Amines

ORGANIC CHEMISTRY TEAM

DEPT OF CHEMISTRY, FACULTY OF SCIENCE AND TECHNOLOGY
UNIVERSITAS AIRLANGGA
Key Questions

1. What Are Amines?

2. How Do We Name Amines?
3. What Are the Physical Properties of Amines?
4. How Do We Describe the Basicity of Amines?
5. What Are the Characteristic Reactions of Amines?
AMINE IN A LIFE

Epinephrine Structure

albuterol Structure

This inhaler delivers a puff of albuterol (Proventil), a potent synthetic

bronchodilator whose structure is patterned after that of epinephrine.
1. What Are Amines?

Compound containing NR2 as functional group

 Structure : R-NR2 (R=H, alkyl, aryl)

Amines, depending on the number of carbon groups bonded to nitrogen, are

classified as:

1. primary (1°),

2. secondary (2°), or

3. tertiary (3°)
1. What Are Amines?
Compound containing NR2 as functional group
 Structure : R-NR2 (R=H, alkyl, aryl)

Aliphatic amine Aromatic amine

An amine in which nitrogen is bonded only to An amine in which nitrogen is bonded to one or
alkyl groups or hydrogens more aromatic rings

CH3 CH3

:
N H2 N -H CH2 - N- CH3

:
Aniline N-Methylaniline Benzyldimethylamine
(a 1° aromatic amine) (a 2° aromatic amine) (a 3° aliphatic amine)
 1. What Are Amines?
Compound containing NR2 as functional group
 Structure : R-NR2 (R=H, alkyl, aryl)
Heterocyclic amine Heterocyclic aromatic amine

An amine in which nitrogen is one of the atoms of an

An amine in which the nitrogen atom is part of a ring aromatic ring

N N N N
H H H
Pyrrolidine Piperidine Pyrrole Pyridine
(heterocyclic aliphatic amines) (heterocyclic aromatic amines)
 CLASIFICATION OF
AMINES
 Primery Amines (1):

N binding with one R group , and two H atoms.

 Secondary Amines(2):

N binding with two R groups , and one H atoms..

 Tertiery Amines(3):

N binding with three R groups.

 Quartenery Amines(4):

N binding with four R groups and have positively charged (+).

CLASIFICATION OF
AMINES
Amine examples: 1 o
, 2 o
, 3 o
& 4 o

Isobutylamine (1o) Etylisopropylamine (2o) Trietylamine (3o)

Free electron pairs

are used to bind, so
that the N atom is
positively charged

Tetrametylamoniumchloryde (4o) Tetrametylamoniumhydrokside (4o)

 2. How Do We Name Amines?
IUPAC Names of aliphatic amines
 IUPAC names for aliphatic amines are derived just as they are for alco- hols.
 The final -e of the parent alkane is dropped and replaced with -amine.
 Indicate the location of the amino group on the parent chain by a number.

1,6-Hexanediamine
2-Propanamine
Cyclohexanamine
 IUPAC Names of simples aromatic amines

 IUPAC nomenclature retains the common name aniline for C6H5NH2,

 the simplest aromatic amine. Its simple derivatives are named using num- bers to locate substituents or,
alternatively, using the locators ortho (o), meta (m), and para (p).
 Several derivatives of aniline have common names that remain in use. Among them is toluidine for a methyl-
substituted aniline.

Aniline 4-Nitroaniline ( p-Nitroaniline) 3-Methylaniline (m-Toluidine)

IUPAC Names of Unsymmetrical secondary and tertiary amines

 Unsymmetrical secondary and tertiary amines are commonly named as N-substituted primary amines.
 The largest group bonded to nitrogen is taken as the parent amine;
 the smaller groups bonded to nitrogen are named, and their locations are indicated by the prefix N
(indicating that they are bonded to nitrogen).

N-Methylaniline N,N-Dimethylcyclopentanamine
 Problems of IUPAC NAMES

Write the IUPAC name for each amine

Common Names
 Common names for most aliphatic amines list the groups bonded to nitro- gen in alphabetical order in one word ending in the suffix -amine.

 When four atoms or groups of atoms are bonded to a nitrogen atom—as, for example, in NH4+ and CH3NH3+, nitrogen bears a positive charge and is associated with an anion as a salt.
The compound is named as a salt of the corresponding amine. The ending -amine (or aniline, pyridine, or the like) is replaced with -ammonium (or anilinium, pyridinium, or the like), and the name of the anion (chloride, acetate, and so on) is added.
(CH3CH2)3NH+Cl-
Triethylammonium chloride
 Problem
1. Write a structural formula for each amine.
(a) Isopropylamine
(b) Cyclohexylmethylamine
(c) Triethylamine
2. Write a structural formula for each amine.
(a) 2-Aminoethanol
(b) Diphenylamine
(c) Diisopropylamine
 Physical Properties of Amines
 Like ammonia, low-molecular-weight amines have very sharp, penetrating odors.
a. Trimethylamine, for example, is the pungent principle in the smell of rotting fish.
b. Two other particularly pungent amines are 1,4-butanediamine (putrescine) and 1,5-pentanediamine
(cadaverine).
 Amines are polar compounds because of the difference in electronegativity between nitrogen and hydrogen (3.0
- 2.1 = 0.9).
 Both primary and secondary amines have N - H bonds and can form hydrogen bonds with one another (please
Figure bellow).
 Tertiary amines do not have a hydrogen bonded to nitrogen and, therefore, do not form hydrogen bonds with one
another.
 Physical Properties of Amines
 An N-H---N hydrogen bond is weaker than an N-H---O hydrogen bond, because the
difference in electronegativity between nitrogen and hydrogen (3.0 - 2.1 = 0.9) is less than
that between oxygen and hydrogen (3.5 - 2.1 = 1.4).

CH3CH3 CH3NH2 CH3OH

Molecular weight (amu) 30.1 31.1 32.0
Boiling point (°C) 288.6 26.3 65.0
 All classes of amines form hydrogen bonds with water and are more soluble in water than
are hydrocarbons of comparable molecular weight.
 Most low-molecular-weight amines are completely soluble in water, but higher-
molecular-weight amines are only moderately soluble in water or are insoluble.
The Basicity of Amines
 Like ammonia, amines are weak bases, and aqueous solutions of amines are basic. the unshared pair of
electrons on nitrogen forms a new covalent bond with hydrogen and displaces a hydroxide ion.
 All aliphatic amines have approximately the same base strength (pK 3.0 - 4.0), and are slightly stronger bases
than ammonia.
 Aromatic amines and heterocyclic aromatic amines (pK 8.5 - 9.5) are considerably weaker bases than aliphatic
amines.
 One additional point about the basicities of amines: While aliphatic amines are weak bases by comparison with
inorganic bases such as NaOH, they are strong bases among organic compounds.

Class pKb Example Name

Aliphatic 3.0-4.0 CH3CH2NH2 ethanamine Stronger base

Ammonia 4.74

Aromatic 8.5-9.5 aniline Weaker base

 Characteristic Reactions of Amines

 The most important chemical property of amines is their basicity.

 Amines, whether soluble or insoluble in water, react quantitatively with
strong acids to form water-soluble salts
 Many drugs have “•HCl” or some other acid as part of their chemical formula and occasionally as part of
their generic name. Invariably, these drugs are amines that are insoluble in aqueous body fluids such as
blood plasma and cerebrospinal fluid. For the administered drug to be absorbed and carried by body fluids,
it must be treated with an acid to form a water-soluble ammonium salt. Methadone, a narcotic analgesic, is
marketed as its water- soluble hydrochloride salt. Novocain, one of the first local anesthetics, is the
hydrochloride salt of procaine.

 There is another reason besides increased water solu- bility for preparing these and other amine drugs as salts. Amines
are very susceptible to oxidation and decomposi- tion by atmospheric oxygen, with a corresponding loss of biological
activity. By comparison, their amine salts are far less susceptible to oxidation; they retain their effec- tiveness for a
much longer time.
 SUMMARY
1 What Are Amines?
 Amines are classified as primary, secondary, or tertiary, depending on the number of carbon atoms bonded to nitrogen.
 In an aliphatic amine, all carbon atoms bonded to nitrogen are derived from alkyl groups.
 In an aromatic amine, one or more of the groups bonded to nitrogen are aryl groups.
 In a heterocyclic amine, the nitrogen atom is part of a ring.
2 How Do We Name Amines?
 In IUPAC nomenclature, aliphatic amines are named by changing the final -e of the parent alkane to -amine and using a
number to locate the amino group on the parent chain.
 In the common system of nomenclature, aliphatic amines are named by listing the carbon groups bonded to nitrogen in
alphabetical order in one word ending in the suffix -amine.
3 What Are the Physical Properties of Amines?
 Amines are polar compounds, and primary and secondary amines associate by intermolecular hydrogen bonding.
 All classes of amines form hydrogen bonds with water and are more soluble in water than are hydrocarbons of comparable
molecular weight.
 SUMMARY
4 How Do We Describe the Basicity of Amines?
 Amines are weak bases, and aqueous solutions of amines are basic.
 The base ionization constant for an amine in water is denoted by the symbol Kb.
 Aliphatic amines are stronger bases than aromatic amines.
5 What Are the Characteristic Reactions of Amines?
 All amines, whether soluble or insoluble in water, react with strong acids to form water-
soluble salts.
 We can use this property to separate water-insoluble amines from water-insoluble
nonbasic compounds.
PROBLEM

1. Draw a structural formula for each amine.

(a) 2-Butanamine (b) 1-Octanamine
(c) 2,2-Dimethyl-1-propanamine (d) 1,5-Pentanediamine
(e) 2-Bromoaniline (f) Tributylamine

2. Draw a structural formula for each amine.

(a) 4-Methyl-2-pentanamine (b) trans-2-Aminocyclohexanol
(c) N,N-Dimethylaniline (d) Dicyclohexylamine
(e) sec-Butylamine. (f) 2,4-Dimethylaniline
 PROBLEM

3. There are eight constitutional isomers with the molecular formula C 4H11N.
 (a) Name and draw a structural formula for each amine.
 (b) Classify each amine as primary, secondary, or tertiary.

4. There are eight primary amines with the molecular formula C 5H13N.
 Name and draw a structural formula for each amine.
 PROBLEM
5. Answer true or false.
a) In the IUPAC system, primary aliphatic amines are named as alkanamines.
b) The IUPAC name of CH3CH2CH2CH2CH2NH2 is 1-pentylamine.
c) 2-Butanamine is chiral and shows enantiomerism.
d) N,N-Dimethylaniline is a 3° aromatic amine.
e) Hydrogen bonding between 2° amines is stronger than that between 2° alcohols.
f) Primary and secondary amines generally have higher boiling points than
hydrocarbons with comparable carbon skeletons.
g) The boiling points of amines increase as the molecular weight of the amine
increases.
 PROBLEM
6. Propylamine (bp 48°C), ethylmethylamine (bp 37°C), and trimethylamine (bp 3°C) are
constitutional iso- mers with the molecular formula C3H9N. Account for the fact that
trimethylamine has the lowest boil- ing point of the three and propylamine has the high-
est boiling point.
7. Account for the fact that 1-butanamine (bp 78°C) has a lower boiling point than 1-
butanol (bp 117°C).
8. 2-Methylpropane (bp 212°C), 2-propanol (bp 82°C),
9. and 2-propanamine (bp 32°C) all have approxi- mately the same molecular weight, yet
their boiling points are quite different. Explain the reason for these differences.
10. Account for the fact that most low-molecular-weight amines are very soluble in water,
whereas low- molecular-weight hydrocarbons are not.
 PROBLEM

 Draw a structural formula for a compound with the given molecular formula that is:
(a) A 2° aromatic amine, C7H9N
(b) A 3° aromatic amine, C8H11N
(c) A 1° aliphatic amine, C7H9N
(d) A chiral 1° amine, C4H11N
(e) A 3° heterocyclic amine, C5H11N
(f) A trisubstituted 1° aromatic amine, C9H13N