Stoker7e PPT CH17

Section 17.
Bonding Characteristics of Nitrogen Atoms in Organic Compounds
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Copyright © Cengage Learning. All rights reserved 1

Chapter 17
Chapter Outline
17.1Bonding characteristics of nitrogen atoms in organic co

mpounds
17.2Structure and classification of amines
17.3Nomenclature for amines
17.4Isomerism for amines
17.5Physical properties of amines
17.6Basicity of amines
17.7 Reaction of amines with acids
17.8 Alkylation of ammonia and amines
17.9 Heterocyclic amines
17.10 Selected biochemically important amines
Copyright ©2016 Cengage Learning. All Rights Reserved. 2

Chapter 17
Chapter Outline
17.11Alkaloids
17.12 Structure of and classification of amides
17.13 Nomenclature for amides
17.14 Selected amides and their uses
17.15Basicity of amides
17.16 Physical properties of amides
17.17 Preparation of amides
17.18 Hydrolysis of amides
17.19 Polyamides and polyurethanes

Section 17.1
Bonding Characteristics of Nitrogen Atoms in Organic Compounds
Nitrogen
• Member of Group VA of the periodic table
• Has five valence electrons
• Forms three covalent bonds to complete its octet of electrons
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Section 17.2
Structure and Classification of Amines
Amine
• Organic derivative of ammonia (NH3) in which

one or more alkyl, cycloalkyl, or aryl groups
have replaced ammonia hydrogen atoms
• Classification
– Primary amine (1°): Nitrogen atom is bonded to one
hydrocarbon group and two hydrogen atoms
– Secondary amine (2°): Nitrogen atom is bonded to
two hydrocarbon groups and one hydrogen atom
– Tertiary amine (3°): Nitrogen atom is bonded to three
hydrocarbon groups and no hydrogen atoms
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Section 17.2
Structure and Classification of Amines
Cyclic Amines
• Either secondary or tertiary amines
• Designated as heterocyclic compounds
• Numerous cyclic amine compounds are found in
biochemical systems
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Section 17.3
Nomenclature for Amines
IUPAC Rules for Naming Primary Amines

• Rule 1 - Select the longest chain to which the
nitrogen atom is attached as the parent carbon
chain
• Rule 2 - Name the parent chain by changing the
-e ending of the corresponding alkane name to -
amine
• Rule 3 - Number the parent chain from the end
nearest to the nitrogen atom
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Section 17.3
IUPAC Rules for Naming Primary Amines

• Rule 4 - Position of attachment of the nitrogen
atom is indicated by a number in front of the
parent chain name
• Rule 5 - Identity and location of any substituents
are appended to the front of the parent chain
name
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Section 17.3
• Secondary and tertiary amines are named as N-

substituted primary amines
• Largest carbon group bonded to the nitrogen is
used as the parent amine name
• Names of the other groups attached to the
nitrogen are appended to the front of the base
name
– N- or N,N- prefixes are used to indicate that the
groups are attached to the nitrogen atom
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Section 17.3
• In amines with additional functional groups, the

amine group is treated as a substituent
– —NH2 group is called an amino group
• Aniline - A benzene ring bearing an amino group
– Other simple aromatic amines are named as
derivatives of aniline
• In secondary and tertiary aromatic amines, the
additional group(s) attached to the nitrogen atom
are located using a capital N-
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Section 17.4
Isomerism for Amines
Reasons for the Occurrence of Constitutional Isomerism in

Amines
• Different carbon atom arrangements
• Different positioning of the nitrogen atom on a
carbon chain
• In secondary and tertiary amines, different
partitioning of carbon atoms among the carbon
chains present
• C4 secondary amines
– Carbon atom partitioning can be two ethyl groups
– Propyl group and a methyl group
– Isopropyl group and a methyl group
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Section 17.5
Physical Properties of Amines
Physical State
• Methylamines (mono-, di-, and tri-) and
ethylamine are gases at room temperature
• Most other amines are liquids at room
temperature
• Physical state summary for unbranched primary
amines at room temperature:
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Section 17.5
Odor (Smell)
• Methylamines (mono-, di-, and tri-) and
ethylamines (gases) have ammonia-like smell
• Most other amines have odors resembling that
of raw fish
• Few amines have strong, disagreeable odors
– Foul smell from dead fish and decaying flesh is due
to diamines released by the bacterial decomposition
of protein
• Odoriferous compounds - Putrescine and cadaverine
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Section 17.5
Boiling Points
• Intermediate between those of alkanes and
alcohols of similar masses
• Lower in 3° amines than 1° and 2° amines
• H-bonding is not possible between the
molecules of 3° amines
• H and N hydrogen bonds are weaker than H and
O hydrogen bonds
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Section 17.5
Figure 17.5 - A Comparison Of Boiling Points
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Section 17.5
Solubility in Water
• Amines with fewer than six carbon atoms are
infinitely soluble in water
– Solubility results from hydrogen bonding between the
amines and water
• Even tertiary amines are water-soluble
– Amine nitrogen atom has a nonbonding electron pair
that can form a hydrogen bond with a hydrogen atom
of water
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Section 17.6
Basicity of Amines
• Amines behave like NH3

– Exhibit Brønsted-Lowry base behavior
– Produce a basic solution when they dissolve in water
– A proton is transferred from a water molecule to the
lone-pair site on the nitrogen atom
• In the example above, water acts as an acid

– The resulting solution is alkaline due to OH– ion and a
substituted ammonium ion Return to TOC

Section 17.6
Basicity of Amines
• Substituted ammonium ion forms four bonds with N

and carries a + charge
– Naming the positive ion
• Alkylamines - The ending of the name of the amine is
changed from amine to ammonium ion
• Aromatic amines - Final -e in the name aniline is
replaced by -ium ion
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Section 17.7
Reactions of Amines with Acids
• Reaction of an acid with a base (neutralization)

produces a salt
– Amines are bases, and their reaction with an acid
produces an amine salt
Amine + acid  amine salt
• Amine salt: Ionic compound in which the positive ion
is a mono-, di-, or trisubstituted ammonium ion (RNH3+,
R2NH2+, or R3NH+) and the negative ion comes from an
acid
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Section 17.7
Reactions of Amines with Acids
• Names of amines salts are written in the

following order:
– Name of the substituted ammonium or anilinium ion
is given first, followed by a separate word for the
name of the negative ion
• All amine salts are water soluble
– Drugs that contain amine functional groups are
administered in the form of amine salts
• Pouring vinegar (acid) on fish to remove odor
– Results in the formation of odorless amine salts
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Section 17.8
Alkylation of Ammonia and Amines
• Alkylation reaction: Chemical reaction in which

alkyl group is transferred from one molecule to
another molecule
• Primary amines are obtained by alkylation of
ammonia in the presence of a base
– If the primary amines are not quickly removed from
alkylation reaction mixture, nitrogen atom of the
amine may react with further alkyl halide molecules
• Produces secondary and tertiary amines in succession
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Section 17.8
Alkylation of Ammonia and Amines
• Secondary and tertiary amines are produced via

the alkylation of primary and secondary amines
respectively
• Tertiary amines react with alkyl halides in the
presence of a strong base to produce a
quaternary ammonium salt
– Quaternary ammonium salt
• Colorless and odorless crystalline solid
• Has a high melting point and is water soluble
• Addition of a strong base does not convert it back to its
parent amine
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Section 17.9
Heterocyclic Amines
• Organic compounds in which nitrogen atoms of

amine groups are part of either an aromatic or a
nonaromatic ring system
• Ring systems may be saturated, unsaturated, or
aromatic
– >1 nitrogen atom may be present in a given ring
– Fused ring systems often occur
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Section 17.9
Heterocyclic Amines
• Important starting material in medicinal,

agricultural, food, and industrial chemistry and in
the functioning of the human body
– Nicotine and caffeine - Stimulants of the central
nervous system
– Porphyrin ring, a component of hemoglobin
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Section 17.10
Selected Biochemically Important Amines
Neurotransmitters
• Substances present in the human body that
assist in passing nerve impulses from one cell to
another
– Acetylcholine - Involved in the transmission of nerve
impulses
– Dopamine - Deficiency may cause Parkinson’s
disease
– Norepinephrine - Neurotransmitter and a stimulant of
the central nervous system
– Serotonin - Involved in sleep, sensory perception, and
the regulation of body temperature
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Section 17.10
Selected Biochemically Important Amines
Central Nervous System Stimulants and Decongestants
• Central nervous system stimulants

– Epinephrine
• Important central nervous system stimulant
• Released into the bloodstream in response to pain,
excitement, and fear
• Increases rate and force of heart contraction and
muscular strength
– Phenethylamine derivative structures - Amphetamine
and methamphetamine
• Decongestants - Pseudoephedrine and
phenylephrine
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Section 17.11
Alkaloids
• Nitrogen-containing organic compounds

extracted from plant material
• Well known alkaloids
– Nicotine (tobacco plant)
– Caffeine (coffee beans and tea leaves)
– Cocaine (coca plant)
– Morphine and codeine (opium plant)
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Section 17.11
Alkaloids
• Used in medicines
– Quinine - Isolated from the cinchona tree bark and
used to treat malaria
– Atropine - Isolated from the belladonna plant and
used as a preoperative muscle relaxant
– Morphine and codeine - Narcotic painkillers
• Codeine derivatives - Hydrocodone and oxycodone
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Section 17.12
Structure and Classification of Amides
• Amides: Derivatives of carboxylic acids in which

the —OH group of the carboxylic acid is
replaced by an amino (NH2) or a substituted
amino (NHR or NR2)
– Classified as primary, secondary, or tertiary
• Amide groups are considered as —R groups
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Section 17.12
Figure 17.12 - Primary, Secondary, and Tertiary Amines and

Amides
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Section 17.12
Amide Classification
• Primary amide (1°): An amide in which two
hydrogen atoms are bonded to the amide
nitrogen atom
• Secondary amide (2°): An amide in which alkyl
(or aryl) group and a hydrogen atom are bonded
to the amide nitrogen atom
• Tertiary amides (3°): An amide in which two
alkyl (or aryl) groups and no hydrogen atoms are
bonded to the amide nitrogen atom
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Section 17.12
Lactam
• Cyclic amide
• Ring size is indicated using a Greek letter
– -lactam - Lactam with a four-membered ring
• -carbon from the carbonyl group is bonded to the
heteroatom
• Members of the penicillin family of antibiotics have
four-membered lactam ring
– γ-lactam - Lactam with a five-membered ring
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Section 17.13
Nomenclature for Amides
• Amides are derivatives of carboxylic acids

• Rules
– Ending of the name of the carboxylic acid is changed
from -ic acid (common) or -oic acid (IUPAC) to -
amide
• Example: Benzoic acid becomes benzamide
– Names of groups attached to the nitrogen (2° and 3°
amides) are appended to the front of the base name,
using an N- prefix as a locator
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Section 17.13
Nomenclature for Amides
• Nomenclature for secondary and tertiary amides

involves use of the prefix N-, a practice used in
amine nomenclature
• Benzamide - A benzene ring that bears an
unsubstituted amide group
– Simplest aromatic amide
– Other aromatic amides are named as benzamide
derivatives
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Section 17.14
Selected Amides and Their Uses
Urea
• Naturally occurring amide, water-soluble white
solid produced in the human body from carbon
dioxide and ammonia through a series of
reactions
CO2 + 2NH3  (H2N)2CO + H2O
• Urea formation - Human body’s method for
eliminating waste nitrogen
– Removed by the kidneys and is excreted via urine
– Uremia - Accumulation of urea in the body due to
kidney malfunction
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Section 17.14
Melatonin
• Polyfunctional amide
• Hormone synthesized by the pineal gland that
regulates the sleep–wake cycle in humans
– Melatonin levels increase in evening hours and
decrease as morning approaches
• High levels are associated with longer and more sound
sleep
• Levels in the blood decreases with age
• Used in the treatment for insomnia and jet lag
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Section 17.14
Acetaminophen
• Synthetic amide that exhibits physiological
activity
• Used as a drug
– Top-selling over-the-counter pain reliever
• Derivative of acetamide
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Section 17.15
Basicity of Amides
• Amide nitrogen is bonded to the carbon atom of

a carbonyl group
– Carbonyl group is polar, the carbonyl C carries a
partial positive charge and the oxygen carries a partial
negative charge
– Partial positive charge on C attracts the lone pair of
electrons on nitrogen atom and causes them to be
tightly held by nitrogen
• Prevents the nitrogen atom of the amide from acting as
a Brønsted–Lowry base
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Section 17.16
Physical Properties of Amides
• Primary amides are solids at room temperature,

except for methanamide
– Methanamide and its N-methyl and N,N-dimethyl are
all liquids at room temperature
• Low molecular mass amides with 5 or 6 carbon
atoms are soluble in water
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Section 17.17
Preparation of Amides
Amidification Reaction
• Reaction of carboxylic acid with ammonia or a
primary or a secondary amine produces an
amide at elevated temperature
– Reaction with ammonia produces a primary amide
• Reaction with a primary amine produces a secondary
amide, and reaction with a secondary amine produces
a tertiary amide
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Section 17.18
Hydrolysis of Amides
• Amides are the least reactive of the carboxylic

acid derivatives
• Under certain conditions, amides undergo
hydrolysis to produce free acid and amine
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Section 17.18
Hydrolysis of Amides
• Catalyzed by acids, bases, or certain enzymes

– Sustained heating may be needed in certain cases
• Under acidic conditions, the amine is converted
to an amine salt
• Under basic conditions, the carboxylic acid is
converted to a carboxylic acid salt
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Section 17.19
Polyamides and Polyurethanes
Polyamide
• Condensation polymer in which the monomers
are joined by amide linkages
• Synthesized by combining diamines and
dicarboxylic acids
• Nylon
– Different types of nylons are based on diamine and
diacid monomers
• Nylon 66 - Polymer of 1,6-hexanediamine and
hexanedioic acid as monomers
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Section 17.19
Nylon Polymer
• White strand of a nylon polymer forms between
two layers of a solution containing a diacid
(bottom layer) and a diamine (top layer)
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Section 17.19
Polyamide
• Additional stiffness and toughness are imparted
if aromatic rings are present in the polymer
backbone
• Polyamide Kevlar is used in making bullet-
resistant vests
• Naturally occurring polyamide polymers - Silk
and wool
• Much of the human body is polyamide polymer
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Section 17.19
Urethane and Polyurethane

• Urethane: Hydrocarbon derivative that contains
a carbonyl group bonded to both an —OR group
and a —NHR (or —NR2) group
• Polyurethane: Polymer formed from the
reaction of dialcohol and diisocyanate
monomers
– Has structural aspects of both polyesters and
polyamides
– Examples: Foam rubber, packaging materials, life
preservers, and elastic fibers
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Section 17.

Bonding Characteristics of Nitrogen Atoms in Organic Compounds

Copyright © Cengage Learning. All rights reserved 1

17.1Bonding characteristics of nitrogen atoms in organic co

Copyright ©2016 Cengage Learning. All Rights Reserved. 2

Copyright ©2016 Cengage Learning. All Rights Reserved. 3

Bonding Characteristics of Nitrogen Atoms in Organic Compounds

• Has five valence electrons

• Forms three covalent bonds to complete its octet of electrons

Copyright ©2016 Cengage Learning. All Rights Reserved. 4

Structure and Classification of Amines

• Organic derivative of ammonia (NH3) in which

Copyright ©2016 Cengage Learning. All Rights Reserved. 5

Structure and Classification of Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 6

Nomenclature for Amines

IUPAC Rules for Naming Primary Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 7

Nomenclature for Amines

IUPAC Rules for Naming Primary Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 8

Nomenclature for Amines

• Secondary and tertiary amines are named as N-

Copyright ©2016 Cengage Learning. All Rights Reserved. 9

Nomenclature for Amines

• In amines with additional functional groups, the

Copyright ©2016 Cengage Learning. All Rights Reserved. 10

Isomerism for Amines

Reasons for the Occurrence of Constitutional Isomerism in

Copyright ©2016 Cengage Learning. All Rights Reserved. 11

Physical Properties of Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 12

Physical Properties of Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 13

Physical Properties of Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 14

Physical Properties of Amines

Figure 17.5 - A Comparison Of Boiling Points

Copyright ©2016 Cengage Learning. All Rights Reserved. 15

Physical Properties of Amines

Copyright ©2016 Cengage Learning. All Rights Reserved. 16

• Amines behave like NH3

• In the example above, water acts as an acid

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• Substituted ammonium ion forms four bonds with N

Copyright ©2016 Cengage Learning. All Rights Reserved. 18

Reactions of Amines with Acids

• Reaction of an acid with a base (neutralization)

Copyright ©2016 Cengage Learning. All Rights Reserved. 19

Reactions of Amines with Acids

• Names of amines salts are written in the

Copyright ©2016 Cengage Learning. All Rights Reserved. 20

Alkylation of Ammonia and Amines

• Alkylation reaction: Chemical reaction in which

Copyright ©2016 Cengage Learning. All Rights Reserved. 21

Alkylation of Ammonia and Amines

• Secondary and tertiary amines are produced via

Copyright ©2016 Cengage Learning. All Rights Reserved. 22

• Organic compounds in which nitrogen atoms of

Copyright ©2016 Cengage Learning. All Rights Reserved. 23

• Important starting material in medicinal,

Copyright ©2016 Cengage Learning. All Rights Reserved. 24

Selected Biochemically Important Amines