EDEXCEL
Topic 18B:9.
To understand the
reactions of primary aliphatic amines, using butylamine as an example, with:
. i
water to form an alkaline solution
. ii
acids to form salts
. iii
ethanoyl chloride
. iv
halogenoalkanes
. v
copper(II)ions to form complex ions
AQA
Nucleophilic
properties of Amines
Amines are
nucleophiles.
The nucleophilic
substitution reactions of ammonia and amines with halogenoalkanes to form
primary, secondary, tertiary amines and quaternary ammonium salts.
The use of
quaternary ammonium salts as cationic surfactants.
The nucleophilic
addition–elimination reactions of ammonia and primary amines with acyl
chlorides and acid anhydrides.
Students should be
able to outline the mechanisms of:
.
these nucleophilic substitution reactions
.
the nucleophilic addition–elimination reactions
of ammonia and primary amines with acyl chlorides.
Reactions of Amines
Let’s first look at these simple reactions of amines with butylamine C4H9NH2 as
our example:
1. With water
C4H9NH2 + H2O ⇌ [C4H9NH3]+ +
OH—
Like ammonia, butylamine is a water soluble weak base and forms
butylammonium ( [C4H9NH3]+ ) ions
in aqueous solution.
2. With acids to form salts
C4H9NH2 + HCl
⟶ [C4H9NH3]+ +
Cl—
3. With ethanoyl chloride
C4H9NH2
+ CH3COCl ⟶ C4H9NHCOCH3 +
H+ + Cl—
This very fast room temperature reaction forms N-butyl ethanamide. The picture below shows this reaction and in
particular the evolution of the white fumes of the amine chloride.
4. With excess halogeno alkanes under pressure and at 120oC
C4H9NH2
+ CH3Cl ⟶ [C4H9NH2CH3
]+ + Cl—
Then methyl groups successively replace hydrogen atoms in the amine salts:
[C4H9NH2CH3 ]+ +
CH3Cl ⟶ [C4H9NH(CH3)2]+ +
Cl—
then
[C4H9NH(CH3)2]+ +
CH3Cl ⟶ [C4H9N(CH3)3]+ +
Cl—
The final product is the quaternary amine salt: trimethyl butyl ammonium
chloride.
5. With copper(II) ions to form complex ions
Butylamine acts as if it were ammonia so that the nitrogen lone pair forms
a dative covalent bond with the transition metal ion. 4 moles of the amine react with one mole of
the copper ion as in the ammonia reaction and produce a square planar complex
ion.
4C4H9NH2
+ Cu2+ ⟶ [Cu(C4H9NH2)4
]2+
In the equation above, I have removed all state symbols and other
unnecessary ions (e.g. sulphate SO42—) in order to show
up more clearly the formation of the complex.
In the photo above of the reaction in aqueous solution the pale blue copper
ion solution turns the deeper blue of the copper complex.
Let’s now recap the two significant mechanisms here:
First the mechanism for the reaction between a halogenoalkane and an amine:
The reaction depends on the nucleophilic character of the amine i.e. that
it carries a lone pair of electrons on its nitrogen atom. It is this lone pair that attacks the
electropositive carbon atom in the halogenoalkane in step one. Excess amine is then protonated to leave the
free secondary amine and the amine salt:
In the diagram above note that the amine is shown with a negative charge
rather than a lone pair:
Second, the mechanism for the reaction between an amine and an acyl
chloride
This again illustrates the nucleophilic character of the amine because of
its nitrogen lone pair.
In the illustration below I have kept to the ammonia molecule for
simplicity
But you can see that the first step is the nucleophilic attack on the
electropositive carbon atom of the —COCl group.
This attack leaves a species with a charge separation: the oxygen atom
carries a negative charge and the nitrogen atom a positive charge.
Therefore, the second step is the resolution of this charge separation as
they come together. In doing so, a
molecule of HCl is eliminated.
So an addition step is followed by an elimination step.
Hence this is called an addition-elimination mechanism.
This leaves a new molecule where the ammonia or amine group has replaced
the labile chlorine atom.
Here is summary chart for the substitution mechanism:
In the next blog, we’ll look at amides and amino acids.
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