Chapter 6 Amines and Amides

Chapter 6
Amines and Amides

Chapter Objectives:
• Learn to recognize the amine and amide functional groups.
• Learn the IUPAC system for naming amines and amides.
• Learn the important physical properties of the amines and amides.
• Learn the major chemical reactions of amines and amides, and learn how to predict the
products of amide synthesis and hydrolysis reactions.
• Learn some of the important properties of condensation polymers, especially the
polyamides.

Mr. Kevin A. Boudreaux

Angelo State University
CHEM 2353 Fundamentals of Organic Chemistry
Organic and Biochemistry for Today (Seager & Slabaugh)
www.angelo.edu/faculty/kboudrea

Nitrogen-Containing Functional Groups

• Nitrogen is in Group V of the periodic table, and in
most of its compounds, it has three single bonds and
one lone pair:
N

• In this chapter, we will take a look at two functional

groups which contain nitrogen atoms connected to
carbons: the amines and the amides.
O

R N R'' R C N R'

R' R"
Amine Amide
2
Chapter 6 Amines and Amides

Classification and
Nomenclature of Amines

Amines
• Amines and amides are abundant in nature. They
are a major component of proteins and enzymes,
nucleic acids, alkaloid drugs, etc. (Alkaloids are N-
containing, weakly basic organic compounds;
thousands of these substances are known.)
• Amines are organic derivatives of ammonia, NH3, in
which one or more of the three H’s is replaced by a
carbon group.
• Amines are classified as primary (1°), secondary
(2°), or tertiary (3°), depending on how many
carbon groups are connected to the nitrogen atom.

H N H R N H R N H R N R''

H H R' R'
Ammonia 1° Amine 2° Amine 3° Amine 4
Chapter 6 Amines and Amides

Examples: Classifying Amines

• Classify the following amines as primary (1°),
secondary (2°), or tertiary (3°).

H CH3 NH2

CH3CH2CH2 N H CH3 N CH3 CH3CH2CHCH3

CH3CH2 N CH3 N
N
H

Nomenclature of Amines
• Simple 1°, 2°, and 3° amines: common (trivial)
names are obtained by alphabetically arranging the
names of the alkyl substituents on the nitrogen and
adding the suffix -amine (e.g., ethylmethylamine).
• Amines in the IUPAC system: the “e” ending of
the alkane name for the longest chain is replaced
with –amine. The amine group is located by the
position number. Groups that are attached to the
nitrogen atom are located using “N” as the position
number. More complex primary amines are named
with —NH2 as the amino substituent.
NH2
• Aromatic amines: named as derivatives of the
parent compound aniline. Substituents attached to
the nitrogen are indicated by using “N-” as the
location number.
aniline 6
Chapter 6 Amines and Amides

Examples: Nomenclature of Amines

• Provide common names for the following 2° and 3°
amines; for 1° amines, provide common and/or
IUPAC names where possible.
H

CH3 NH2 CH3 N CH3

CH3 N CH2CH3 CH3CH2CH2 NH2

Examples: Nomenclature of Amines

• Provide common names for the following 2° and 3°
amines; for 1° amines, provide common and/or
IUPAC names where possible.
NH2 CH3

CH3CH2CH2CHCH3 CH3 N CH3

NH CH3 CH3CHCH2CH2 NH2

CH3CH2CH2CHCH3 NH2

8
Chapter 6 Amines and Amides

Examples: Nomenclature of Amines

• Provide common names for the following 2° and 3°
amines; for 1° amines, provide common and/or
IUPAC names where possible.
OH

O NH2 NH2

CH3CCH2CH2CH2CHCH3

Examples: Nomenclature of Amines

• Provide names for the following aromatic amines.
NH CH3 NH2

CH3

CH3 CH3 CH3 CH2CH3

N N

10
Chapter 6 Amines and Amides

Examples: Nomenclature of Amines

• Provide names for the following aromatic amines.

CH3 CH3 CH3 H

N N

CH3 CH2CH3

CH3 CH3
N

CH3CH2 CH3
11

Examples: Nomenclature of Amines

• Draw structural formulas for the following molecules:
– ethylisopropylamine

– tert-butylamine

– 2-pentanamine

12
Chapter 6 Amines and Amides

Examples: Nomenclature of Amines

• Draw structural formulas for the following molecules:
– N-methyl-2-propanamine

– 1,6-diaminohexane

– 3-amino-1-propanol

13

Examples: Nomenclature of Amines

• Draw structural formulas for the following molecules:
– N-methyl-2-chloroaniline

– N,3-diethylaniline

– N,N-dimethylaniline

14
Chapter 6 Amines and Amides

Physical Properties of
Amines

15

Physical Properties of Amines: H-Bonding

• 1° and 2° amines can hydrogen bond to each other:
CH3 N H CH3 N CH3

H H
H H

CH3 N H N H CH3 N H N CH3

H CH3 CH3 CH3

• 3° amines cannot hydrogen bond to each other:
CH3 N CH3

CH3 CH3
X
CH3 N CH3 X N CH3
16
CH3 CH3
Chapter 6 Amines and Amides

Physical Properties of Amines: Boiling Points

• Nitrogen is less electronegative than oxygen, so the
N—H bond is not quite as polar as the O—H bond.
– Hydrogen bonds from N—H’s are not as strong
as those resulting from O—H’s.
– Hydrogen bonding between 1° and 2° amines is
not as strong as those found in alcohols or
carboxylic acids.
• 1° and 2° amines have lower boiling points than
alcohols of similar molecular weight.
• 3° amines, since they do not hydrogen bond to each
other, have boiling points similar to hydrocarbons of
the same molecular weight.

17

Physical Properties of Amines: Boiling Points

Boiling Point:
Carboxylic acid
Alcohols
1°/2° Amines
3° Amines/Alkanes

Name Molecular Boiling

weight point
Acetic acid 60.0 g/mol 118°C
1-propanol 60.1 g/mol 97°C
propyl amine 59.1 g/mol 48°C
ethylmethylamine 59.1 g/mol 36°C
trimethylamine 59.1 g/mol 2.9°C
butane 58.1 g/mol -0.5°C 18
Chapter 6 Amines and Amides

Physical Properties of Amines: Water Solubility

• 1°, 2°, and 3° amines can all form hydrogen bonds
with water.
• Low-molecular weight amines are generally water-
soluble.
H H H
O O O

H H H H H

CH3 N H O CH3 N H O CH3 N CH3

H H CH3 H CH3

O
H H

19

Physical Properties of Amines: Odor

• Low molecular-weight amines tend to have sharp,
penetrating odors similar to ammonia
• Higher molecular-weight amines often smell like
rotting fish, and are often found in decaying animal
tissues.
NH2 NH2

CH3 N CH3 CH2CH2CH2CH2 CH2CH2CH2CH2CH2

CH3 NH2 NH2

Trimethylamine 1,4-Diaminobutane 1,5-Diaminopentane
Responsible for the (Putrescine) (Cadaverine)
odor of rotting fish A poisonous oil present in A poisonous, viscous liquid
rotting flesh; produced present in rotting flesh;
during the decomposition of produced during the
the amino acid arginine; also decomposition of the amino
partially responsible for the acid lysine; also partially
odor of urine and bad breath responsible for the odor of
20
urine and bad breath
Chapter 6 Amines and Amides

Examples: Predicting Physical Properties

• Arrange the following compounds in order of
increasing boiling point. (All of the compounds
have about the same molecular weight.)
propanoic acid, diethylamine, 1-butanol,
ethyldimethylamine

21

Examples: Predicting Physical Properties

• Which member of each of the following pairs of
compounds would you expect to have a higher
boiling point?
– 2-aminopropane or 2-aminohexane

– triethylamine or 1-aminohexane

– propanoic acid or diethylamine

– 1-pentanol or 1-aminopentane
22
Chapter 6 Amines and Amides

Some Important
Alkaloids

23

Important Alkaloids
O O
CH3 CH3 H
CH3 N H
N N
N N

CH3
O N N N N
O N
Nicotene
CH3 CH3 Found in tobacco plants; mild
Caffeine Theobromine stimulant in small doses;
Found in the seeds of Coffea arabica, Found in the seeds of addictive, but not especially
roasted coffee beans; inhibits the action of Theobroma cacao; the harmful itself
phosphodiesterase, an enzyme which stimulating ingredient in
inhibits cyclic adenosine monophosphate chocolate.
(AMP), which is responsible for forming
glucose in the bloodstream
CH3 N
HO
N

CH3O

N
Dextromethorphan Quinine
CH3O Antimalarial drug from cinchona tree 24
Ingredient in cough suppressants.
Chapter 6 Amines and Amides

CH3 CH3 CH3

N O N N

OCH3
O
H
H H H
O O O
O O O OH

OH
Cocaine Atropine
The form which is “snorted” relaxes muscles and reduces secretion
is the hydrochloride salt; the of saliva during surgery; used to Scopolamine
free-base “crack” form is dilate pupils for eye examinations. used in treatment of motion
burned and inhaled, and sickness
reaches the brain in 15
H3C CH3
seconds.
+
N
R
N Zephiran chloride
H H (benzalkonium chloride)
Coniine Antiseptic compound that kills
Poison from hemlock bacteria and fungi on contact
25

O O CH2CH3

H N
N CH2CH3
CH3O H
N
CH3
N H
H
Melatonin
A naturally occuring hormone produced in the
pineal gland; its production is triggered by the N
absence of light; causes drowsiness in humans H
Lysergic acid diethylamide (LSD)
at night, triggers birds to migrate, and signals
A synthetic hallucinogen from alkaloids obtained
dogs to shed their winter coats; sold as a
from ergot, a fungus which grows on rye
treatment for jet lag.
OH

Strychnine N
H N N
A poison from strychnos
O
plant (Nux vomica); used
as a rat and mouse poison N N
H H HO P
O
N OH
H
OH OH
O O
H Inosine Monophosphate (IMP)
With monosodium glutamate (MSG), one of the
major substances responsible for the flavor of meat 26
Chapter 6 Amines and Amides

HO CH3O CH3 O

O O O
N N N
O
CH3 CH3 CH3

HO HO CH3 O
Morphine Codeine Heroin
Found in the opium poppy; a Used in some cough syrups to More fat-soluble than morphine,
CNS depressant; very effective depress the action of the cough and must be injected directly into
painkiller center of the brain the bloodstream, but crosses the
blood-brain barrier more readily,
causing it to be more potent than
morphine

27

Nitrogen Wastes
The disposal of waste nitrogen from the body is a problem which different species of animals
have solved in different ways:
O H O OH
H
O NH2 O
H N
N NH2
N O
O O N N NH2
O N N
O N N
H H
H H
H
H Allantoic acid
Allantoin Marine vertebrates further
Uric acid
Most mammals contain enzymes metabolyze allantoin into
Birds, reptiles and insects excrete nigrogen
which metabolyze uric acid into allantoic acid.
wastes in the form of uric acid. Uric acid can
allantoin.
be eliminated directly in the solid form, without
being dissolved in water. It is produced in the O
body from foods and beverages rich in purines,
such as claret and port. Lactic acid inhibits the H H
removal of salts of uric acid in the urine; these N N NH4+ X–
salts instead deposit in the joints, causing gout. Marine invertebrates excrete
Dalmations have been bred to have black spots H H ammonium salts.
with no white hairs in them on their coats; Urea
however, the gene which determines the Urea is the major organic
presence of white hairs is linked to the gene component of urine; about 25 g
which codes the enzyme which breaks down are excreted every day by
uric acid into allantoin. Dalmations thus humans. Cartilaginous fish and
excrete uric acid instead of allantoin, and are amphibians also excrete urea.
28
very susceptible to gout.
Chapter 6 Amines and Amides

Antihistamines
NH2

N N
H
Histamine
People who are allergic to pollen produce histamine, which causes blood vessels
to dilate and leak, releasing fluid into surrounding tissues, causing watery eyes,
sniffles, congestion, and other symptoms of hay fever (allergic rhinitis); also
causes the symptoms of the common cold and swelling after insect bites.

CH3

N
O CH3 CH3

CH3
N

OH H
Diphenylhydramine Ephedrine / Pseudoephedrine
an antihistamine; active ingredient in Benadryl; found in the Chinese ma-huang plant; a
sometimes used in sleeping pills decongestant used in many cold remedies

29

Antihistamines
O
Cl

HO
N OH

N N
OH

O Fexofenadine (Allegra®)
O
A non-drowsy antihistamine; available by
Loratadine (Claritin®)
perscription only
A non-drowsy antihistamine

N OH
Cl O
Cetrizide (Zyrtec®)
A stronger antihistamine than Allegra or O
Claritin, but causes drowsiness in some people 30
Chapter 6 Amines and Amides

Reactions of Amines

31

Bases
• A base takes a proton (H+) from another species.
A base produces hydroxide ions, OH–, when
dissolved in water:
B + H2O  BH+ + OH–
• A strong base is one that completely dissociates in
water (i.e., every molecule of the acid splits apart).
• A weak base is one in which only a small
percentage of the molecules are dissociated at any
one time.

• Acidic solution: pH < 7.00 ([H3O+] > [OH-])

• Basic solution: pH > 7.00 ([H3O+] < [OH-])
• Neutral solution: pH = 7.00 ([H3O+] = [OH-]) 32
Chapter 6 Amines and Amides

Chemical Properties of Amines: Basicity

• Amines are weak organic bases. They react with
water to produce alkylammonium ions and
hydroxide anions:
H H

R N + H O R N H + OH

H H H

• and with acids to produce alkylammonium salts:

H H

R N + H Cl R N H Cl

H H
33

Alkylammonium Salts
• Salts of amines are named by changing “amine” to
“ammonium” and adding the name of the negative
ion to the end of the word:
H C2H3O2

CH3 NH3 Cl CH3 N CH2CH3

methylammonium
chloride H
ethylmethylammonium
acetate

CH2CH3

CH3CH2 N CH2CH3

H Br
triethylammonium
bromide 34
Chapter 6 Amines and Amides

Alkylammonium Salts
• Salts of amines are generally white crystalline solids
with high melting points.
• The ionic charges makes these salts more soluble in
water than the neutral amines. Many amine-
containing drugs are administered in the form of
alkylammonium salts to increase their solubility in
bodily fluids.
H3C H3C H
-
N HSO4 N

+ H2SO4

O O
HO OH HO OH
Morphine Morphine sulfate 35
water-insoluble water-soluble

Chemical Properties of Amines: Basicity

• Ammonium salts may be converted back into neutral
amines by a strong base:

R—NH3+ Cl- + NaOH  R—NH2 + H2O + NaCl

• Thus, by adjusting the pH of the solution, it is

possible to influence whether an amine is present in
the neutral form or as its ammonium cation form:
acid
(low pH)
-
R NH2 + H2O R NH3+ + OH
base
amine alkylammonium
(high pH)
ion

36
Chapter 6 Amines and Amides

Quaternary Ammonium Salts

• In addition to salts of 1°, 2°, and 3° amines, it is
possible to have amine cations which contain four
alkyl groups attached to a nitrogen atom, which will
always carry a positive charge, regardless of the pH
of the surrounding solution. These are known as
quaternary ammonium salts.
R''' CH2CH3

R N+ R'' X- CH3 N+ CH2CH3 Cl-

R' CH2CH3
quaternary triethylmethylammonium chloride
ammonium salt

• These salts are present in many antiseptics and

antibacterial agents.
37

Examples: Basicity of Amines

• Complete the following reactions:
CH3NH2 + HCl

NHCH3

+ HCl

CH3
Cl
CH3 N H + NaOH

CH3
38
Chapter 6 Amines and Amides

Amides

39

Amides
• Amides contain a nitrogen which is directly attached
to a carbon in a carbonyl group:
O amide linkage (peptide bond)

R C N R'

R"
Amide

O O O

R C N H R C N CH3 R C N CH3

H H CH3
N,N-unsubstituted amide N-substituted amide N,N-disubstituted amide
40
Chapter 6 Amines and Amides

Nomenclature of Amides
• Amides are named by changing the -oic acid ending
of the corresponding carboxylic acid to -amide. If
alkyl groups are attached to the nitrogen, they are
named as N-alkyl substituents.
O O
O
H C OH H C NH2
methanoic acid methanamide C
(formic acid) (formamide) NH2

O O
benzamide
CH3 C OH CH3 C NH2
ethanoic acid ethanamide
(acetic acid) (acetamide)

41

Examples: Nomenclature of Amides

• Name the following compounds:
O O

CH3 C N CH3 CH3 N C CH3

H CH3

O CH3

CH3 N C C CH3

CH3 CH3

42
Chapter 6 Amines and Amides

Examples: Nomenclature of Amides

• Name the following compounds:

O CH3

CH3CH2CH2 C N CH2CH3

NH2 O

CH3CH2CH2CHCH C N CH3

CH3 H

43

Examples: Nomenclature of Amides

• Name the following compounds:
CH2CH3 O CH3

CH3CH2CH2CHCH2 C N CH2CH3

CH3

CH3 O CH2CH3 CH2CHCH3

CH3 N C CHCH2CH2CCH3

CH3
44
Chapter 6 Amines and Amides

Examples: Nomenclature of Amides

• Name the following compounds:
O

C
CH3 N

C
N CH3

CH3

45

Examples: Nomenclature of Amides

• Name the following compounds:
O

CH3 C
N CH3
H

CH3 C
N CH3

CH3

CH3
46
Chapter 6 Amines and Amides

Examples: Nomenclature of Amides

• Draw structural formulas for the following molecules:
– 2-methylpropanamide

– N,2,4-trimethylpentanamide

– N-ethyl-N-methylacetamide

47

Examples: Nomenclature of Amides

• Draw structural formulas for the following molecules:
– N,2-diethylbenzamide

– N,N,2,3,4-pentamethylbenzamide

– N,N,4,4-tetramethylbutanamide (what’s wrong with this name?)

48
Chapter 6 Amines and Amides

Physical Properties of
Amides

49

Physical Properties of Amides

• N,N-unsubstituted amides can form a complex
network of hydrogen bonds. They tend to have high
melting points and also high boiling points.
O

R C N H

H
H

O N H

R C N H O C

H R

R C N H
50
H
Chapter 6 Amines and Amides

Physical Properties of Amides

• N-substituted amides often have lower melting
points and boiling points than N,N-unsubstituted
amides because fewer hydrogen bonds can form.
• N,N-disubstituted amides cannot form hydrogen
bonds, and have even lower melting points and
boiling points.
• All amides can hydrogen bond with water, so low-
molecular weight amides are water-soluble.

Boiling Point:
N,N-unsubstituted amides
N-substituted amides
N,N-disubstituted amides
51

Examples: Predicting Physical Properties

• Arrange the following compounds in order of
increasing boiling point. (All of the compounds
have about the same molecular weight.)
N-ethylethanamide
butanamide
N,N-dimethylethanamide

52
Chapter 6 Amines and Amides

Important Amides

53

Important Amides

H O
O
N
N
CH2CH3
Cl N O
O N
CH2CH3 O N O

H
Thalidomide
Until 1956, a very popular, safe
sedative; the largest market was for
Diazepam (Valium) CH3
pregnant women who were
A benzodiazepene
N,N-Diethyl-m-toluamide experiencing morning sickness.
tranquilizer; acts by
Active ingredient in OFF However, it caused massive birth
enhancing the inhibitory
defects in women who used it in the
neurotransmitter GABA;
early states of pregnancy, and was
since it binds to the same
banned in Europe; it was never
protein as ethanol,
authorized for sale in the U.S.
combinations of valium and
ethanol can be deadly

54
Chapter 6 Amines and Amides

Hot Stuff

O N C S

CH3O
Allyl isocyanate
N
Capsaicin Used in horseradish flavor,
H Found in red and green chili mustard oil, pickles, salad
HO peppers; active component of dressings and sauces; mustard
paprika plasters, medications and
fumigants

O O
Piperine
O Component of white and CH3O
black pepper
N
HO Zingerone
The pungent, hot component of ginger
O

55

Barbiturates
O H
O H
N
N
O
S
N
N
O H
Barbituric acid O H
First synthesized by Adolf von Baeyer in 1864; Thiopental (Pentothal)
barbiturates are soporifics, and are used as An intravenous anesthetic
tranquilizers and anesthetics; many are also
addictive, and overdoses can be fatal. (Other
barbiturates include Seconal, Veronal,
Phenobarbitol, Thiopental, Amobarbitol, etc.)

O H O H

N N

O O

N N
O H
O H
Amobarbital (Amytal) Phenobarbitol
Used in the treatment of insomnia Anti-seizure medication, sedative
56
Chapter 6 Amines and Amides

Sulfa Drugs
N O O

N S NH2 H2N S NH2

NH2 O O
Prontosil Sulfanilamide
O OH
O

OH O
N

H H O OH
O N

H N Folic acid
H2N
N
para-Aminobenzoic aid
(PABA)
H2N N N

Sulfanilamide, the first antibiotic, was discovered by Gerhard Damagk (Nobel Prize,
1939), who observed the antibacterial action of the red dye Protonsil; further researched
showed that it was the metabolic byproduct, sulfanilamide, which was the active form.
It prevents bacteria from synthesizing folic acid, which they need in order to grow.
Bacterial enzymes synthesize folic acid using para-aminobenzoic acid (PABA);
sulfanilamide fits into the enzyme more tightly, blocking it from taking up PABA, and
thus blocking folic acid synthesis. The bacterium cannot grow, and eventually dies.
Humans obtain folic acid from their diet (an essential vitamin), so sulfa drugs do not
harm people in this way (although they can cause allergic reactions). 57

Penicillin
R=

H Penicillin G
O
N
S
CH3
R
O Penicillin V
N CH3
O
CO2H
Penicillin Ampicillin
NH2

OCH3
Penicillin is an antibiotic compound produced by
the molds Penicillium notatum and Penicillium
chrysogenum; it was discovered by Alexander
Fleming in 1928 in a culture of bread mold. There Methicillin
are several varieties: Penicillin G and Methicillin
are administered by injection; Penicillin V is an
oral form which is not broken down in the OCH3
stomach; Ampicillin is a broad spectrum penicillin
which can be administered by injection or orally
58
Chapter 6 Amines and Amides

Molecules To Dye For

• Dyes are compounds that can be used to color other materials, such as
clothing, paper, hair, etc.
• Many organic dyes contain a long series of double bonds that are close
together. If the chain of double bonds is long enough, these molecules
can absorb low-energy light in the visible region of the electromagnetic
spectrum, resulting in colors that are visible to the human eye.

O H O H

N N Br

N Br N

H O H O
Indigo Tyrian purple
A naturally occurring blue dye which has been 6,6'-dibromoindigo
used for thousands of years. It is obtained Tyrian purple, or “royal purple,” is a purple dye
from an Indian plant (Indigofera tinctoria) and originally obtained from a species of mollusk (Murex)
the European woad (Isatis tinctoria). Today, found near the cities of Tyre and Sidon in ancient
indigo can be made synthetically, and is used Phoenicia. It took about 9,000 mollusk shells to
in dyeing denim to make blue jeans. obtain one gram of the dye, making it very expensive.
This dye was used by royalty (hence the name “royal
purple”) and the Roman aristocracy.
59

Molecules To Dye For

CH3 N CH3

H
N N NH2
SO42_

CH3 2

Mauve
This is the first of the synthetic dyes. It was discovered by the
18-year-old English chemist William Henry Perkin in his home
laboratory, while attempting to synthesize quinine (the only known
treatment for malaria at that time). While cleaning up the sludge
from one of his failed attempts, he noticed that the sludge was turning
the water in his sink violet, and that cloth would pick up this purple
color. Perkin patented his serendipitous discovery, and went into
business making dyes, becoming so successful that he was able to
retire at the age of 36 to focus his attention on chemical research.

60
Chapter 6 Amines and Amides

FD&C Dyes
These color additives are approved by the Food and Drug Administration
(FDA) under the Federal Food, Drug, and Cosmetic Act (FD&C, 1938,
amended 1997) for use in foods.
O H
NaO3S N
SO3-
N SO3Na
H O
NaO3S SO3Na FD&C Blue No. 2
N N Indigo Carmine, Indigotine

FD&C Blue No. 1

Brilliant Blue FCF
I I
OH
NaO O O

-
I I
SO3
CO2Na

NaO3S SO3Na
N N FD&C Red No. 3
Erythrosine
FD&C Green No. 3
Fast Green FCF 61

FD&C Dyes
NaO3S
NaO3S

CH3 OCH3

N N
N N
SO3Na
SO3Na
HO
HO

FD&C Red No. 40 CO2Na

Allura Red AC FD&C Yellow No. 6
N Sunset Yellow FCF
N
N
NaO3S N
HO
FD&C Yellow No. 5
SO3Na
Tartrazine
CO2CH2CH3 CH3 OCH3

N
N N N
N
NaO3S N
HO HO

Orange B SO3Na
Used in sausage and Citrus Red No. 2
frankfurter casings Used to color orange skins 62
Chapter 6 Amines and Amides

Molecules To Dye For

CH3
N N
CH3 N SO3Na
Methyl orange N
N NO2
OH OH
CH3 O Para red
CH3
N N
N N
CH3 N
Methyl red CH3 N
Butter yellow

OH HO

N N
N N
HO3S NH2 H2N SO3H
CH3O Chicago blue OCH3
SO3H HO3S 63

Molecules To Dye For

O
H3C CH3
N N

HO O O
Resazurin

N
Cl
CH3 CH3 H3C Cl CH3
N S N N N
CH3 Methylene Blue CH3 Methyl violet 10B
CH3 (crystal violet) CH3

NH2 H2 N

N N
N N
O O
S S
O O
NaO Congo red ONa
64
Chapter 6 Amines and Amides

Reactions of Amides

65

Amide Formation
• Amides are formed when acid chlorides react with
1° or 2° amines; 3° amines cannot form amides:
O H O H

R C Cl + R' N H R C N R' + HCl

O R'' O R''

R C Cl + R' N H R C N R' + HCl

O R''

R C Cl + R' N R''' no reaction

66
Chapter 6 Amines and Amides

Amide Formation
• Amides are also formed when acid anhydrides react
with 1° or 2° amines.
O O H O H O

R C O C R + R' N H R C N R' + HO C R

O O R'' O R'' O

R C O C R + R' N H R C N R' + HO C R

O O R''

R C O C R + R' N R''' no reaction

67

Examples: Formation of Amides

• Complete the following reactions:
O CH3

C Cl + CH3 N H

68
Chapter 6 Amines and Amides

Examples: Formation of Amides

• Complete the following reactions:
O O

CH3 C O C CH3 + CH3CH2CH2NH2

69

Examples: Formation of Amides

• Complete the following reactions:
O CH3

CH3 C Cl + CH3 N CH3

70
Chapter 6 Amines and Amides

Chemical Properties of Amides

• Unlike amines, amides are not basic.
• Amide hydrolysis can take place under acidic or
basic conditions:

O R'' O R''

R C N R' + H2O + HCl R C OH + H N+ R' Cl-

O R'' O R''

R C N R' + NaOH R C O- Na+ + H N R'

71

Examples: Reactions of Amines and Amides

• Complete the following reactions:
O H

CH3 C N CH3 + H2O + HCl

O H

CH3 C N CH3 + NaOH

72
Chapter 6 Amines and Amides

Condensation Polymers:
Polyamides

73

Condensation Polymers: Polyamides

O O
H2N (CH2)6 NH2 C (CH2)10 C H2N (CH2)6 NH2

1,6-diaminohexane Cl sebacoyl chloride Cl 1,6-diaminohexane

O O

C (CH2)10 C

H2N (CH2)6 N N (CH2)6 NH2

H H

O O O O O O

C (CH2)10 C C (CH2)10 C C (CH2)10 C

Cl N (CH2)6 N N (CH2)6 N Cl
H H H H

O O O O O O

C (CH2)10 C C (CH2)10 C C (CH2)10 C

H2N (CH2)6 N N (CH2)6 N N (CH2)6 N N (CH2)6 NH2

H H H H H H

O O O O O O O O O O

C (CH2)10 C C (CH2)10 C C (CH2)10 C C (CH2)10 C C (CH2)10 C

Cl N (CH2)6 N N (CH2)6 N N (CH2)6 N N (CH2)6 N Cl

H H H H H H H H

74
etc.
Chapter 6 Amines and Amides

Condensation Polymers: Polyamides

O O

C (CH2)10 C
Cl NH—(CH2)6—HN H
n
Nylon-6,12
a polyamide
Discovered by Wallace Carrothers at DuPont in 1934; polymers
average about 10,000 g/mol; 3 billion pound of Nylon made per
year; 60% used for nylon fiber in home furnishings (carpet); also
used in textile fibers, tire cord, rope, parachutes, paint brushes,
Velcro, electrical parts, medical applications (sutures, etc.)
O O O O

C N N C C N N C

H H H H
O O O O

C N N C C N N C

H H H H
O O O O

C N N C C N N C
75
H H H H

Polyamides

NH2 O

H
H2N
N
+ O
O
O
N
Cl
H
Kevlar
Cl used in bullet-proof vests and tire cords
O (an aramid, "aromatic polyamide")

76
Chapter 6 Amines and Amides

Polyamides

H2N NH2

O O O O
+

O O N N

H H
Cl Cl
Nomex
Insulates ceramic tiles on the space shuttle; used in firefighting
equipment, race car driver suits, flight suits, the airbags on the Mars
Pathfinder, Spirit, and Opportunity rovers (less strong than Kevlar,
but has excellent thermal, chemical, and radiation resistance)

77

Polyurethanes
R N C O R N C O
O
H OR H OR
C
Isocyanate + alcohol A Urethane
N

OH
H3C N C O
HO OH

Toluene diisocyanate Glycerol

OH

O OH
O C

HN
OH

O OH
H3C H C
N
O
78
A Polyurethane
Chapter 6 Amines and Amides

Neurotransmitters

79

Neurotransmitters
• Neurotransmitters are small molecules that carry
nerve impulses from one neuron to the next.
• Neurons consist of the main cell body (the soma),
long stemlike projections (the axons), and short
fibers connected to the soma (the dendrites).
• Neurons are not connected directly to each other, but
are separated by a small gap called a synapse.
• When an electrical current originating in a neuron
reaches the synaptic terminals at the end of the
axon, the terminals release neurotransmitter
molecules into the synapse; these molecules diffuse
across the synapse and bind to receptors on the
dendrites of the next neuron, stimulating an
electrical current, which travels along that neuron
until it reaches the next synapse, and so on until the
nerve impulse reaches the brain. 80
Chapter 6 Amines and Amides

Figure 6.5 A nerve cell

and the transmission of a
nerve signal.

81

HO

HO
HO NH2

CO2H
Dopa
HO NH2
Synthesized from the amino acid tyrosine; used as a
treatment for Parkinson's disease, which is caused by a Dopamine
breakdown of dopamine-based neurons that control the Synthesized from dopa; used as a
brain's motor system (dopamine cannot be administered treatment for low blood pressure
directly because it does not cross the blood-brain barrier;
however, the L-form of dopa does)

HO
NH2

HO NH2
N
OH H
Norepinephrine (NE) Serotonin
Synthesized from dopamine; an excess of NE in the Synthesized from the amino acid tryptophan;
brain is related to feelings of elation or manic states; influences sleeping, body temperature, and
low NE levels are linked to depression; the stimulant sensory perception; drugs that mimic serotonin
action of epinephrine and NE in some cells can be are used to treat depression, anxiety, and
reduced by beta blockers, which are used to treat obsessive-compulsive disorder; serotonin
cardiac arrhythmias, angina, and hypertension blockers are used to treat migraine headaches
and nausea resulting from chemotherapy 82
Chapter 6 Amines and Amides

HO

CH3
HO N

OH H
Epinephrine (Adrenalin)
More important as a hormone than a neurotransmitter;
synthesized in the adrenal glad; release of adrenalin into
the bloodstream in response to pain, anger, or fear
increases blood glucose levels, and provides a sudden
burst of energy (fight-or-flight response); increases force
of heart contractions (raising blood pressure); also a
vasoconstrictor; used in local anesthetics to keep the
anesthetic from being washed away

O
O CH3 CH3
H2N
N+ OH
O CH3
Acetylcholine Gamma-aminobutanoic acid (GABA)
A inhibitory neurotransmitter

83

Pheynlephrines and Amphetamines

CH3 CH3 CH3
CH3 CH3
NH2 N N
Amphetamine (Benzedrine) H OH H
a powerful nervous stimulant; raises N-Methylamphetamine
blood glucose levels, increases heart (Methedrine, "speed") Ephedrine / Pseudoephedrine
rate and blood pressure Also a powerful nervous found in the Chinese ma-huang plant; a
stimulant decongestant used in many cold remedies

O
CH3

CH3 CH3
HO N O N
CH3O
OH H H
CH3O 3,4-Methylenedioxymethamphetamine
Phenylephrine (MDMA), "Ectasy"
Common decongestant

CH3O NH2
Mescaline
Hallucinogen from peyote cactus 84
Chapter 6 Amines and Amides

Amino Acids and

Proteins

85

Amino Acids
O
H
H2N
OH

R
Amino Acids

O O O O

H2N H2N H2N H2N

OH OH OH OH
Glycine (Gly)
CH3
Alanine (Ala)
Valine (Val)
Leucine (Leu)

O O H O O

H2N H2N N H2N

OH OH OH OH

S
Proline (Pro)
Isoleucine (Ile) Methionine (Met)

86
Phenylalanine (Phe)
Chapter 6 Amines and Amides

O O O O

H2N H2N H2N H2N

OH OH OH OH

OH OH
Serine (Ser) Threonine (Thr)

OH N
Tyrosine (Tyr) H
Tryptophan (Try)
O O O O

H2N H2N H2N H2N

OH OH OH OH
O
NH2
SH
NH2 NH
Cysteine (Cys)
Glutamine (Gln) N O
Histidine (His) Asparagine (Asn)
O O O O

H2N H2N H2N H2N

OH OH OH OH O
O
NH2 OH
N NH2
Lysine (Lys) OH H
Glutamate (Glu) Arginine (Arg)
O 87
Aspartate (Asp)

H2N
O OH
H2N OH
OH O
O O
H
CH3 H2N O
H2N Alanine (Ala) N
OH Aspartate (Asp)
Glycine (Gly) OH
Glycine (Gly)
CH3
Alanine (Ala)

H2N
OH

O
H O
H2N H O
N
Glycine (Gly) N N
OH H
Tryptophan (Try)
CH3
Alanine (Ala) OH

O
Aspartate (Asp) 88
Chapter 6 Amines and Amides

O
H O
H2N H O
N H O
Glycine (Gly) N
N
CH3 OH
Alanine (Ala) OH etc.

O
Aspartate (Asp)
N
H
Tryptophan (Try)

Gly Ala Asp Try

a protein
(a polyamide)
Instructions for making proteins
are encoded in DNA.

89

Three levels of structure in a telephone cord 90

Chapter 6 Amines and Amides

R-group interactions leading to a protein tertiary structure 91

Segment of a protein showing -helix, -pleated sheet,

and random coil structures 92
Chapter 6 Amines and Amides

Some Hideously Complex

Molecules

93

OH
O

O N(CH3)2
H
OH
O
H
Erythromycin
an antibiotic
O

OCH3
OH H
H N NH2 CH3
OH H2N N H N OH
NH H
NH O H O
HO OH
H H
OH O
O CHO
Streptomycin OH OH
an antibiotic CH3 94
Chapter 6 Amines and Amides

O O
OH
O

HN O
O
H
N OH H
O HO O
H Taxol O O O
N NH2 potential anti-cancer
drug isolated from the
O Pacific yew tree
Bufotoxin O
isolated from the toad Bufo
OH marinus; increases the
contractive power of weak O
O N heart muscles; also causes
H terrifying hallucinations

O
OH O
O 95

O
H2N
O

O
CH3 NH2
CH3 O
H2N
H3C NH2
N N
H3C
Co
H
N N
CH3
CH3

H2N O
O CH3 CH3
O
NH2 Vitamin B12
(cobalamine)
Found in meat, fish, eggs, and milk; a
NH coenzyme involved in amino acid
metabolism; needed for the production
O of red blood cells (a deficiency in
N vitamin B12 results in anemia)
H3C O P O OH
O N
CH3
O
HO 96
CH3
Chapter 6 Amines and Amides

Functional Groups
O H
H H
R R
H C C H C C R C C R
H H R R
alkane alkene alkyne aromatic ring phenol
(-ane) (-ene) (-yne) (phenyl-, -benzene) (-phenol)

H H R

R C OH R C OH R C OH R O R R SH
ether thiol
H R R (alkoxy-, -ether)
primary (1°) alcohol secondary (2°) alcohol tertiary (3°) alcohol
(-ol) (-ol) (-ol)

O O OH OR OH OR

R C H R C H R C H R C R R C R
R C R
aldehyde ketone OR OR OR OR
(-al) (-one)
hemiacetal acetal hemiketal ketal 97

O O O O O O

R C OH R C O- M + R C O R R C Cl R C O C R
carboxylic acid carboxylate salt ester acid chloride acid anhydride
(-oic acid) (metal + -oate) (alkyl + -oate)

R N H R N H R N R R N+ R

H R R R
primary (1°) amine secondary (2°) amine tertiary (3°) amine quaternary ammonium salt
(amino-, -amine) (-amine) (-amine) (alkyl ammonium + anion)

O O O O

R C NH2 R C NHR R C N R RO P OH
R OH
amide phosphate ester
(N-alkyl + -amide) 98
Chapter 6 Amines and Amides

Reactions of Amines and Amides

1. Reaction of an amine with water to produce an alkylammonium ion.
H H

R N + H O R N H + -OH

H H H
amine alkylammonium ion

2. Reaction of an amine with acid to produce an alkylammonium salt.

H H
R N + H Cl R N H -Cl

H H
amine hydrochloric alkylammonium
acid chloride

3. Conversion of an alkylammonium salt back to an amine.

+ -
R—NH3 Cl + NaOH  R—NH2 + H2O + NaCl

99

4. Formation of an amide. (NR with tertiary amines.)

O R O R

R' C Cl + R N H R' C N R + HCl

acid chloride amine amide
(1° or 2°)
O O R O R O

R' C O C R + R N H R' C N R + R' C OH

acid anhydride amine amide carboxylic
(1° or 2°) acid
5. Hydrolysis of amides under acidic and basic conditions.
O O H

R' C N R + H2O + HCl R' C OH + H N+ R Cl-

carboxylic
R acid R
amide alkylammonium
salt
O O
R' C N R + NaOH R' C O- Na+ + H N R
carboxylate
R salt R
amide amine 100