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cyanide to give products in which the diazonium group has been replaced by C ,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diazonium group has been replaced by .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%)