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+
H
N
H
H
O
N
+
+
O
N
+
N
+
N
H
N
+
nitrosation of
secondary amines
gives an N-nitroso
amine
Example
(CH3)2NH
NaNO2, HCl
H2O
(CH3)2N
(88-90%)
(CH3)2N
N-nitrosodimethylamine
(leather tanning)
N-nitrosopyrrolidine
(nitrite-cured bacon)
N-nitrosonornicotine
(tobacco smoke)
H
H
N
+
H
N
H
N
+
analogous to
nitrosation of
secondary amines
to this point
H
R
N
H
this species reacts further
R
H
N
O
+
H
nitrosation of a
primary alkylamine
gives an alkyl
diazonium ion
process is called
diazotization
H
R
+
N
H
R
O
+
H
+ +
R
N
+
N
+
N
HONO
NH2
OH
(80%)
H2O
N2
+
(3%)
(2%)
N
R
R
R
+
N
R
Nitrosation of Arylamines
N(CH2CH3)2
1. NaNO2, HCl,
H2O, 8C
N(CH2CH3)2
2. HO
N
(95%)
Nitrosation of N-Alkylarylamines
similar to secondary alkylamines;
gives N-nitroso amines
NHCH3
NaNO2, HCl,
H2O, 10C
NCH3
(87-93%)
N
N
fast
+
R
+ N2
slow
+
Ar
+ N2
Example:
(CH3)2CH
NH2
NaNO2, H2SO4
H2O, 0-5C
(CH3)2CH
+
N
N HSO4
H
Ar
NO2
Ar
NH2
Ar
+
N
Synthetic Transformations
ofAryl Diazonium Salts
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Preparation of Phenols
+
N
Ar
N
H2O, heat
Ar
OH
Example
NH2
(CH3)2CH
1. NaNO2, H2SO4
H2O, 0-5C
2. H2O, heat
OH
(CH3)2CH
(73%)
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Ar
+
N
KI
Ar
Example
NH2
Br
1. NaNO2, HCl
H2O, 0-5C
I
Br
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Ar
Ar
+
N
Example
NH2
1. NaNO2, HCl,
H2O, 0-5C
CCH2CH3
O
2. HBF4
3. heat
CCH2CH3
O
(68%)
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Cl
Ar
Ar
+
N
Br
Example
NH2
1. NaNO2, HCl,
Cl
H2O, 0-5C
NO2
2. CuCl, heat
NO2
(68-71%)
Example
1. NaNO2, HBr,
NH2
Cl
H2O, 0-10C
Br
Cl
2. CuBr, heat
(89-95%)
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Ar
CN
Ar
+
N
Example
1. NaNO2, HCl,
NH2
CH3
H2O, 0C
CN
CH3
2. CuCN, heat
(64-70%)
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
+
N
Example
NaNO2, H2SO4,
NH2
CH3
H3PO2
CH3
(70-75%)
Example
NH2
Br2
NH2
Br
NaNO2, H2SO4,
Br
H2O, CH3CH2OH
H2O
Br
Br
Br
(100%)
Br
(74-77%)
Azo Coupling
Azo Coupling
Diazonium salts are weak electrophiles.
React with strongly activated aromatic
compounds by electrophilic aromatic
substitution.
Ar
+
N
N + Ar'
Ar
Ar'
an azo compound
Ar' must bear a strongly electron-releasing group
such as OH, OR, or NR2.
Example
OH
+
+ C6H5N
OH
N
NC6H5
Cl