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Amines:
derivatives of ammonia (NH3) with one or more alkyl or
aryl group bonded to the N atom
contain N attached to one or more alkyl (aliphatic amine)
or aromatic groups (aromatic amine).
amino
R-NH2 group
NH
CH22 CH3
CH3-NH2 CH3-NH-CH3
Aliphatic amine
Ethylbenzene
Aromatic amine
Structure &
Classification
CH3 CH3
:
:
Aniline N-Methylaniline Benzyldimethylamine
(a 1 aromatic amine) (a 2 aromatic amine) (a 3 aliphatic amine)
Structure & Classification
c. Heterocyclic amine:
An amine in which nitrogen is one of the atoms of a ring.
N N N N
H H H
Pyrrolidine Piperidine Pyrrole Pyridine
(heterocyclic aliphatic amines) (heterocyclic aromatic amines)
Structure & Classification
Example:
Classify each amino group by type.
CH3
N
H
H COOCH3
(a) (b) N (c)
N
CH3 O C6 H5
H N
(S)-Coniine (S)-Nicotine Cocaine O
Nomenclature
Common name
names the alkyl groups bonded to Nitrogen, followed by
the suffix amine. Arrange the alkyl groups into
alphabetical order.
Give prefixes di-, tri-, tetra- to describe the number of
identical substituent
Nomenclature
OCH3
NO2 CH3
Aniline 4-Nitroaniline 4-Methylaniline 3-Methoxyaniline
(p-Nitroaniline) (p-Toluidine) (m-Anisidine)
Nomenclature
Heterocylic amines:
When N is one of the atoms of a ring.
The heteroatom is usually assigned position number 1
Nomenclature
IUPAC name
The longest continuous chain of carbon atoms become
the root name.
Change the e ending in the alkane to amine.
Show the position of the amino group along the chain.
The position of amino group should be the smallest.
Give numbers for the other substituents and the prefix
N- is used for each substituent on Nitrogen
Nomenclature
OH OH
H2 N H2 N COOH
NH2
2-Aminoethanol (S)-2-Amino-3-methyl- 4-Aminobenzoic acid
1-butanol
Nomenclature
H H
.. ......O H
-
N.
. +
CH3 + H ..
OH CH3 N H
H H
.
Solutions:
Values of Kb for most amines are fairly small (< 10-3) and the
equilibrium for this dissociation lies toward the left
Aqueous solutions of amines are distinctly basic
Basicity
Effects on basicity
Some factors influence amine basicity:
1. Substitution by alkyl groups
e.g. : ammonia (NH3) vs methylamine (CH3NH2)
Simple alkylamines are generally stronger bases than
ammonia
Alkyl groups are electron-donating (-CH3, -NH2, -OCH3)
toward cations, it increase the basicity of amines
Electron-withdrawing groups such as halogens, nitro
groups, and carbonyl groups, decrease the basicity of
aromatic amines by a combination of resonance and
inductive effects.
Basicity
(aniline
) (cyclohexyla
mine)
Basicity
2. Resonance effects
Aromatic amines (anilines and their derivatives) or
arylamines are weaker bases than simple aliphatic amines.
The reduced basicity is due to resonance delocalization of
the non bonding electrons in the free amine.
Stabilization of the reactant (free amine) makes the amine
less basic. In aniline, overlap between the aromatic ring and
the orbital containing nitrogens lone pair stabilizes the lone
pair and makes it less reactive. The overlap is lost in the
anilinium ion
Basicity
3. Hybridization effects
Electrons are held more tightly by s orbital.
Unsaturated amines tend to be weaker bases than simple
aliphatic amines.
In pyridine, the nonbonding electrons occupy an sp2 orbital
with greater s character and more tightly held electrons
than those in sp3 orbital of an aliphatic amine.
Pyridines nonbonding electrons are less available for
bonding to a proton. Pyridine does not lose its aromaticity
on protonation, however and it is much stronger base than
pyrrole
Basicity
H H
+ -
CH3 -N + H-O-H CH3 -N-H O-H
H H
Methylamine Methylammonium hydroxide
+ -
CH3NH2 + CH3 COOH CH3NH3 + CH3COO pK eq = -5.88
pKa 4.76 pKa 10.64 Keq = 7.6 x 10
5
(stronger (weaker
acid) acid)
Basicity
Aromatic amines:
N
Intermediate
Imidazole
6.95
N
H
Basicity
NH2 + H2 O
+
NH3 OH
-
pK a = 10.66
Cyclohexylamine Cyclohexylammonium
hydroxide
Aromatic amines are weaker bases than aliphatic amines because of two
factors:
Basicity
. . H unhybridized 2p orbital of N
H
. . ..
H
H . . N
H
nitrogen is sp2 hybridized
H H
O2N
3-Nitroaniline 4-Nitroaniline
pK a 2.47 pK a 1.0
O -O
+
+N NH2 +N NH2
O
- -O
N
N N N
H H
Piperidine Pyridine Imidazole
pKa 10.75 pKa 5.25 pK a 6.95
Imidazole
Which N lone pair is protonated? The one which is not part
of the aromatic system.
:
N N
sextet
H H
Imidazole Imidazolium ion
Basicity
Guanidine
Guanidine is the strongest base among neutral organic
compounds.
+
NH NH2
-
H2 N C NH2 + H2 O H2 N C NH2 OH+ pKa = 13.6
Guanidine Guanidinium ion
:
NH2 NH2 NH2
+ +
:
:
H2 N C NH2 H2 N C NH2 H2 N C NH2
Amine salts:
ionic, high-melting, non volatile solids
soluble in water than parent amines
slightly soluble in nonpolar organic solvents
Reaction with acids
amine
salts
Synthesis of amines
2. Acylation-reduction of amines
acyl
Synthesis of amines
3. Reduction of azides
(Azide = compound having azido group, N3)
4. Reduction of nitriles
Synthesis of amines
5. Reduction of amides
1. Alkylation
3. Hoffman elimination
Tiffeneau-Demjanov reaction:
Treatment of a -aminoalcohol with HNO2 gives a ketone
and N2.
OH O
CH2 NH2 + HNO2 + H2 O + N2
A-aminoalcohol Cycloheptanone
(1-aminomethyl-
Reaction of amines
:
:
: OH :O-H
HNO 2 + -N2
CH2NH2 CH2 N N:
(A diazonium ion)
proton transfer
:
+ O H O
:
:
:O H
to H2O
+ CH2 CH2
Mechanism:
+ (1) (2) +
+ N O + + H O H
N N N H
H N=O
H N=O
H O
H
Reaction of amines