Amines S-3

Chemistry Sem IV Amines
Session 1: Reactions of aliphatic and aromatic amines with nitrous

acid, replacement reaction of arenediazonium salt (replacement by
–Cl/-Br, -CN, -I, -F, -OH, -H), coupling reaction of arenediazonium salt
Reactions of Amines with Nitrous Acid

Nitrous acid (HONO) is a weak, unstable acid. It is always prepared in situ, usually by
treating sodium nitrite (NaNO2) with an aqueous solution of a strong acid:
Nitrous acid reacts with all classes of amines. The products that we obtain from these
reactions depend on whether the amine is primary, secondary, or tertiary and whether the
amine is aliphatic or aromatic.
Reactions of Primary Aliphatic Amines with Nitrous Acid

Primary aliphatic amines react with nitrous acid through a reaction called diazotization
to yield highly unstable aliphatic diazonium salts. Even at low temperatures, aliphatic
diazonium salts decompose spontaneously by losing nitrogen to form carbocations. The
carbocations go on to produce mixtures of alkenes, alcohols, and alkyl halides by removal of
a proton, reaction with H2O, and reaction with X-:
Diazotizations of primary aliphatic amines are of little synthetic importance because

they yield such a complex mixture of products. Diazotizations of primary aliphatic amines are
used in some analytical procedures, however, because the evolution of nitrogen is
quantitative. They can also be used to generate and thus study the behaviour of carbocations
in water, acetic acid, and other solvents.
Reactions of Secondary Amines with Nitrous Acid

Secondary amines—both aryl and alkyl—react with nitrous acid to yield N-nitrosoamines.
N-Nitrosoamines usually separate from the reaction mixture as oily yellow liquids:
Examples:
1
Digital Learning-DCE Karnatak University
Reactions of Tertiary Amines with Nitrous Acid

When a tertiary aliphatic amine is mixed with nitrous acid, an equilibrium is established
among the tertiary amine, its salt, and an N-nitrosoammonium compound:
Although N-nitrosoammonium compounds are stable at low temperatures, at higher

temperatures and in aqueous acid they decompose to produce aldehydes or ketones. These
reactions are of little synthetic importance, however.
Tertiary arylamines react with nitrous acid to form C-nitroso aromatic compounds.
Nitrosation takes place almost exclusively at the para position if it is open and, if not, at
the ortho position.
Reactions of Primary Arylamines with Nitrous Acid

The most important reaction of amines with nitrous acid, by far, is the reaction of
primary arylamines. Primary arylamines react with nitrous acid to give arenediazonium salts.
Even though arenediazonium salts are unstable, they are still far more stable than aliphatic
diazonium salts; they do not decompose at an appreciable rate in solution when the
temperature of the reaction mixture is kept below 5°C:
Diazotization of a primary amine takes place through a series of steps. In the presence
of strong acid, nitrous acid dissociates to produce +NO ions. These ions then react with the
nitrogen of the amine to form an unstable N-nitrosoaminium ion as an intermediate. This
2
intermediate then loses a proton to form an N-nitrosoamine, which, in turn, tautomerizes

to a diazohydroxide in a reaction that is similar to keto–enol tautomerization. Then, in the
presence of acid, the diazohydroxide loses water to form the diazonium ion.
Diazotization reactions of primary arylamines are of considerable synthetic

importance because the diazonium group, can be replaced by a variety of other functional
groups.
Replacement Reactions of Arenediazonium Salts

Arenediazonium salts are highly useful intermediates in the synthesis of aromatic
compounds, because the diazonium group can be replaced by any one of a number
of other atoms or groups, including -F, -Cl, -Br, -I, -CN, -OH, and -H.
Diazonium salts are almost always prepared by diazotizing primary aromatic amines.
Primary arylamines can be synthesized through reduction of nitro compounds that are readily
available through direct nitration reactions.
Syntheses Using Diazonium Salts

Most arenediazonium salts are unstable at temperatures above 5–10°C, and many
explode when dry. Fortunately, however, most of the replacement reactions of diazonium
salts do not require their isolation. We simply add another reagent (CuCl, CuBr, KI, etc.) to the
mixture, gently warm the solution, and the replacement (accompanied by the evolution of
nitrogen) takes place:
3
Only in the replacement of the diazonium group by F- need we isolate a diazonium

salt. We do this by adding HBF4 to the mixture, causing the sparingly soluble and reasonably
stable arenediazonium fluoroborate, ArN2+ BF4-, to precipitate.
The Sandmeyer Reaction: Replacement of the Diazonium Group by -Cl, -Br, or -CN
Arenediazonium salts react with cuprous chloride, cuprous bromide, and cuprous
cyanide to give products in which the diazonium group has been replaced by Cl, Br, and
CN, respectively. These reactions are known generally as Sandmeyer reactions. Several
specific examples follow. The mechanisms of these replacement reactions are not fully
understood; the reactions appear to be radical in nature, not ionic.
Replacement by -I
4
Arenediazonium salts react with potassium iodide to give products in which the diazonium
group has been replaced by I. An example is the synthesis of p-iodonitrobenzene:
Replacement by -OH
The diazonium group can be replaced by a hydroxyl group by adding cuprous oxide to
a dilute solution of the diazonium salt containing a large excess of cupric nitrate:
Replacement by Hydrogen: Deamination by Diazotization

Arenediazonium salts react with hypophosphorous acid (H3PO2) to yield products in
which the diazonium group has been replaced by -H.
Since we usually begin a synthesis using diazonium salts by nitrating an aromatic
compound, that is, replacing H by NO2 and then by NH2, it may seem strange that we
would ever want to replace a diazonium group by H. However, replacement of the diazonium
group by H can be a useful reaction. We can introduce an amino group into an
aromatic ring to influence the orientation of a subsequent reaction. Later we can remove the
amino group (i.e., carry out a deamination) by diazotizing it and treating the diazonium
salt with H3PO2.
We can see an example of the usefulness of a deamination reaction in the following
synthesis of m-bromotoluene.
5
Coupling Reactions of Arenediazonium Salts

Arenediazonium ions are weak electrophiles; they react with highly reactive aromatic
compounds—with phenols and tertiary arylamines—to yield azo compounds. This
electrophilic aromatic substitution is often called a diazo coupling reaction.
6
Couplings between arenediazonium cations and phenols take place most rapidly in
slightly alkaline solution. Under these conditions an appreciable amount of the phenol is
present as a phenoxide ion, ArO, and phenoxide ions are even more reactive toward
electrophilic substitution than are phenols themselves. (Why?) If the solution is too alkaline
(pH 10), however, the arenediazonium salt itself reacts with hydroxide ion to form a relatively
unreactive diazohydroxide or diazotate ion:
Couplings between arenediazonium cations and amines take place most rapidly in
slightly acidic solutions (pH 5–7). Under these conditions the concentration of the
arenediazonium cation is at a maximum; at the same time an excessive amount of the amine
has not been converted to an unreactive aminium salt:
If the pH of the solution is lower than 5, the rate of amine coupling is low.
With phenols and aniline derivatives, coupling takes place almost exclusively at the
para position if it is open. If it is not, coupling takes place at the ortho position.
7
8

Amines S-3

Uploaded by

Copyright:

Available Formats

Amines S-3

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Amines S-3

Uploaded by

Copyright:

Available Formats

Chemistry Sem IV Amines

Session 1: Reactions of aliphatic and aromatic amines with nitrous

Reactions of Amines with Nitrous Acid

Reactions of Primary Aliphatic Amines with Nitrous Acid

Diazotizations of primary aliphatic amines are of little synthetic importance because

Reactions of Secondary Amines with Nitrous Acid

Reactions of Tertiary Amines with Nitrous Acid

Although N-nitrosoammonium compounds are stable at low temperatures, at higher

Reactions of Primary Arylamines with Nitrous Acid

intermediate then loses a proton to form an N-nitrosoamine, which, in turn, tautomerizes

Diazotization reactions of primary arylamines are of considerable synthetic

Replacement Reactions of Arenediazonium Salts

Syntheses Using Diazonium Salts

Only in the replacement of the diazonium group by F- need we isolate a diazonium

Replacement by Hydrogen: Deamination by Diazotization

Coupling Reactions of Arenediazonium Salts

You might also like