One-pot three-component synthesis of α-aminonitriles using potassium hexacyanoferrate(II) as an eco-friendly cyanide source

Article abstract of DOI:10.1016/j.tetlet.2010.05.088

An efficient and environmentally friendly method has been developed for the synthesis of α-aminonitriles via one-pot three-component condensation of carbonyl compounds, amines, and potassium hexacyanoferrate(II) in the presence of benzoyl chloride as a promoter. This protocol has the features of use of eco-friendly cyanide source, high yield, and simple work-up procedure.

Full text of DOI:10.1016/j.tetlet.2010.05.088

Tetrahedron Letters 51 (2010) 3922–3926
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Tetrahedron Letters
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One-pot three-component synthesis of
a-aminonitriles using potassium
hexacyanoferrate(II) as an eco-friendly cyanide source
*
Zheng Li , Yuanhong Ma, Jun Xu, Jinghong Shi, Hongfang Cai
Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu 730070, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
An efficient and environmentally friendly method has been developed for the synthesis of a-aminonitr-
Received 2 April 2010
Revised 13 May 2010
Accepted 21 May 2010
Available online 25 May 2010
iles via one-pot three-component condensation of carbonyl compounds, amines, and potassium hexacy-
anoferrate(II) in the presence of benzoyl chloride as a promoter. This protocol has the features of use of
eco-friendly cyanide source, high yield, and simple work-up procedure.
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
a-Aminonitrile
Green chemistry
Multicomponent reactions
Nucleophilic addition
Potassium hexacyanoferrate(II)
Strecker reaction
a
-Aminonitriles are significantly important intermediates for
ical waste.22 Implementation of methods that avoid the use of toxic
reagents and/or metal-based catalysts is a fundamental strategy in
this field. Therefore, it is still desirable to search for an environ-
mentally friendly cyanating agent and develop an efficient and
practical method for the Strecker reaction under mild conditions.
Potassium hexacyanoferrate(II), K4[Fe(CN)6], is non-toxic and is
even used in the food industry for metal precipitation. In addition,
it has been described as an anti-agglutinating auxiliary for table
salt (NaCl). K4[Fe(CN)6] is a by-product of coal chemical industry
and commercially available on a ton scale, and is even cheaper
than KCN. Very recently, K4[Fe(CN)6] has been used as a cyanide
source in the synthesis of benzonitriles23 and aroyl cyanides.24
However, it is noteworthy to mention that all the reported reac-
tions using K4[Fe(CN)6] as a cyanide source belong to substitution
reactions. There are no examples reported for nucleophilic addition
reactions. In this study, we report an efficient method for the
the synthesis of a wide variety of amino acids, amides, diamines,
and nitrogen-containing heterocycles.1 Among the methods re-
ported for the synthesis of
nucleophilic addition of cyanide ion to imines, is of great impor-
tance to modern organic chemistry as it offers one of the most
direct and viable methods for the synthesis of
In general, -aminonitriles are synthesized by the reactions of
a-aminonitriles, Strecker reaction,
a
-aminonitriles.2
a
aldehydes/ketones with amines in the presence of a cyanide source
such as HCN,3 KCN,4 TMSCN,5 (EtO)2P(O)CN,6 Et2AlCN,7 Bu3SnCN,8
MeCOCN,9 acetone cyanohydrin,10 and ethyl cyanoformate,11
which are often hazardous, toxic, and involve harsh reaction condi-
tions. Recently, modified methods using one-pot procedure via
three-component condensation of aldehyde/ketone, amine, and
trimethylsilyl cyanide catalyzed by Cu(OTf)2,12 BiCl3,13 NiCl2,14
InI3,15 RuCl3,16 Sc(OTf)3,17 La(NO3)3Á6H2O or GdCl3Á6H2O,18 I2,19
H4SiW12O40/Al2O3,20 and metal complexes21 in conventional
organic solvents have been described. However, trimethylsilyl cya-
nide is sensitive to moisture and can easily liberate toxic hydrogen
cyanide. Meanwhile many of these reported methods involve the
use of expensive reagents, toxic organic solvents, tedious work-
up procedure, and longer reaction times. The development of envi-
ronmentally friendly organic reactions (green chemistry) is a very
active field of research, emerging as a response to the increasing
regulatory pressure directed to the elimination/reduction of chem-
synthesis of
a-aminonitriles using K4[Fe(CN)6] as an efficient
nucleophilic addition reagent and as an environmentally friendly
cyanide source.
In order to explore the use of K4[Fe(CN)6] as an environmentally
friendly addition reagent in cyanation reactions, the initial research
was focused on the synthesis of
a-aminonitrile by one-pot three-
component reaction of benzaldehyde, aniline, and K4[Fe(CN)6]. The
three-component reaction was attempted at different catalytic sys-
tems such as Lewis acids, Lewis bases, and some metal complexes
under different temperature in various solvents. Unfortunately, no
products were observed in the studied conditions. However, in the
later research, it was found that some acyl chlorides could efficiently
* Corresponding author.
E-mail address: lizheng@nwnu.edu.cn (Z. Li).
0040-4039/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2010.05.088

Z. Li et al. / Tetrahedron Letters 51 (2010) 3922–3926
3923
Table 2
One-pot synthesis of
promote the three-component reaction of benzaldehyde, aniline,
and K4[Fe(CN)6] (Table 1). Among the selected acyl chlorides, acetyl
chloride and oxalyl chloride were not valid for the reaction because
of their volatility and instability (Table 1, entries 1 and 2), phenylsul-
fonyl chloride and furoyl chloride could promote the reaction to give
a
-aminonitrile under different solventsa
Entry
Solvent
Reaction time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
Et2O
PhMe
THF
MeCN
CH2Cl2
DMF
MeOH
EtOH
24
24
22
19
24
18
10
8
0
0
55
60
84
71
80
88
the corresponding
5 and 6), meanwhile aroyl chlorides could promote the reaction to
afford the desired -aminonitrile in high yield (Table 1, entries 3
a-aminonitrile in moderate yield (Table 1, entries
a
and 4), especially benzoyl chloride could afford the best result
(Table 1, entry 3). In addition, it was also found that for 1 mol of
benzaldehyde and aniline, only 0.2 equiv of K4[Fe(CN)6] was
required, which indicated that six CNÀ in K4[Fe(CN)6] could be read-
ily utilized in this reaction.
a
Reaction conditions: benzaldehyde (2 mmol), aniline (2 mmol), benzoyl chlo-
ride (2 mmol), and K4[Fe(CN)6] (0.4 mmol) in 5 mL of solvent.
b
Isolated yield.
The further research showed that solvents also played a crucial
role in the one-pot three-component reaction of benzaldehyde,
aniline, and K4[Fe(CN)6] using benzoyl chloride as a promoter
aromatic amines were effective to the one-pot three-component
reactions except for the amines bearing strong electron-withdraw-
ing groups on the aryl ring, such as nitro, which could not give
(Table 2). It was found that no
a-aminonitrile was observed in
some nonpolar solvents such as diethyl ether and toluene
(Table 2, entries 1 and 2). However, the reaction in polar solvents
such as THF, CH3CN, CH2Cl2, DMF, MeOH, and EtOH could give
the desired product in moderate to high yield (Table 2, entries
a-aminonitriles because the nucleophilic property of amines was
weakened by nitro. The promoter, benzoyl chloride, was trans-
formed into benzoic acid in the reactions, which could be easily
recovered from the reaction system and further reused after
regeneration.
3–8). Especially the reaction in EtOH afforded
highest yield within shortest time.
a-aminonitrile in
A plausible mechanism for the synthesis of a-aminonitriles using
Based on these promising findings, a series of one-pot three-
component reactions of aldehydes or ketones, amines, and
K4[Fe(CN)6] were investigated in EtOH using benzoyl chloride as
a promoter (Scheme 1).25 Aromatic aldehydes bearing electron-
donating or electron-withdrawing groups could participate in the
K4[Fe(CN)6] as a cyanide source, according to Hunig’s review,26 is
shown in Scheme 2. Firstly K4[Fe(CN)6] reacts with benzoyl chloride
to form benzoyl cyanide. Then benzoyl cyanide is attacked by water
to produce hydrogen cyanide in situ. Finally, nucleophilic addition
of cyanide ion to the imines, which is formed from condensation
reactions to afford the desired
a-aminonitriles in high yield. The
of aldehydes and amines, yields
In summary, an efficient and environmentally friendly method
for the synthesis of -aminonitriles through one-pot three-compo-
nent condensation of aldehydes/ketones, amines, and K4[Fe(CN)6]
using benzoyl chloride as a promoter in ethanol was developed.
The significant features of this method are the use of non-toxic,
inexpensive K4[Fe(CN)6] as the cyanide source to replace the tradi-
tional strong toxic and volatile cyanating agents, the simplicity of
a-aminonitriles.
substituents on the aryl rings have no obvious effect on the yield
of reactions. Aliphatic aldehydes were also effective for the reac-
tions to produce the corresponding product in slightly lower yield.
Heteroaromatic aldehyde such as furaldehyde had the similar
manner to that of aromatic aldehydes for the reactions. Ketones,
such as acetophenone, cyclopentanone, and cyclohexanone, are
also suitable for the three-component reactions although the reac-
tion rate is slightly slower than aldehydes. Meanwhile most
a
Table 1
One-pot synthesis of
a
-aminonitrile using different promotersa
Entry
Promoter
Reaction time (h)
8
Reaction temperature (°C)
Yieldb (%)
0
O
1
2
50
Cl
O
Cl
Cl
8
8
63
0
O
O
Cl
3
4
5
160
88
O
Cl
8
8
8
160
160
160
76
62
66
Cl
O
Cl
O
O
6
S
Cl
O
a
Reaction condition: benzaldehyde (2 mmol), aniline (2 mmol), promoter (2 mmol), and K4[Fe(CN)6] (0.4 mmol).
Isolated yield.
b

3924
Z. Li et al. / Tetrahedron Letters 51 (2010) 3922–3926
Table 3
One-pot three-component synthesis of a
-aminonitriles using K4[Fe(CN)6] as cyanide sourcea
Entry
Aldehyde or ketone
Amine
Reaction time (h)
8
Yieldb (%)
88
Mp (°C)
CHO
NH2
NH2
1
76–78
CHO
CHO
2
3
7
7
89
85
86–87
94–96
CH3
NH2
CH3
CH3
Cl
CHO
NH2
4
5
8
8
90
82
81–83
91–92
CHO
CHO
NH2
NH2
6
7
8
5
5
8
83
84
87
112–113
135–136
120–121
CHO
CHO
NH2
NH2
Cl
CHO
NH2
CH3
9
10
11
12
13
14
6
9
8
8
5
4
87
80
84
81
84
79
110–112
144–145
61–62
Cl
CHO
NH2
Cl
Cl
CHO
NH2
NH2
NH2
OCH3
CHO
95–97
CH3O
CHO
153–154
157–160
OH
CH3
NH2
CHO
NO2
CH3
NH2
CHO
15
16
4
6
83
80
85–87
Oil
NO2
NO2
CHO
NH2
CHO
Cl
CHO
CHO
NH2
17
18
6
7
89
78
112–114
67–68
Cl
O
NH2
CH3
NH2
NH2
19
20
9
9
70
72
Oil
Oil
CHO

Z. Li et al. / Tetrahedron Letters 51 (2010) 3922–3926
3925
Table 3 (continued)
Entry
Aldehyde or ketone
Amine
Reaction time (h)
Yieldb (%)
74
Mp (°C)
O
NH2
21
10
10
152–154
138–140
CH3
O
NH2
22
23
70
NH2
NH2
O
O
12
11
73
76
67–68
70–71
24
a
Reaction condition: aldehyde or ketone (2 mmol), amine (2 mmol), benzoyl chloride (2 mmol), and K4[Fe(CN)6] (0.4 mmol) in 5 mL of ethanol.
Isolated yield.
b
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CN
R1
R2
Promoter
EtOH
R3
+
O
R3NH2
K4[Fe(CN)6]
+
R1
N
H
R2
Scheme 1. Synthesis of a-aminonitriles using K4[Fe(CN)6] as cyanide source.
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O
H
C
CN
Ph
OH
CN
R1
R2
R3
O
R1
N
H
R1
R2
R2
N R3
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R3 NH2
H2O
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Scheme 2. Proposed mechanism for Strecker reactions using K4[Fe(CN)6] as
cyanide source.
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reaction and work-up procedure, the high yield, and the avoiding
use of acids or metal catalysts.
Acknowledgments
The authors thank the National Natural Science Foundation of
China (20772096) and Key Laboratory of Eco-Environment-Related
Polymer Materials (Northwest Normal University), Ministry of
Education of China for the financial support of this work.
24. Li, Z.; Shi, S. Y.; Yang, J. Y. Synlett 2006, 2495–2497.
25. The general procedure for the synthesis of
a-aminonitriles: The mixture of
References and notes
K4[Fe(CN)6] (0.4 mmol) and benzoyl chloride (2 mmol) was heated at 160 °C
for 2 h, then the reaction system was cooled to room temperature; carbonyl
compound (2 mmol) and aniline (2 mmol) in 5 mL of ethanol were added. The
resulting mixture was stirred at room temperature to 80 °C for appropriate
time indicated in Table 3. After completion of the reaction, monitored by TLC,
the resulting mixture was filtered to remove the solids and the liquor was
1. (a) Shafran, Y. M.; Bakulev, V. A.; Mokrushin, V. S. Russ. Chem. Rev. 1989, 58,
148–160; (b) Duthaler, R. O. Tetrahedron 1994, 50, 1539–1650; (c) Matier, W.
L.; Owens, D. A.; Comer, W. T.; Deitchman, D.; Ferguson, H. C.; Seidehamel, R. J.;
Young, J. R. J. Med. Chem. 1973, 16, 901–908; (d) Dyker, G. Angew. Chem., Int. Ed.

3926
Z. Li et al. / Tetrahedron Letters 51 (2010) 3922–3926
concentrated and isolated by column chromatography to give pure product.
112–114 °C; IR (KBr): 3323, 3018, 2949, 2241, 1598, 1514, 1383, 1288, 937,
748 cmÀ1 1H NMR (CDCl3, 400 MHz): d 4.00 (br s, 1H), 5.68 (s, 1H), 6.76–6.78
The analytical data of representative compounds are given below. 2-Anilino-2-
phenylacetonitrile (Table 3, entry 1): Yellow solid, mp 76–78 °C; IR (KBr): 3337,
;
(m, 2H), 6.91–6.95 (m, 1H), 7.28–7.30 (m, 2H), 7.37–7.40 (m, 1H), 7.51–7.52 (d,
1H, J = 2.4 Hz), 7.68–7.70 (d, 1H, J = 8.0 Hz); 13C NMR (CDCl3, 100 MHz): d 47.6,
114.3, 117.3, 120.7, 128.1, 129.6, 129.9, 130.3, 130.4, 134.3, 136.5, 144.2. Anal.
Calcd for C14H10Cl2N2: C, 60.67; H, 3.64; N, 10.11. Found: C, 60.63; H, 3.65; N,
10.07. 2-(4-Toluidino)-2-phenylpropanenitrile (Table 3, entry 21): White solid,
mp 152–153 °C; IR (KBr): 3386, 3024, 2988, 2226, 1618, 1519, 1302, 1258, 807,
3030, 2942, 2236, 1599, 1514, 1446, 1282, 924, 752 cmÀ1 1H NMR (CDCl3,
;
400 MHz): d 4.04 (br s, 1H), 5.42 (s, 1H), 6.76–6.79 (m, 2H), 6.88–6.92 (m, 1H),
7.25–7.30 (m, 2H), 7.41–7.48 (m, 3H), 7.58–7.61 (m, 2H); 13C NMR (CDCl3,
100 MHz): d 50.2, 114.1, 118.1, 120.3, 127.2, 129.3, 129.5, 129.6, 133.9, 144.6.
Anal. Calcd for C14H12N2: C, 80.74; H, 5.81; N, 13.45. Found: C, 80.67; H, 5.80;
N, 13.41. 2-(4-Toluidino)-2-phenylacetonitrile (Table 3, entry 4): Yellow solid,
mp 81–83 °C; IR (KBr): 3329, 3026, 2922, 2241, 1615, 1520, 1449, 1282, 926,
696 cmÀ1 1H NMR (CDCl3, 400 MHz): d 1.94 (s, 3H), 2.19 (s, 3H), 4.16 (s, 1H),
;
6.45–6.47 (d, 2H, J = 8.4 Hz), 6.92–6.94 (d, 2H, J = 8.4 Hz), 7.33–7.42 (m, 3H),
7.62–7.64 (m, 2H). 13C NMR (CDCl3, 100 MHz): d 20.4, 33.3, 57.4, 116.1, 120.8,
124.9, 128.5, 129.2, 129.4, 129.5, 140.0, 141.0. Anal. Calcd for C16H16N2: C,
81.32; H, 6.82; N, 11.85. Found: C, 81.25; H, 6.83; N, 11.82. 1-
(Anilino)cyclopentanecarbonitrile (Table 3, entry 23): White solid, mp 67–
68 °C; IR (KBr): 3365, 2982, 2942, 2235, 1602, 1520, 1310, 1258, 747,
750 cmÀ1 1H NMR (CDCl3, 400 MHz): d 2.28 (s, 3H), 3.90 (s, 1H), 5.40 (s, 1H),
;
6.69–6.72 (m, 2H), 7.07–7.09 (m, 2H), 7.43–7.48 (m, 3H), 7.59–7.61 (m, 2H);
13C NMR (CDCl3, 100 MHz): d 20.5, 50.7, 114.5, 118.3, 127.2, 129.3, 129.5,
129.8, 130.0, 134.1, 142.4. Anal. Calcd for C15H14N2: C, 81.05; H, 6.35; N, 12.60.
Found: C, 81.11; H, 6.37; N, 12.55. 2-Anilino-2-(4-methoxyphenyl)acetonitrile
(Table 3, entry 12): White solid, mp: 95–97 °C; IR (KBr): 3329, 3011, 2932,
691 cmÀ1 1H NMR (CDCl3, 400 MHz): d 1.89–1.92 (m, 4H), 2.12–2.17 (m,
;
2210, 1602, 1507, 1436, 1241, 1023, 757 cmÀ1
.
1H NMR (CDCl3, 400 MHz): d
2H), 2.36–2.41 (m, 2H), 3.84 (s, 1H), 6.81–6.89 (m, 3H), 7.23–7.27 (m, 2H). 13
C
3.84 (s, 3H), 4.00 (br s, 1H), 5.36 (s, 1H), 6.76–6.78 (m, 2H), 6.96–6.98 (m, 2H),
7.25–7.30 (m, 3H), 7.50–7.52 (m, 2H); 13C NMR (CDCl3, 100 MHz): d 49.6, 55.4,
114.0, 114.6, 118.4, 120.2, 125.9, 128.6, 129.5, 144.7, 160.4. Anal. Calcd for
NMR (CDCl3, 100 MHz): d 23.8, 40.2, 57.4, 115.6, 119.8, 122.2, 129.3, 144.0.
Anal. Calcd for C12H14N2: C, 77.38; H, 7.58; N, 15.04. Found: C, 77.45; H, 7.56;
N, 15.01.
C15H14N2O: C, 75.61; H, 5.92; N, 11.76. Found: C, 75.67; H, 5.90; N, 11.79. 2-
26. Hunig, S.; Schaller, R. Angew. Chem., Int. Ed. Engl. 1982, 21, 36–49.
Anilino-2-(2,4-dichlorophenyl)acetonitrile (Table 3, entry 17): White solid, mp