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The Sandmeyer Reaction: Replacement of The Diazonium Group by CL, BR, or CN

The Sandmeyer Reaction involves replacing the diazonium group of arenediazonium salts with halides (Cl, Br, CN) or other groups. Specific examples show o-toluidine reacted with copper chloride to form o-chlorotoluene. m-Chloroaniline reacted with copper bromide to form m-bromochlorobenzene. o-Nitroaniline reacted with copper cyanide to form o-nitrobenzonitrile. p-Nitroaniline reacted with potassium iodide to form p-iodonitrobenzene. m-Toluidine reacted with fluoroboric acid and heat to form m-fluorotoluene

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790 views2 pages

The Sandmeyer Reaction: Replacement of The Diazonium Group by CL, BR, or CN

The Sandmeyer Reaction involves replacing the diazonium group of arenediazonium salts with halides (Cl, Br, CN) or other groups. Specific examples show o-toluidine reacted with copper chloride to form o-chlorotoluene. m-Chloroaniline reacted with copper bromide to form m-bromochlorobenzene. o-Nitroaniline reacted with copper cyanide to form o-nitrobenzonitrile. p-Nitroaniline reacted with potassium iodide to form p-iodonitrobenzene. m-Toluidine reacted with fluoroboric acid and heat to form m-fluorotoluene

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Usman Ghani
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© © All Rights Reserved
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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cyanide to give products in which the diazonium group has been replaced by C ,
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.

CH3 CH3 CH3


+
NH2 N2 Cl – Cl
HCl, NaNO2 CuCl
+ N 2
H2O 15– 60
(0 – 5 °C
o-Toluidine °C) o-Chlorotoluene
(74–79%
overall)
+
NH2 N2 Br – Br
HBr, NaNO2 CuBr
+N 2
H2O 100 °C
(0 – 10
°C)
Cl Cl Cl
m-Chloroaniline m- Bromochlorobenzene
(70% overall)

NO2 NO2 NO2


+
–
NH 2 N2 Cl CN
HCl, NaNO2 CuCN
+ N 2
H2O 90– 100 °C
(25 °C)
o-Nitroaniline o-Nitrobenzonitrile
(65% overall)

Replacement by
Arenediazonium salts react with potassium iodide to give products in which the
diazonium group has been replaced by . An example is the synthesis of p-
iodonitrobenzene:

NO2 NO2 NO2

H2SO4 , KI
+ N2
NaNO2
(0 – 5
H2O
°C)
NH2 N + HSO –
I
2 4
p-Nitroaniline p-Iodonitrobenzene
(81% overall)

Replacement by F
The diazonium group can be replaced by fluorine by treating the diazonium salt with
fluoroboric acid ( HBF 4 ). The diazonium fluoroborate that precipitates is isolated,
dried, and heated until decomposition occurs. An aryl fluoride is produced:
CH3 CH3 CH3

(1) HONO, H +
heat
+ N2 + 3
(2) HBF 4
NH2 N2+ BF − F BF
m-Toluidine 4
m -F luorotoluene
m-Toluenediazonium (69%)
fluoroborate
(79%)

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