11/2/23
General, Organic, and Biological Chemistry:
Structures of Life
Sixth Edition
Chapter 18
Amines and Amides
Amines and Amides
Amines and amides are organic compounds that contain nitrogen.
Learning Goal: Write the IUPAC and common names for amines; draw the condensed
structural and line-angle formulas when given their names. Classify amines as primary
(1°), secondary (2°), or tertiary (3°)
1
11/2/23
18.1 Amines
Amines
• are derivatives of ammonia, NH3, in which one or more
hydrogen atoms are replaced with alkyl or aromatic groups.
• contain N attached to one or more alkyl or aromatic groups.
Naming Amines, IUPAC (1 of 2)
In the IUPAC names for amines, the e in the corresponding alkane name is
replaced with amine.
Amines with three or more carbon atoms are numbered to show the position of
the –NH2 group and any other substituents.
2
11/2/23
Naming Amines, IUPAC (2 of 2)
• If there is are 2 alkyl group attached to the nitrogen atom, the
prefix N and the alkyl name are placed in front of the amine name.
• If there are 3 alkyl groups bonded to the N atom, the prefix N is
used for each, and they are listed alphabetically.
Learning Check 1
Write the IUPAC name for the following amine:
3
11/2/23
Solution 1 (1 of 3)
Write the IUPAC name for the following amine:
Step 1 Name the longest carbon chain bonded to the N
atom by replacing the e of its alkane name with amine.
Solution 1 (2 of 3)
Give the IUPAC name for the following amine:
Step 2 Number the carbon chain to show the position of
the amine group and other substituents.
4
11/2/23
Solution 1 (3 of 3)
Give the IUPAC name for the following amine:
Step 3 Any alkyl group attached to the nitrogen atom is
indicated by the prefix N- and the alkyl name, which is
placed in front of the amine name.
Aromatic Amines
• Aromatic amines are called aniline, IUPAC, simplest amine.
• When alkyl groups attached to the nitrogen, use the prefix N
with the alkyl name.
• Aniline is used to make many dyes, blue jeans.
10
5
11/2/23
Classification of Amines
Amines are classified as primary, secondary, or tertiary.
• A primary 1° amine has one carbon bonded to the nitrogen atom
• A secondary 2° amine has two carbons bonded to the nitrogen atom
• A tertiary 3° amine has three carbons bonded to the nitrogen atom
1° 2° 3°
11
Learning Check 2
Give the IUPAC name for each amine and classify it as primary,
secondary, or tertiary.
A. CH3 ¾ CH2 ¾ CH2 ¾ NH2
B.
12
6
11/2/23
Solution 2
Give the IUPAC name for each amine and classify it as
primary, secondary, or tertiary.
A. CH3 ¾ CH2 ¾ CH2 ¾ NH2 1-propylamine 1°
B. N,N-dimethylethylamine 3°
13
Learning Check 3
Give the IUPAC name of each amine compound.
A.
B.
14
7
11/2/23
Solution 3
Give the IUPAC name of each amine compound.
A.
N-ethyl-N-methylethanamine
B. N-ethylaniline
15
Line-Angle Formulas of Amines
16
8
11/2/23
18.2 Properties of Amines
Learning Goal: Describe the boiling points and solubility of amines; write balanced
chemical equations for the reaction of amines with water and with acids.
17
Hydrogen Bonding in Amines
• Amines contain polar N—H bonds.
• Primary and secondary amines, can form hydrogen bonds with each
other and with water molecules.
• Tertiary amines can only form hydrogen bonds with water molecules.
• Nitrogen is not as electronegative as oxygen, so hydrogen bonds in
amines are weaker than the hydrogen bonds in alcohols.
18
9
11/2/23
Boiling Points of Amines
• Amines have boiling points that are higher than those of alkanes but
lower than those of alcohols.
• Primary amines can form more hydrogen bonds than secondary amines
of the same mass and therefore, they have higher boiling points.
• Tertiary amines cannot form hydrogen bonds with each other and have
lower boiling points than primary or secondary amines of the same mass.
19
Solubility of Amines in H2O
• Amines that contain a polar N—H bond can form hydrogen bonds
with water.
• Primary, secondary, and tertiary amines with one to six carbon
atoms are soluble in water.
• As the number of carbon atoms in amine increases in the nonpolar
alkyl portions, the effect of hydrogen bonding is diminished.
20
10
11/2/23
Solubility of Amines in H2O (3 of 3) H sub 2 O
Amines with more than six carbon atoms,
• the nonpolar hydrocarbon chains of the amine decrease its
solubility in water.
21
Learning Check 1
Which of the following compounds are soluble in water?
A. CH3 — CH2 — CH2 — NH2
B. CH3 — CH2 — NH — CH3
C. CH3 — CH2 — CH2 — CH3
D.
22
11
11/2/23
Solution 1
Which of the following compounds are soluble in water?
A. CH3 — CH2 — CH2 — NH2 soluble in water
B. CH3 — CH2 — NH — CH3 soluble in water
C. CH3 — CH2 — CH2 — CH3 alkane, not soluble in water
D.
more than six carbons,
not soluble in water
23
Amines React as Bases in Water (1of 2)
Ammonia, primary, and secondary amines act as a Brønsted–Lowry
base by accepting H+ from water to produce an ammonium ion NH4+
and a hydroxide ion OH-
24
12
11/2/23
Amines React as Bases in Water (2 of 2)
25
Neutralization of Amines (1 of 2)
Lemon removes the “fishy” odor
from amines is removed by
converting them to their
ammonium salts.
26
13
11/2/23
Neutralization of Amines (2 of 2)
In a neutralization reaction,
• amines are bases. They reacts with acid to form ammonium salt.
• the nitrogen atom accepts H+ from the acid to give ammonium salt.
• ammonium salt is named by using its alkylammonium ion name
followed by the name of the negative ion.
27
Quaternary Ammonium Salts
In a quaternary ammonium salt,
• nitrogen atom is bonded to four carbon groups, which classifies it
as a quaternary (4°) amines.
• nitrogen atom has a positive charge and is not bonded to H atom.
Choline, a component of glycerophospholipids, is a quaternary
ammonium ion.
28
14
11/2/23
Properties of Ammonium Salts
Ammonium salts are
• ionic compounds with strong attractions between the positively
charged ammonium ion and anions, usually chlorides.
• solids at room temperature, odorless, and soluble in water and
body fluids.
Amines are usually converted to their ammonium salt before being
used as drugs.
29
Learning Check 2
Draw the condensed structural formula for the ammonium
salt formed by the reaction of trimethylamine and HCl.
30
15
11/2/23
Solution 2
Draw the condensed structural formula for the ammonium
salt formed by the reaction of trimethylamine and HCl.
31
18.3 Heterocyclic Amines
A heterocyclic amine is a cyclic organic compound that consists of a
ring of five or six atoms, of which one or two are nitrogen atoms.
The aroma of pepper is due to piperidine, a heterocyclic amine.
Learning Goal: Identify heterocyclic amines; distinguish between the types of heterocyclic amines.
32
16
11/2/23
Heterocyclic Amines, Five-atom Rings
Of the five-atom rings,
• the simplest one is pyrrolidine, which is a ring of four carbon atoms and
one nitrogen atom, all with single bonds.
• pyrrole is a five-atom ring with one nitrogen atom and two double bonds.
• imidazole is a five-atom ring that contains two nitrogen atoms.
33
Heterocyclic Amines, Six-atom Rings
Of the six-atom rings,
• piperidine, responsible for the pungent aroma and taste of black
pepper, is a six-atom heterocyclic ring with a nitrogen atom.
• purine and pyrimidine rings are found in DNA and RNA.
In purine, the structures of six-atom pyrimidine and five-atom imidazole
are combined.
34
17
11/2/23
Alkaloids: Amines in Plants (1 of 4)
Alkaloids are
• physiologically active compounds produced by plants that contain
heterocyclic amines.
• used in anesthetics, in antidepressants, and as stimulants.
Nicotine, an alkaloid.
35
Alkaloids: Amines in Plants (2 of 4)
Caffeine
• is an alkaloid found in coffee beans, tea, chocolate, and soft drinks.
• is a stimulant of the central nervous system.
36
18
11/2/23
Learning Check
Identify the heterocyclic amines in the following:
A. B. C. D.
37
Solution
Identify the heterocyclic amines in the following:
A. B. C. D.
A, B, and C are heterocyclic amines; D is not.
38
19
11/2/23
18.5 Amides
Tylenol, an aspirin substitute,
contains acetaminophen.
Acetaminophen is an amide; it acts
to reduce fever and pain; however,
it has little anti-inflammatory effect.
Learning Goal: Draw the amide product from amidation, and write the IUPAC and
common names.
39
Preparation of Amides (1 of 2)
Amides
are derivatives of carboxylic acids in which a nitrogen group
replaces the hydroxyl –OH group of carboxylic acids.
40
20
11/2/23
Preparation of Amides (2 of 2)
Amides are produced
• in a reaction called amidation or condensation.
• when a carboxylic acid reacts with ammonia or a primary or
secondary amine and heat.
Amide production is accompanied by the production of water.
41
Learning Check 1
Predict the products of the following amidation reaction:
42
21
11/2/23
Solution 1
Predict the products of the following amidation reaction:
43
Naming Amides (1 of 4)
• In both the common and IUPAC names, amides are named by
dropping the oic acid (IUPAC) or ic acid (common) from the
carboxylic acid name and adding the suffix amide.
44
22
11/2/23
Naming Amides (2 of 4)
• Alkyl groups attached to the nitrogen of an amide are named
with the prefix N followed by the alkyl name.
45
Naming Amides (3 of 4)
Give the IUPAC name for the following amide:
46
23
11/2/23
Naming Amides (3 of 4)
Give the IUPAC name for the following amide:
Analyze The
Given Need Connect
Problem
Analyze The Replace oic acid with amide,
amide IUPAC name
Problem alkyl substituent has prefix N-
Step 1 Replace oic acid in the carboxylic acid name with amide.
47
Naming Amides (4 of 4)
Give the IUPAC name for the following amide:
Step 2 Name each substituent on the N atom using the prefix N- and
the alkyl name.
48
24
11/2/23
Learning Check 2
Give the IUPAC name for the following amides:
A.
B.
49
Solution 2
Give the IUPAC and common names for the following amides:
A. ethanamide (IUPAC)
B.
N-ethylpropanamide (IUPAC)
50
25
11/2/23
Physical Properties of Amides (1 of 2)
• Amides do not have the properties of bases seen in amines.
• Only methanamide is a liquid at room temperature, while other
amides are solids.
• Primary amides have the highest melting points because the –NH2
group can form more hydrogen bonds.
• Melting points of the secondary amides are lower because they form
fewer hydrogen bonds, –NH
• Tertiary amides cannot form hydrogen bonds; they have the lowest
melting points (see Table below).
51
H-Bonding in 1° Amides firstdegree
Primary amides, can form
• hydrogen bonds with each other.
• hydrogen bonds with water molecules making them soluble in
water as long as they have less than five carbons.
52
26
11/2/23
H-Bonding in 2° Amides Twodegree
Secondary amides
• have lower melting points because they form fewer hydrogen
bonds with each other.
• form hydrogen bonds with water molecules, making them
soluble in water as long as they have fewer than five carbons.
53
H-Bonding in 3° Amides Threedegree
Tertiary amides
• have the lowest melting points because cannot form hydrogen
bonds with each other.
• can only form one hydrogen bond with H2O
54
27
11/2/23
Chemistry Link to Health: Amides and Medicine
Urea is
• excreted in the urine and the
simplest natural amide.
• the end product of protein
metabolism in the body.
• Acetaminophen, reduce fever
and pain.
55
18.6 Hydrolysis of Amides
In a reverse reaction of amidation, hydrolysis occurs when water
and an acid or a base split an amide.
Learning Goal: Write balanced chemical equations for the hydrolysis of amides.
56
28
11/2/23
Acid Hydrolysis of Amides
Amides undergo acid hydrolysis with heat to produce a
carboxylic acid and an ammonium salt.
57
Base Hydrolysis of Amides (1 of 3)
Amides undergo base hydrolysis with heat to produce a
carboxylate salt and an amine or ammonia.
58
29
11/2/23
Base Hydrolysis of Amides (2 of 3)
Draw the condensed structural formulas and write the IUPAC
names for the products from the hydrolysis of
N-methylpentanamide with NaOH.
59
Base Hydrolysis of Amides (3 of 3)
Draw the condensed structural formulas and write the IUPAC names
for the products from the hydrolysis of N-methylpentanamide with NaO
H in the base hydrolysis of the amide,
• the amide bond is broken between the carboxyl carbon atom and the
nitrogen atom.
• the products are the carboxylate salt and an amine.
60
30
11/2/23
Learning Check
Draw the condensed structural formulas for the products from
the hydrolysis of the following amide with HCl:
61
Solution
Draw the condensed structural formulas for the products
from the hydrolysis of the following amide with HCl:
62
31
11/2/23
Concept Map
63
32
