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RESEARCH PAPER
AUGUST, 460462
A simple and selective conversion of aldehydes into the corresponding nitriles and primary amides in aqueous
ammonia has been developed. The aldehydes were efficiently converted to the corresponding nitriles in moderate to
excellent yields using tetrabutylammonium iodide/tert-butyl hydroperoxide system. The primary amides, however,
can be selectively synthesised only in the presence of tert-butyl hydroperoxide.
Entry
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
a
Amine
Catalyst
/mmol
Oxidant
/mmol
T/C
Yield
/%b
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH3.H2O
NH4Cl
HCOONH4
CH3COONH4
(NH4)2CO3
TBAI (0.2)
TBAI (0.2)
TBAI (0.2)
TBAI (0.2)
TBAI (0.1)
TBAI (0.05)
TBAI (0.2)
TBAI (0.2)
TBAI (0.2)
KI (0.2)
TBAI (0.2)
TBAI (0.2)
TBAI (0.2)
TBAI (0.2)
TBHP (3)
TBHP (3)
TBHP (1.2)
TBHP (1.2)
TBHP (1.2)
TBHP (1.2)
TBHP (1.2)
H2O2 (1.2)
NaOCl (1.2)
TBHP (1.2)
TBHP (1.2)
TBHP (1.2)
TBHP (1.2)
TBHP (1.2)
80
80
80
60
rt
80
80
80
80
80
80
80
80
80
80
95c
92
90
74
13
85
71
NRd
NRd
NRd
81
NRd
NRd
NRd
NRd
t (h)
Yield/%b
Mp/Clit.
C6H54-MeC6H44-MeOC6H44-ClC6H43-ClC6H42-ClC6H44-BrC6H44-FC6H44-CF3C6H42-FurylC6H5CH2CH3(CH2)3CH3(CH2)5-
12
12
16
12
12
12
12
12
12
12
16
24
24
92
90
85
95
90
82
93
87
89
90
82
65
60
Oil6
Oil25
5860(5859)26
9092(9192)26
3840(3940)25
4345(4244)25
110112(110115)27
3234(3234)27
3840(3738)25
Oil28
Oil28
Oil25
Oil25
Entry
1
2
3
4
5
6
7
8
9
10
11
12
13
a
Reaction conditions: aldehyde (1 mmol), NH3.H2O (3 mL), TBAI
(0.2 mmol), TBHP (1.2 mmol), 80 C.
b
Isolated yields.
Entry
1
2
3
4
5
6
7
8
9
10
11
t/h
Yield/%b
M.p. /Clit.
C6H54-MeC6H44-MeOC6H44-ClC6H43-ClC6H42-ClC6H44-BrC6H44-FC6H44-NO2C6H44-CF3C6H4CH3(CH2)3-
12
12
12
12
12
12
12
12
12
12
24
93
88
91
95
92
83
93
84
97c
90
67
125126(125127)29
159160(161163)29
164167(166167)30
177179(178180)31
135136(135137)31
139140(140141)31
190193(190192)32
154156(153154)32
198200(199201)30
182184(182183)32
104106(102104)30
a
Reaction conditions: aldehyde (1 mmol), NH3.H2O (3 mL),
TBHP (1.2 mmol), 80 C.
b
Isolated yields.
c
CH3CN was the solvent.
461
Scheme 2
462
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19
20
21
22
23
24
25
26
27
28
29
30
31
32
33