Chemistry Sem IV Amines
Session 1: Structure of amines, basicity of aliphatic amines, aryl
amines and heterocyclic amines, effect of substituents on basicity
of aliphatic and aromatic amine
Introduction
Colombian poison dart frogs are tiny, beautiful, and deadly. They produce a poison
called histrionicotoxin, which is an amine that causes paralysis. Death from
histrionicotoxin results by suffocation through paralysis of the victim’s respiratory
muscles. (A molecular model of histrionicotoxin is shown above.) Curare, the Amazonian
arrow poison that is a mixture of compounds from a woody vine, contains another
paralytic neurotoxin, called d-tubocurarine. Histrionicotoxin and d-tubocurarine both
block the action of acetylcholine, an important neurotransmitter. Amines like these and
others have fascinating roles in biological systems, as we shall see in this chapter
while studying the properties, reactivity, and synthesis of amines.
Nomenclature
In common nomenclature most primary amines are named as alkylamines. In
systematic nomenclature (blue names in parentheses below) they are named by adding
the suffix -amine to the name of the chain or ring system to which the NH2 group is
attached with replacement of the final -e. Amines are classified as being primary (1°),
secondary (2°), or tertiary (3°) on the basis of the number of organic groups attached to
the nitrogen
Most secondary and tertiary amines are named in the same general way. In common
nomenclature we either designate the organic groups individually if they are different or
use the prefixes di- or tri- if they are the same. In systematic nomenclature we use the locant
N to designate substituents attached to a nitrogen atom.
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Chemistry Sem IV Amines
Arylamines
Heterocyclic amines
The important heterocyclic amines all have common names. In systematic
replacement nomenclature the prefixes aza-, diaza-, and triaza- are used to indicate that
nitrogen atoms have replaced carbon atoms in the corresponding hydrocarbon. A nitrogen
atom in the ring (or the highest atomic weight heteroatom, as in the case of thiazole) is
designated position 1 and numbering proceeds to give the lowest overall set of locants to the
heteroatoms:
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Chemistry Sem IV Amines
Structure of Amines
The nitrogen atom of most amines is like that of ammonia; it is approximately sp3
hybridized. The three alkyl groups (or hydrogen atoms) occupy corners of a tetrahedron;
the sp3 orbital containing the unshared electron pair is directed toward the other corner. We
describe the shape of the amine by the location of the atoms as being trigonal pyramidal.
However, if we were to consider the unshared electron pair as being a group
we would describe the geometry of the amine as being tetrahedral. The electrostatic potential
map for the van der Waals surface of trimethylamine indicates localization of negative
charge where the nonbonding electrons are found on the nitrogen:
The bond angles are what one would expect of a tetrahedral structure; they are very
close to 109.5°. The bond angles for trimethylamine, for example, are 108°.
If the alkyl groups of a tertiary amine are all different, the amine will be chiral. There
will be two enantiomeric forms of the tertiary amine, and, theoretically, we ought to be able
to resolve (separate) these enantiomers. In practice, however, resolution is usually impossible
because the enantiomers interconvert rapidly:
This interconversion occurs through what is called a pyramidal or nitrogen inversion.
The barrier to the interconversion is about 25 kJ mol1 for most simple amines, low enough
to occur readily at room temperature. In the transition state for the inversion, the nitrogen
atom becomes sp2 hybridized with the unshared electron pair occupying a p orbital.
Ammonium salts cannot undergo nitrogen inversion because they do not have an
unshared pair. Therefore, those quaternary ammonium salts with four different groups are
chiral and can be resolved into separate (relatively stable) enantiomers:
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Chemistry Sem IV Amines
Basicity of Amines: Amine Salts
Amines are relatively weak bases. Most are stronger bases than water but are far
weaker bases than hydroxide ions, alkoxide ions, and alkanide anions.
A convenient way to compare the base strengths of amines is to compare the pKa values of
their conjugate acids, the corresponding alkylaminium ions
The equilibrium for an amine that is relatively more basic will lie more toward the left
in the above chemical equation than for an amine that is less basic.
The aminium ion of a more basic amine will have a larger pKa than the aminium
ion of a less basic amine.
When we compare aminium ion acidities in terms of this equilibrium, we see that most
primary alkylaminium ions (RNH3+) are less acidic than ammonium ion (NH4+). In other
words, primary alkylamines (RHN2) are more basic than ammonia (NH3):
Basicity of Aryl Amines
Aromatic amines are much weaker bases than alkylamines.
Considering amine basicity from the perspective of aminium ion acidity, when we examine
the pKa values of the conjugate acids of aromatic amines (e.g., aniline and 4-methylaniline),
we see that they are much weaker bases than the nonaromatic amine, cyclohexylamine:
We can account for this effect, in part, on the basis of resonance contributions to the
overall hybrid of an arylamine. For aniline, the following contributors are important:
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Chemistry Sem IV Amines
Structures 1 and 2 are the Kekulé structures that contribute to any benzene derivative.
Structures 3–5, however, delocalize the unshared electron pair of the nitrogen over the ortho
and para positions of the ring. This delocalization of the electron pair makes it less available
to a proton, and delocalization of the electron pair stabilizes aniline.
Basicity of Heterocyclic Amines
Nonaromatic heterocyclic amines have basicities that are approximately the same as
those of acyclic amines
In aqueous solution, aromatic heterocyclic amines such as pyridine, pyrimidine, and
pyrrole are much weaker bases than nonaromatic amines or ammonia. (In the gas phase,
however, pyridine and pyrrole are more basic than ammonia, indicating that solvation has a
very important effect on their relative basicities:
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