Example 9-1
Give the IUPAC name for each of the following compounds:
Br
a) (CH3)3C-COOH
b)
CH3 - CH - CH2 - COOH
COOH
O
c)
d)
OH
NO2
Solution
a) 2,2-dimethylpropanoic acid
b) 3-bromobutanoic acid
c) 4-nitrobenzoic acid
d) 3,4-dimethylhexanoic acid
Practice 9-1
Name each of the following acids:
OH
a) CH3CH2CF2CH2COOH
b) CH3 - CH2 - CH - COOH
COOH
COOH
c)
d)
HO
CH3
OH
O
NH2
e) CH3 - CH - COOH
f)
OH
Answer
a) 3,3-difluoropentanoic acid
b) 2-hydroxybutanoic acid
c) 3,4-dihydroxybenzoic acid
d) 3-methylbenzoic acid
e) 2-aminopropanoic acid
f) 2-ethylhexanoic acid
9-2
9.3 Acidity of Carboxylic Acids
Carboxylic acids are weak acids. When a carboxylic acid is placed in water, the following
equilibrium is established.
RCOOH + H2O
RCOO - + H3O +
carboxylic
acid
carboxylate
ion
Carboxylate ions are named by dropping the –ic ending from the name of the parent acid
and replacing it with –ate.
CH3COOH + H2O
CH3COO-
acetic acid
acetate ion
+ H3O +
Neutralization of Carboxylic Acids (reaction of acids with bases)
Carboxylic acids undergo neutralization reactions with strong bases as you have seen in
unit 6.in a manner similar to that of inorganic acids. Neutralization of carboxylic acids
produce a carboxylic acid salt and water.
CH3COOH + NaOH
acetic acid
carboxylic acid
CH3COO-Na+ + H2O
*sodium acetate
carboxylic acid salt
*Note that carboxylic acid salts are named similarly to other ionic compounds (unit 4).
The cation is named first, followed by the name of the anion.
Worked Example 9-2
Complete the following reaction and name the carboxylic acid salt formed.
COOH
+ KOH
Solution
The “protons” of the acid are removed by the OH- of the base to produce water.
The cation of the base, in this case K+, forms the salt of the carboxylic acid.
COO - K+
COOH
+ KOH
benzoic acid
+ H 2O
potassium
benzoate
9-3
Practice 9-2
Complete the following reaction and name the carboxylic acid salt formed.
CH3 - CH2 - COOH + NaOH
Answer
-
CH3 - CH2 - COOH + NaOH
+
CH3 - CH2 - COO Na + H2O
sodium propanoate
9.4 Esters
Esters are derivative of carboxylic acids in which the –OH group on the carboxyl has
been replaced with an –OR group.
O
O
R - C - OH
R- C - OR
carboxylic acid
ester
Esterification (Preparation of Esters)
The process of esterification involves the reaction of a carboxylic acid with an alcohol in
the presence of an acid catalyst. Water is also a product in this reaction.
The generalized reaction can be shown as:
O
R-C-OH +
carboxylic
acid
R'-OH
O
[H2SO4]
R-C-OR' + H2O
ester
alcohol
When ethanol is added to acetic acid and a drop of sulfuric acid (symbolized as H+), the
following equilibrium will result:
O
CH3 - C - OH + CH3-CH2-OH
[H+]
O
CH3 - C - O - CH2-CH3 + H2O
9-4
Worked Example 9-3
What carboxylic acid and alcohol are required to produce the following ester?
O
CH3 - CH2 - C - O - CH2-CH2-CH2-CH3
Solution
Separate the molecule by drawing a line down through the oxygen in the carbon
chain. Add an –OH on both sides of your line to create the carboxylic acid on the
carbonyl side and the alcohol on the alkyl side.
O
HO - CH2-CH2-CH2-CH3
alcohol
CH3 - CH2 - C - OH
carboxylic acid
(propanoic acid)
(1-butanol)
Worked Example 9-4
Complete the following esterification reaction:
O
[H+]
CH3-C-OH
+
CH3-OH
Solution
Each ester has an “acid part” and an “alcohol part”. The acid part is the carboxylic
acid minus the –OH group. The alcohol part is an alcohol molecule, minus the H
atom of the –OH group. The –OH of the acid and the H of the alcohol form H2O
molecule.
removal of OH
and H produces the ester
O
CH3-C-OH
[H+]
+
CH3-OH
O
CH3-C-OCH3
+
H2O
9-5
Practice 9-3
Complete the following esterification reaction:
[H+]
O
OH
+
CH3 - CH2 -OH
Answer
removal of OH
and H produces the ester
O
O
[H+]
OH + CH3 - CH2 -OH
O- CH2 - CH3
+ H2O
9.5 Naming Esters
Ester names consist of two words.
Use the alkyl portion of the alcohol name first.
The -ic acid ending of the name of the carboxylic acid is replaced with –ate and follows
the first name.
Examples:
O
O
CH 3CH2COCH3
CH 3COCH2CH2CH2CH3
Methyl propanoate
Butyl acetate
Worked Example 9-5
Name each of the following esters:
O
a) CH3CH2COCH2CH3
O
b)
O
c) CH3CH2CO
Solution
a) ethyl propanoate
c) cyclopentyl propanoate
COCH3
O
d)
CO
b) methyl benzoate
d) cyclobutyl benzoate
9-6
Practice 9-4
Write the name for each of the following esters.
O
a) CH 3(CH 2)5 CH2COCH 3
O
CO
b)
CH3
CH
CH3
O
c)
O
OCH 2CH3
d) CH3CH2CO
CH 2CH2CH3
Answer
a) methyl octanate
b) isopropyl benzoate
c) ethyl butanoate
e) propyl propanoate
9.6 The Hydrolysis of Esters
Hydrolysis is a reaction in which an organic molecule reacting with water splits into two
parts, each of which has fewer carbons than the original organic molecule.
Esters hydrolysis is a very slow reaction. The reaction is considerably more rapid under
either acidic or basic conditions.
Ester hydrolysis under acidic condition (acid hydrolysis) is the reverse of acid-catalyzed
ester formation.
Ester hydrolysis under basic condition (base hydrolysis) produces the metal carboxylate
salt instead of the carboxylic acid.
I) Acid Hydrolysis of Esters
Acid hydrolysis of esters requires the presence of a strong acid catalyst such as sulfuric
acid. This reaction requires heat. The generalized hydrolysis can be shown as:
O
R - C - O - R'
H+, heat
+
H2O
O
R - C - OH
Ester
Acid
(This hydrolysis is the reverse of esterification.)
+
R' - OH
Alcohol
9-7
Worked Example 9-6
Complete the following reactions:
O
H+
CH3-C-OCH3
+
H2O
O
-C-OCH2CH3
H+
H2O
+
Solution
To write the hydrolysis product, under acidic condition, separate the compound at
the ester bond, producing the “parent” carboxylic acid and alcohol.
O
O
H+
+
CH3-C-OCH3
H2O
O
-C-OCH2CH3
+
H2O
CH3-OH
+
CH3-C-OH
O
H+
-C-OH
+
CH3CH2-OH
II) Base Hydrolysis of Esters
Base hydrolysis of esters is called saponification and it is used to manufacture soaps from
animal fats and vegetable oils.
The generalized hydrolysis can be shown as:
O
O
R - C - O - R'
Ester
+
NaOH
H2O
R - C - O-Na+
Carboxylate
salt
+
R' - OH
Alcohol
Notice that this reaction is not an equilibrium reaction (see arrow). The formation of salt
drives the equilibrium to the right, making the reaction irreversible.
9-8
Worked Example 9-7
Complete the following saponification (base hydrolysis) reactions:
O
CH3 - C - OCH2CH3
+ NaOH
H2O
O
-C-OCH3
NaOH
+
H2O
Solution
The hydrolysis of ester, under the basic condition, produces the carboxylic acid
salt and an alcohol
O
O
CH3 - C - OCH2CH3
+
NaOH
H2O
ethyl acetate
O
-C-OCH3
methyl benzoate
CH3 - C - O-Na+
+
CH3CH2 - OH
sodium acetate
O
H2O
+
NaOH
-C-O-Na+
+ CH3 - OH
sodium benzoate
9-9
Practice 9-5
Complete the following reactions:
O
H+
CH3CH2-C-OCH2CH3 + H2O
O
H2O
CH3CH2-C-OCH2CH3 + NaOH
Answer
O
CH3CH2-C-OCH2CH3+ H2O
O
CH3CH2-C-OCH2CH3+ NaOH
H
O
+
CH3CH2-C-OH +
CH3CH2OH
O
H2O
-
+
CH3CH2-C-O Na +
CH3CH2OH
9.7 Amines
The three most common elements in organic compounds are carbon, hydrogen, and
oxygen. Amines contain nitrogen and are commonly found in a wide variety of
biomolecules and important pharmaceutical compounds. For this reason, nitrogen ranks
fourth on the list of common elements found in organic compounds.
Amines are considered organic derivatives of ammonia (NH3) in which one or more
hydrogen atoms are replaced by an alkyl or aromatic group.
Amines are classified as primary, secondary, or tertiary, depending on the number of
organic groups directly attached to the nitrogen atom.
H
H
R
R
H-N-H
R-N-H
R-N-H
R - N -R
Ammonia
primary
amine
secondary
amine
tertiary
amine
9-10
9.8 Naming Amines
Common names are often used to name simple amines. If two or three alkyl groups are
present, they are listed alphabetically along with the suffix –amine. The name is written
as one word. Aromatic amines are usually named based on aniline.
Examples:
CH3
CH3 - NH2
CH3CH2 - NH2
CH3CH2- NH - CH3
methylamine
ethylamine
ethylmethylamine
CH3 - N - CH3
trimethylamine
NH2
NH2
Cl
3-chloroaniline
aniline
Worked Example 9-8
Name each of the following:
a)
CH3CH2CH2CH2CH2 - NH2
CH3CHCH3
c) CH3CH2CH2- N - CH3
b)
d)
CH3CH2CH2CH2 - NH-CH2CH2CH2CH3
N(CH3)2
Solution
a) pentylamine
(This amine has one alkyl group (pentyl) attached to the nitrogen atom.)
b) dibutylamine
(This amine has two identical alkyl groups (butyl) attached to the nitrogen
atom.)
c) isopropylmethylpropylamine
(This amine has three alkyl groups (isopropyl, methyl, and propyl) attached to
the nitrogen atom.)
d) cyclohexyldimethylamine
(This amine has three alkyl groups (a cyclohexyl and two methyl group)
attached to the nitrogen atom.)
9-11
Practice 9-6
Name each of the following:
NH2
NH2
a)
b)
Br
Br
c) CH3(CH2)5-NH-CH2CH3
d)
N
Answer
a) cyclopentylamine
b) 3,4-dibromoaniline
c) ethylhexylamine
d) diethylmethylamine
9.9 Basicity of Amines
Recall (unit 6) that ammonia is also a weak base and accepts H+ from water to produce
ammonium ion (NH4+) and hydroxide ion (OH-):
NH3 + H2O
ammonia
NH4+ +
ammonium
ion
OH-
Because the amines are derivatives of ammonia, they react in a similar ways.
General reaction
R-NH2 + H2O Specific reaction
CH3 - NH2 + H2O
Methylamine
RNH3+ + OH
CH3- NH3+ + OHmethylammonium
ion
Just as amines accept H+ from water, they can accept H+ from acids and form salts. For
example, when methylamine reacts with HCl, the acid-base reaction produces
methylammonium chloride.
CH3 – NH3+ClCH3 – NH2 + HCl →
methylamine
acid
methylammonium chloride
9-12
9.10 Amides
The functional group of an amide is a carbonyl group (C = O) linked to a nitrogen atom
(N). Amides are classified as primary, secondary, and tertiary amides.
O
O
O
R - C - N - R'
R-C-N- H
R - C - N - R'
H
H
primary
R''
secondary
tertiary
R, R′, and R′′ could be aliphatic or aromatic.
9.11 Naming Amides
Naming Primary Amides
The ending of the name of the carboxylic acid is changed from –ic acid (common) or –oic
acid (IUPAC) to –amide.
Examples
O
O
O
CH3CH2CNH2
CH3CH2CH2CNH2
Propanamide
butanamide
NH2
hexanamide
Naming Secondary and Tertiary Amides
The names of groups attached to nitrogen are placed first, using an N-prefix for each
group.
O CH3
O CH3
CH3 - CH2 - C - N - H
CH 3 - CH2 - C - N - CH3
N-methylpropanamide
N,N-dimethylpropanamide
O CH3
CH3 - CH2 - C - N - CH2-CH3
N-ethyl-N-methylpropanamide
9-13
Worked Example 9-9
Name each of the following amides:
O
C - NH2
O
a) CH 3 - CH2 - CH2 - CH2 - C -NH2
b)
O
O
c) CH 3 - C - NH 2
d)
H - C - NH2
Solution
a) pentanamide
c) acetamide (ethanamide)
b) benzamide
d) formamide (methanamide)
Practice 9-7
Name each of the following amides:
O
O H
C - NH - CH2-CH3
a) CH 3 - C - N
b)
O
c) CH3 - CH2 - CH3 - CH2 - C - NH
Answer
a) N-cyclohexylacetamide
c) N-isopropylpentanamide
b) N-ethylbenzamide
9-14
9.12 Hydrolysis of Amides
Amides are very stable in water. Hydrolysis requires the heating of the amide in the
presence of strong acid or base. Acidic hydrolysis gives a carboxylic acid and an amine
salt.
In aqueous base, the products of hydrolysis are a carboxylic acid salt and ammonia or an
amine.
General Reactions:
Acid Hydrolysis of Amides
O
R - C - NH - R' +
H2O
O
heat
+ HCl
Base Hydrolysis of Amides
O
+ NaOH
R - C - NH - R'
R' - NH3+Cl-
+
R - C - OH
O
heat
R - C - O - Na+
R' - NH2
+
Example of Acid Hydrolysis of Amide:
O
O
CH3 - C - NH2
acetamide
+
H2O
+
water
CH3-C-OH
HCl
hydrochloric
acid
+
NH4Cl
ammonium
chloride
acetic acid
Example of Base Hydrolysis of Amide:
O
O
CH3 - C - NH2
acetamide
+ NaOH
sodium
hydroxide
CH3 - C - O- Na+
sodium
acetate
+
NH3
ammonia
9-15
Worked Example 9-10
Draw the structures of the products in each of the following hydrolysis reactions.
O
C - NH
2
heat
+ NaOH
O
CH3 - CH2 - C - NH - CH3 +
H2O +
heat
HCl
Answer
O
C
O
NH2
C
O-Na+
heat
+
NaOH
O
CH3 - CH2 - C - NH - CH3+ H2O + HCl
+ NH3
heat
O
CH3 - CH2 - C - OH + CH3-NH3+Cl-
9-16
Practice 9-8
Draw the structures of the products in each of the following hydrolysis reactions.
O
C - NH 2
heat
+ HCl
+ H2O
O
CH3 - CH2 - C - NH - CH3
heat
+ NaOH
Answer
O
O
C
C
NH2
+ H2O
+ HCl
O
CH3 - CH2 - C - NH - CH3 + NaOH
heat
heat
OH
+ NH4+Cl-
O
-
+
CH3 - CH2 - C - O Na + CH3-NH2
9-17
Homework Problems
9.1 Give the name for each of the following:
COOH
a.
Cl
Cl
O
b.
OH
CH3
c.
CH3 - CH -CH2 - COOH
d.
( CH 3CH 2)3CCOOH
9.2 Draw the structural formula for each of the following compounds:
a. sodium hexanoate
b. potassium acetate
c. zinc benzoate
d. calcium propanoate
9.3 Complete the following reactions:
O
[H+]
a. CH3-C-OH
+
CH3CH2CH2OH
[H+]
b. (CH3)3CCH2CH2COOH +
(CH3)2CHOH
[H+]
COOH
c.
d. CH3(CH2)2COOH
+
+
CH3CH2OH
OH
[H+]
9-18
9.4 Draw a structural formula for each of the following esters:
a. cyclohexyl propanoate
b. methyl formate
c. ethyl benzoate
d. isopropyl acetate
e. butyl butanoate
f. propyl pentanoate
9.5 Assign names to each of the following amines:
a.
b.
c.
d.
NH2
CH3- NH - CH2 - CH3
(CH3CH2)3N
NH - CH3
e. CH3CH2CH2 - NH2
f.
N
9.6 Complete the following equations:
a.
b.
c.
d.
+
CH3CH2NH2
NH2
+
HCl
HCl
CH3CH2NH-CH3
N(CH3)2
+
+
HBr
HBr
9.7 Draw the structures of 4 isomers of amides of formula C5H11NO.
9-19