Organic Chemistry

Amines

Laboratorium Kimia Organik – Jurusan Kimia

Fakultas Matematikan dan Ilmu Pengetahuan Alam
Universitas Padjadjaran
2009
 Amine

1. What are the different types of amines?

Be able to recognize primary, secondary, tertiary, and
heterocyclic amines.
2. How are amines named?
Be able to name simple aminers and write their structures, given
the names.
3. What are the general properties of amines?
Be able to describe amine properties such as hydrogen bonding,
solubility, boiling point, and basicity.
4. How do amines react with water and acids?
Be able to predict the structure of the ammonium ions and of the
salts formed by reactions of amines with water and acids..
5. What are some natually occuring types of amines and some
amine-containing drugs?
Be able to describe some types of amines found in biomolecules,
plants, and drugs. substitution reactions.
 AMINES
Amine are compounds that contain one or more organic groups bonded to
nitrogen: RNH2, R2NH, or R3N.
Amine are classified as primary, secondary, or tertiary, depending on how
many organic substituents are bonded to the nitrogen atom.

Primary Amine, an amine that has one organic group bonded to nitrogen RNH2.
Secondary Amine, an amine that two one organic group bonded to nitrogen R2NH.
Tertiary Amine, an amine that has three organic group bonded to nitrogen R3N.
 AMINES

The groups bonded to the amine nitrogen may be alkyl or aryl groups.
 NAMING AMINES
Primary alkyl amines, RNH2, are named simply by ientifying the alkyl group
attached to nitrogen and adding the suffix –amine to the alkyl group name.

Secondary and tertiary amines with two or three identical groups are
named by adding the appropiate prefix, di- or tri-, to the alkyl group name
 NAMING AMINES
Secondary and tertiary amines with nonidentical R- groups are named as N-
substituted derivatives of a primary amine.
The largest of the organic groups bonded to nitrogen is chosen as the parent
compound, and the other groups are considered N-substituents (N-because
they’r attached directly to nitrogen).

The simplest aromatic amine is known by the commom name anline. When the –NH2
group must be named as a substituent, amino- is used as a prefix
 Heterocyclic Nitrogen Compounds

Heterocycle, a ring that contains nitrogen or some other atom in addition to carbon
Heterocyclic nitrogen compounds may be nonaromatic or aromatic.
Heterocyclic Nitrogen Compounds
 PROPERTIES OF AMINES
Amine are analogous to amonia in many of their physical properties, just as alcohols
are analogous to water

Like amonia, amines have an unshared electron pair onthe nitrogen atom and have
poar bonds because the nitrogen atom is electronegative.

Amine form hydrogen bonds in the same way that ammonia does and are higher
boiling han alkanes of similar size.
 PROPERTIES OF AMINES
The differences in properties between amines and alcohols are accounted for by
hydrogen bonding.
Because nitrogen atoms are less electronegative than oxygen atoms, they form
weaker hydrogen bonds, and di-, and trimethylamine and ethylamine are gases at
room temperature.
Tertiary amine molecules have no hydrogen atoms attashed to nitrogen and, because
they cannot hydrogen-bond with each other, are lower boiling than either amines or
alcohols of similar molecular weight.

All amine, however, can hydrogen-bond to water molecules throught the lone
electron pair on their nitrogen atoms, as a result, amines with up to about six carbon
atoms are quite soluble in water.
PROPERTIES OF AMINES
 PROPERTIES OF AMINES
 Primary and secondary amines are hydrogen-bonded and
higher boiling than alkanes, but lower boiling point than
alcohols.
 Tertiary amine are lower boiling than secondary or primary
amines because hydrogen bonding is not possible.
 The simplest amines are gases; other common amines are
liquids.
 Volatile amines have unpleasant odors.
 Simple amines are water-soluble because of hydrogen
bonding.
 Amines are weak Brønsted-Lowry bases.
 Many amines are physiologically active, and many are toxic.
 BASICITY OF AMINES
Amonia is a weak Brønsted-Lowry base, that is, ammonia can use its lone pair of
electrons to accept a hydrogen ion (proton) from an acid and form the ammonium
ion, NH4+.

The aqueous solution of many amines are basic because of the following
equilibrium:
 BASICITY OF AMINES
Amines react with strong acids such as hydrochloric acid to yield ammonium salts
according to the general equation:
 BASICITY OF AMINES
The reaction between amines and acids is reversible and can be made to take place
in either direction depending on the reaction conditions.
An amine is protonated to yield an ammonium ion when treated with acid, and an
ammonium ion is deprotonated to yield a neutral amine when treated with base.

The positive ions formed by protonation of alkylamines are named by replacing the
ending –amine by the ending –ammonium. To name the ions of heterocyclic amines,
the amine name is modified by replacing the –e with –ium.
 AMMONIUM SALTS
An amine salt is composed of a cation and an anion and is usually named by
combining the cation and anion names.

(C6H5)CHOCH2CH2N(CH3)2∙Cl or (C6H5)CHOCH2CH2NH+(CH3)2.Cl-

Ammonium salt formation, like carboxylate saltformation, provides a means for

converting an insoluble compound into a water-soluble derivative.
 AMMONIUM SALTS
Because many amines are unstable in air, salt formation allows the amine to be
stored in a more stable form.
When the free amine is needed, it is easily regenerated by treatmen with a base:

CH3NH3+ Cl- (aq) + NaOH (aq) CH3NH2(aq) + NaCl (aq) + H2O (l)

Ammonium salts can be formed by reaction of an amine with an acid, as shown

above, and also by reaction of an alkyl halide with an amine:
 AMMONIUM SALTS
The reaction of a tertiary amine with an alkyl halide produces a quaternary
ammonium salt , an ammonium salt with four —R groups on the nitrogen atom:
 AMMONIUM SALTS
Quaternary ammonium salts have no H atom that can be removed by a base and no
lone pair that can be protonated, so their structure in solution is uneffected by
changes in pH.
One commonly encountered quternary amonium salt has the following structure,
where R reprsents a range of C8 to C18 alkyl groups.
 AMINES IN BIOMOLECULES
Protein are polymers of amino acids, which all contain an amino group and a
carboxylic acid group.

A second major class of biomolecules, the nucleotides, all contain nitrogen

heterocyclic rings derived from either purine or pyrimidine. Nitrogen heterocycles
are also part of several vitamins, including the B vitamins:
 AMINES IN BIOMOLECULES

Several members of the diverse class of compounds known as neurotransmitters,

which transmit nerve impulses throughout the body, are amines, including serotonin
and dophamin.
 AMINES IN PLANTS

The roots, leaves, and fruits of flowering plants (angiosperms) are a rich source of
amines, including many thar are physiologically active.
These compounds, once called ”vegetable alkali” because their water solution are
basic, are now referred to as alkaloids.
The molecular structures of approximately 5500 alkaloids have been determined.

The potato growns in the absence of sunlight and should also be stored awy from
sunlight, which causes formation of poisonous solanine (along with green
chlorophyl) under the skin.
 AMINES IN PLANTS

Coniine is extracted Atropine is the toxic substance in the herb

from poison hemlock known as deadly nightshade or belladonna
(Conium maculatum) (Atropa belladonna).
 AMINES IN PLANTS

Poppy,
“Papaver somniferum”

Morphine and Codeine was the first pure compound Heroin, another close
to be isolated from the poppy (Papaver relative of morphine, does
somniferum). not occur naturally but is
easily synthesize in chemical
laboratory.
 AMINES IN DRUGS
Given the variety of nitrogen-containing compounds that are physiologically active,
it’s not surprising that many drugs are amines or nitrogen heterocycles.
The relationship between molecular structure and physiological activity is the key to
understanding drug action and to discovering new drugs.
Histamin is the biomolecules responsible for symptoms of allergic reaction familiar
to hay fever sufferers.
It’s also the chemial that causes an itchy bump when an insect bites you.

The mosquito injects antigen,

substances that triger a response by
the body’s immune system.
The immune system in turn triggers
release of histamine, which causes
swelling, itchiness, and redness
around the bite.
The antihistamines are a family of drugs than counteract histamine, and members of
this family have in common a disubstituted ethylene side chain, usually with two N-
methyl groups.
 AMINES IN DRUGS
Neurotranmitters and Drugs that Mimic Their Action (Sympathomimetics)

Dopamine is a precursor of norepinephrine, a principal messenger in the nervous

system.
Epinephrine (adrenaline) is the compound specifically responsible for causing the
surge of energy we feel in a frightening situation.
Ephedrine and its salts are used in over-the counter medications for atshma and
nasal congestion because they dilate bronchial and nasal passageways.
 AMINES IN DRUGS
Neurotranmitters and Drugs that Mimic Their Action (Sympathomimetics)

Isoproterenol is a presciption drug for bronchial asthma.

Amphetamine is the parent compound of a family of central-nervous system
stimulant that produce an array of effects like those of epinephrine, including
excitment, increased blood pressure, quickened reflexes, and appetite suppression.
 AMINES IN DRUGS

Demerol (Meperidine) is widely used as a painkiller

Methadone is used in the tritment of heroin addiction.