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16
Nitrosation of Alkylamines
+
H
H
O
N
H
N
+
+
O
O
H
N
+
N
+
N
+
N
+
nitrosation of
secondary amines
gives an N-nitroso
amine
Example
(CH3)2NH
NaNO2, HCl
H 2O
(CH3)2N
(88-90%)
(CH3)2N
N-nitrosodimethylamine
(leather tanning)
N
N
O
N-nitrosopyrrolidine
(nitrite-cured bacon)
N
O
N-nitrosonornicotine
(tobacco smoke)
+
N
H
H
N
+
N
+
H
R
N
analogous to
nitrosation of
secondary amines
to this point
H
this species reacts further
R
N
H
R
N
R
N
+
N
O
+
H
R
N
O
+
H
nitrosation of a
primary alkylamine
gives an alkyl
diazonium ion
process is called
diazotization
H
R
+
N
H
R
N
O
+
H
+ +
R
N
+
N
NH2
OH
+
N
HONO
H 2O
N2
(80%)
+
Fig. 22.5 (p 890)
(3%)
(2%)
R
R
+
N
N
R
22.17
Nitrosation of Arylamines
1. NaNO2, HCl,
H2O, 8C
N(CH2CH3)2
2. HO
N
(95%)
Nitrosation of N -Alkylarylamines
similar to secondary alkylamines;
gives N-nitroso amines
NaNO2, HCl,
H2O, 10C
NHCH3
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
Ar
N O2
Ar
NH2
Ar
+
N
22.18
Synthetic Transformations of Aryl Diazonium Salts
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Preparation of Phenols
hydrolysis of a diazonium salt
+
N
Ar
N
H2O, heat
Ar
OH
Example
NH2
(CH3)2CH
1. NaNO2, H 2SO4
H2O, 0 -5C
2. H2O, heat
OH
(CH3)2CH
(73%)
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
Ar
+
N
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,
H2O, 0 -5C
NO2
2. CuCl, heat
Cl
NO2
(68-71%)
Example
NH2
Cl
1. NaNO2, HBr,
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
NH2
CH3
1. NaNO2, HCl,
H2O, 0C
CN
CH3
2. CuCN, heat
(64-70%)
Cl
Ar
CN
+
N
Ar
Ar
Ar
Ar
H
Ar
Br
OH
+
N
Example
NH2
CH3
NaNO2, H2SO4,
H3PO2
CH3
(70-75%)
Example
NH2
NH2
Br2
NaNO2, H2SO4,
Br H O, CH CH OH
2
3
2
Br
H 2O
Br
Br
Br
(100%)
Br
(74-77%)
22.19
Azo Coupling
Azo Coupling
Diazonium salts are weak electrophiles.
React with strongly activated aromatic
compounds by electrophilic aromatic
substitution.
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 NR 2.
Example
OH
+
+ C 6H 5N
OH
N
NC6H5
Cl