Aqueous formic acid: An efficient, inexpensive and environmentally friendly organocatalyst for three-component Strecker synthesis of α-aminonitriles and imines with excellent yields

Article abstract of DOI:10.1039/c4ra11957f

Aqueous formic acid (37%) which is an efficient, inexpensive and environmentally friendly organocatalyst was used in the Strecker reaction to afford α-aminonitriles and imines. Reaction was carried out under mild conditions and room temperature in high yi

Full text of DOI:10.1039/c4ra11957f

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Graphical Abstract
Aqueous formic acid: an efficient, inexpensive and
environmentally friendly organocatalyst for threeꢀcomponent
Strecker synthesis of αꢀaminonitriles and imines with excellent
yields.
Hossein Ghafuri ,*a Mahdi Roshani a
a Department of Chemistry, Iran University of Science and Technology,16846 Tehran, Iran eꢀmail: ghafuri@iust.ac.ir
Text: Aqueous Formic acid (37%) was effectively used as catalyst in Strecker reaction to afford αꢀaminonitriles and imines in
high yields.

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Journal Name
RSCPublishing
ARTICLE
Aqueous formic acid: an efficient, inexpensive and
environmentally friendly organocatalyst for threeꢀ
component Strecker synthesis of αꢀaminonitriles and
imines with excellent yields
Cite this: DOI: 10.1039/x0xx00000x
Received 00th January 2012,
Accepted 00th January 2012
Hossein Ghafuri ,*a Mahdi Roshani a
DOI: 10.1039/x0xx00000x
www.rsc.org/
Aqueous Formic acid (37%) which is an efficient, inexpensive and environmentally friendly
organocatalyst was used in Strecker reaction to afford αꢀaminonitriles and imines. Reaction
was carried out under mild condition and room temperature in high yields. We obtained αꢀ
aminonitriles derives by using of trimethylsilyl cyanide through Strecker reaction. The most
important feature of formic acid as a catalyst is affordability and availability.
formic acid as catalyst in the synthesis of αꢀaminonitriles and
imine compounds. Formic acid is an important intermediate
Introduction
Strecker reaction is a significant and useful reaction in organic
chemistry. This reaction afford αꢀaminonitriles which are
versatile intermediates that can be used for synthesis of
building blocks such as αꢀamino acids, 1,2ꢀdiamines, and
nitrogenꢀcontaining heterocycles.1 As you know strecker
in chemical synthesis and occurs naturally, most notably in ant
venom24 and Urtica. Its name comes from the Latin word for
ant, Formica, referring to its early Isolation by the distillation of
ant bodies. Urtica is a genus of flowering plants in the family
Urticaceae. Many species have stinging hairs and may be
called nettles or stinging nettles, although the latter name
applies particularly to Urtica dioica. In synthetic organic
chemistry, formic acid is often used as a source of hydride ion.
The EschweilerꢀClarke reaction and the LeuckartꢀWallach
reaction are examples of this application. It, or more commonly
its azeotrope with triethylamine, is also used as a source of
reaction is
a
significant step in the preparation of
pharmaceuticals such as Saframycin A,2 Ecteinascidin 743,3
and Phtalascidin.4 In the classic strecker reaction researchers
use HCN, KCN or NaCN as cyanide sources5ꢀ13 but these
sources are toxic. In order to overcome safety problems,
various cyanide sources such as Bu3SnCN,14 K4[Fe (CN)6]15
and TMSCN16 have been used for srecker reaction. Among of
these cyanide sources which can attack as nucleophile to
different electrophiles, trimethylsilyl cyanide (TMSCN) is a
significant one, due to its safety, efficiency and availability. It
is noteworthy that TMSCN cannot transfer to electrophiles by
itself and need a catalyst in order to its activation. Therefore a
wide range of acid catalysts have been used17ꢀ22 but many of
them have disadvantages such as: long reaction time, toxicity
and high price of catalyst. For example TiO2 (P 25) which has
been used as catalyst for this reaction is expensive and is not
environmentally friendly.23 In order to overcome these issues
and to facilitate product formation, we decided to use aqueous
hydrogen
in transfer
hydrogenation.
Like acetic
acid and trifluoroacetic acid, formic acid is commonly used as a
volatile pH modifier in HPLC and capillary electrophoresis. As
mentioned below, formic acid may serve as a convenient source
of carbon monoxide by being readily decomposed by sulfuric
acid.
Furthermore, effect of formic acid on growth, nutrient
digestibility, Intestine mucosa morphology, and meat yield of
broilers a positive effect of formic acid on intestine mucosa was
investigated in some papers.25 using formic acid as reductant in
combination with an catalyst, for the transfer hydrogenation of
αꢀsubstituted acetophenones,26βꢀketo esters27 and nitroarenes to
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DOI: 10.1039/C4RA11957F
anilines28 were also investigated. Reduction of alkynes can
selectively produce cis,transꢀalkenes and alkanes.29 And also
using formic acid for oxidation of alkynes to αꢀdicarbonyl in
high yields has been studied.30 In comparison to other acid
catalysts, formic acid is very environmentally friendly and
effective.
Table 1. Screening of formic acid amount for Strecker reaction of 4ꢀ
chlorobenzaldehyde and aniline with TMSCN.
Entry
Amount of
formic acid
(mol %)
Solvent
Time(min)
Yield(%)a
Herein, we wish to report a superior, green, and facile synthesis
of αꢀaminonitriles and imines compounds through strecker
reaction of aromatic aldehydes, aniline derives and
trimethylsilyl cyanide at room temperature in high yields
(Scheme 1).
1
2
3
4
5
6
7
0
ꢀ
24h
19h
12h
1h
Trace
48
5
ꢀ
10
15
20
25
30
ꢀ
63
EtOH
EtOH
EtOH
EtOH
75
5
99
30
85
50
60
a Reaction conditions: 1 mmol of 4ꢀchlorobenzaldehyde, 1 mmol
of aniline and 130µl of TMSCN at room temperature.solvent is
2ml EtOH.
We investigated aldehyde containing both electronꢀ
withdrawing and electronꢀdonating groups. The results show
that being electronꢀwithdrawing or electronꢀdonating does not
determine the general trend of the reactivity. The reaction time
for the Strecker reaction catalyzed by formic acid has a
remarkable decrease in comparison to former methodologies20,
32.According to the obtained results we present a plausible
mechanism for synthesis of αꢀaminonitriles through strecker
reaction catalyzed by aqueous formic acid (Scheme 2).The
acidic hydrogen of formic acid active the carbonyl group of the
aldehydes through hydrogen bonding for nucleophilic attack
of amines to produce the corresponding imine. In the next
step CN group of TMSCN attack to imine to produce αꢀ
aminonitriles. We synthesis imine separately and then add
TMSCN to reaction pot. The product was same with concurrent
manner which confirms that this mechanism is reliable.
Scheme 1. The Strecker reaction of carbonyl compounds and amines with
TMSCN catalyzed by formic acid (A), synthesis of imines by formic acid (B).
Results and discussion
Synthesis of αꢀamino nitriles catalyzed by formic acid
According to our previous studies concerning the use of
aqueous formic acid as an efficient acid catalyst for
diastereoselective synthesis of βꢀamino carbonyl derivatives31
we used this green acid catalyst for strecker reaction .In order to
optimize reaction condition we considered the reaction of 4ꢀ
chlorobenzaldehyde, aniline and TMSCN (mol ratio 1:1:1.2) in
the presence of formic acid as a model reaction. The results
have been showed in Table 1. As you see in Table 1 we
haven’t desired yield in the absence of formic acid even after
24h, so the use of catalyst is necessary for reaction progress.
Increasing the amount of catalyst increases the yield of reaction
until catalyst amount reaches 20%mol. The higher amount of
20%mol causes gradual decrease in yield of reaction. Therefore
the optimize amount of catalyst is 20%mol. Monitoring of
reaction condition shows that in the presence of ethanol as
solvent, reaction will progress in a better way rather than
solventꢀfree condition. This result inspires us to developed
optimized condition to other aromatic carbonyl compounds and
amines for synthesis of αꢀaminonitriles (Table 2) and imines
(Table3).
Scheme 2. The plausible mechanism for synthesis of αꢀaminonitriles through
strecker reaction.
2 | J. Name., 2012, 00, 1-3
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Table 2. Synthesis of αꢀaminonitriles through strecker reaction of aldehyde with amines and TMSCN catalyzed by aqueous formic acid.
Time
(min)
Yield
(%)a
Entry
1
Amine
Aldehyde
Mp
Mpref
Product
CN
110ꢀ
Cl
CHO
5
94 108ꢀ110
NH2
11233
N
H
Cl
CN
CHO
CHO
2
3
55
26
96 86ꢀ89 86 – 8833
O2N
NH2
NH2
N
H
O2N
CN
120ꢀ
98 117ꢀ120
12234
HO
N
H
HO
CN
4
5
6
32
48
42
94 96ꢀ98 94ꢀ9716
NH2
NH2
NH2
CHO
CHO
MeO
N
H
MeO
CN
123ꢀ
91 121ꢀ123
12533
N
H
CN
90 88ꢀ90 87ꢀ8833
Br
CHO
N
H
Br
CN
7
8
25
51
95 80ꢀ81 77ꢀ8835
88 95ꢀ98 98ꢀ10033
NH2
NH2
CHO
N
H
Me
CN
S
CHO
N
H
S
CHO
9
72
89 94ꢀ97 97ꢀ9836
NH2
NC
N
H
OH CN
124ꢀ
95 126ꢀ129
12637
CHO
10
11
32
40
NH2
NH2
N
H
OH
CN
90
Oil
Oil33
N
O2N
CHO
H
O2N
CN
12
40
76 78ꢀ80 80ꢀ8238
N
NH2
CHO
H
Me
Cl
Cl
Cl
CN
13
14
CHO
54
36
89 71ꢀ73 73ꢀ7640
84 61ꢀ64 64ꢀ6738
NH2
NH2
N
H
Cl
CN
O
CHO
N
H
O
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CN
N
157ꢀ
68b 159ꢀ160
16040
H
N
15
16
OHC
NC
40
39
CHO
H
NH2
CN
CN
109ꢀ
86 107ꢀ109
11138
NH2
NH2
CHO
N
H
NC
Cl
CN
Cl
17
18
16
*
89 64ꢀ65 63ꢀ6632
N
CHO
CHO
H
NO2
CN
O2N
*
*
ꢀ
ꢀ
ꢀ
ꢀ
O2N
NH2
N
H
O2N
n-Bu
CN
19
20
21
*
n-Butyl
NH2
CHO
CHO
CHO
N
H
Me
Me
CN
104ꢀ
46
40
86 103ꢀ106
NH2
10638
N
H
Me
CN
80 85ꢀ88 83ꢀ8538
NH2
NH2
NH2
NH2
NH2
O2N
N
H
O2N
Me
Me
Me
Me
CN
107ꢀ
80 104ꢀ107
10938
22
23
24
25
13
67
48
52
CHO
N
H
CN
100ꢀ
96 103ꢀ105
10339
CHO
MeO
N
H
MeO
CN
95 81ꢀ83 83ꢀ8533
Cl
CHO
N
H
Cl
CN
CHO
114ꢀ
88 112ꢀ114
11639
O2N
N
H
O2N
a Reaction conditions: 1 mmol of aldehyde, 1 mmol of aniline,130µl TMSCN, 2ml EtOH as solvent and 30 µl formic acid at room temperature. *No
Reaction. b Reaction conditions: 1 mmol of aldehyde, 2 mmol of aniline,260µl TMSCN, 2ml EtOH as solvent and 30 µl formic acid at room temperature.
*No Reaction
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In order to show the efficiency of formic acid as a convenient Synthesis of imines (5) catalyzed by aqueous formic acid
catalyst for strecker reaction we compare our results with other
results which has been reported using various catalysts in Table
We investigated the imine formation from aldehydes
2
and
amines
1 in the presence of aqueous formic acid as catalyst.
3
.
The reaction condition of imines and αꢀaminonitriles was same.
The result have been summarized in Table 4. It is noteworthy
that separation of product is very simple.
Table 3. Comparison of the catalytic efficiency of formic acid with other
catalysts for Strecker reaction.
Entry
Catalyst
Solvent
Time
(min)
5
6
30
10
90
30
6h
Yield
(%)a
99
90
98
92
98
92
89
Ref
1
2
3
4
5
6
7
Formic acid
SnꢀMontmorillonite
MCMꢀ41ꢀSO3H
PEGꢀOSO3H
BꢀMCMꢀ41
EtOH
ꢀ
EtOH
H2O
EtOH
ꢀ
This work
41
33
42
43
11
44
GaꢀTUD
PVPꢀSO2
CH2Cl2
a 4ꢀChlorobenzaldehyde (1 mmol ), aniline (1 mmol),TMSCN (1.2 eq) and 2
ml of ETOH as solvent were used at rt.
Table 4. Synthesis of imines through reaction of aldehydes with amines catalyzed by aqueous formic acid.
Entry
1
Amine
Aldehyde
product
Time
(min)
Yield
(%)a
Mp
Mpref
1
99
64ꢀ65
62ꢀ6438
Cl
CHO
NH2
N
Cl
2
1
81
190ꢀ
193
193ꢀ19445
NH2
CHO
CHO
HO
N
HO
3
4
1
1
96
96
102ꢀ
104
100ꢀ10246
37ꢀ3847
NH2
NH2
NH2
N
N
38ꢀ41
71ꢀ73
CHO
CHO
Me
72ꢀ7438
Me
N
5
6
1
96
Me
Me
N
No
reaction
No
reaction
ꢀ
ꢀ
NH2
CHO
O2N
O2N
a Aldehyde (1 mmol ), aniline (1 mmol), 2ml EtOH as solvent and formic acid(30 µl) were used at rt.
KBr pellets on a Shimadzu FT IRꢀ8400S spectrometer.
Analytical TLC was carried out using Merck 0.2 mm silica gel
60 Fꢀ254 Alꢀplates. 1H NMR (500 MHz) and 13C NMR (125
or 75 MHz) spectra were obtained using Bruker DRXꢀ500
Avance and Bruker DRXꢀ300 Avance spectrometers at ambient
temperature, respectively.
Conclusion
In conclusion aqueous formic acid has been demonstrated to
be an effective and inexpensive catalyst for synthesis of αꢀamino
nitriles and imines through strecker reaction in high yield and
mild condition. To conclude, easy work up, low cost of catalyst
and high efficiency make our method to be efficient and practical
for synthesis of αꢀamino nitriles and imines.
General procedure for synthesis of αꢀamino nitriles 4 catalysed
by formic acid
Experimental
A mixture of aldehyde
2 (1 mmol), amine 1 (1 mmol),
All chemicals were purchased from Merck or Aldrich and
used as received. Melting points were determined using an
Electro thermal 9100 apparatus. FTꢀIR spectra were recorded as
trimethylsilyl cyanide (130µl), 30 µl of formic acid (20 mol %)
and 2 ml of ETOH as solvent was stirred vigorously in a 5 mL
round bottom flask equipped with a magnetic bar at room
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temperature for a sufficient amount of time. After completion
of the reaction as monitored by TLC the solid product was 2ꢀAnilinoꢀ2ꢀ(2ꢀthienyl) acetonitrile (Table 2, entry 8):
filtered, washed with deionized water, and dried.
IR (KBr): 3378, 2243 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 3.92
(d, J=8.73 Hz, 1H), 5.58 (d, J=9.35 Hz, 1H), 6.93 (d, J=7.72
Hz, 2H), 7.29 (t, J=7.43 Hz, 1H), 7.38 (q, J=2.96 Hz, 1H),
7.41–7.53 (m, 4H).
General procedure for synthesis of imines 5 catalysed by formic
acid
A mixture of aldehyde
2 (1 mmol), amine 1 (1 mmol), 30 µl of
formic acid (20 mol %) and 2 ml of ETOH as solvent was 2ꢀ(4ꢀmethyl anilino)ꢀ2ꢀ(4ꢀchloro phenyl) acetonitrile (Table
stirred vigorously in a 5 mL round bottom flask equipped with 2, entry 24):
a magnetic bar at room temperature for a sufficient amount of IR (KBr): 3351, 2893 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 3.22
time. After completion of the reaction as monitored by TLC the (s,3H), 4.06 (br s, 1H), 6.21 (s, 1H), 6.87 (d, J=7.8 Hz, 2H),
solid product was filtered, washed with deionized water, and 7.50 (d, J=7.9 Hz, 2H), 7.66 (d, J=8.2 Hz, 2H), 7.57 (d, J=8.1
dried.
Hz, 2H).
Spectral data of representative compounds:
2ꢀAnilinoꢀ2ꢀ(2, 6ꢀdichloro phenyl) acetonitrile (Table 2,
2ꢀAnilinoꢀ2ꢀ(4ꢀmethoxy phenyl) acetonitrile (Table 2, entry 25):
IR (KBr): 3391, 2223 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 5.23 (d,
1H, J = 10.7 Hz), 6.29 (d, 1H, J = 11.1 Hz), 6.86 (d, 2H, J = 8.7 Hz),
6.92 (t, 1H, J = 7.9 Hz), 7.27ꢀ7.34 (m, 3H), 7.41 (d, 2H, J = 7.6 Hz).
entry4):
IR(KBr): 3347, 2299 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 3.72
(s, 3H), 3.89 (br s, 1H), 5.36 (d, 1H, J = 6.6 Hz), 6.63 (d, 2H, J
= 8.2 Hz), 6.89ꢀ6.99 (m, 3H), 7.29 (d, 2H, J = 8.2 Hz), 7.82 (d,
2H, J = 8.2 Hz).
2ꢀAnilinoꢀ2ꢀcinnamyl acetonitrile (Table 2, entry 5):
IR (KBr): 3372, 2231 cmꢀ1; 1H NMR (CDCl3, 300 MHz) δ 4.02
(br s, 1H), 5.39 (d, J= 1.6 Hz, 1H), 6.33 (dd, J= 5.2 Hz, J= 16.1
Hz, 1H), 6.97 (d, J= 8.1 Hz, 2H), 7.23 (t, J= 7.4 Hz,1H), 7.36
(d, J= 16.1 Hz, 1H), 7.42–7.66 (m, 7H).
2ꢀAnilinoꢀ2ꢀ(4ꢀchloro phenyl) acetonitrile (Table 2, entry 1):
IR (KBr): 3291, 2268 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 3.74
(br s, 1H), 5.33 (d, 1H, J = 6.0 Hz), 6.76 (d, 2H, J = 7.9 Hz),
6.93 (t, 1H, J = 7.3 Hz), 7.39 (t, 2H, J = 8.1 Hz), 785 (d, 2H, J =
8.9 Hz), 8.07 (d, 2H, J = 8.5 Hz).
2ꢀAnilinoꢀ2ꢀ(1ꢀnaphthyl) acetonitrile (Table 2, entry9):
IR (KBr): 3345, 2251 cmꢀ1; 1H NMR (CDCl3, 300 MHz) δ 4.23
(d, J= 8.4 Hz, 1H), 6.26 (d, J= 8.1 Hz, 1H), 6.97 (d, J= 8.0 Hz,
2H),7.04 (t, J= 7.7Hz, 1H), 7.44 (t, J= 7.3 Hz, 2H), 7.63–7.69
(m, 3H),8.1–8.25 (m, 4H).
2ꢀAnilinoꢀ2ꢀ(4ꢀcyano phenyl) acetonitrile (Table 2, entry22):
IR (KBr): 3324, 2257 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 4.37
(br s, 1H), 5.86 (s, 1H), 6.90(d, 2H, J = 7.8 Hz), 7.01 (t, 1H, J=
7.6 Hz), 7.33 (t, 2H, J = 7.8 Hz), 7.92 (s, 4H).
2ꢀ(4ꢀmethyl anilino) phenyl acetonitrile (Table 2, entry22):
IR (KBr): 3335, 2239 cmꢀ1; 1H NMR (CDCl3, 300 MHz) δ 2.43
(s, 3H), 3.83 (br s, 1H), 5.64 (s, 1H), 6.67 (d, J= 8.5 Hz,
2H),7.02 (d, J= 8.1 Hz, 2H), 7.46 (d, J= 6.8 Hz, 3H), 7.84 (d, J=
5.7 Hz, 2H).
2ꢀAnilinoꢀ2ꢀ(4ꢀmethyl phenyl) acetonitrile (Table 2, entry7):
IR (KBr): 3298, 2273 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 2.61
(s, 3H) 4.03 (br s, 1H), 5.40 (s, 1H), 6.85 (d, 2H, J = 8.2 Hz),
6.91 (t, 1H, J = 7.4 Hz), 7.37ꢀ7.41 (m, 4H), 7.86 (d, 2H, J =7.8
Hz).
2ꢀAnilinoꢀ2ꢀ(4ꢀnitro phenyl) acetonitrile (Table 2, entry11):
IR (KBr): 3332, 2229 cmꢀ1; 1H NMR (CDCl3, 300 MHz) δ 3.96
(d, 1H), 5.32 (d, J=8.3 Hz, 1H), 6.63 (d J=7.3 Hz, 2H), 6.81 (t,
J=7.4 Hz, 1H), 7.29–7.34 (m, 3H), 7.79–7.81 (m, 2H), 8.29–
8.31 (m, 2H).
2ꢀAnilinoꢀ2ꢀ(phenyl) acetonitrile (Table 2, entry18):
1
IR (KBr): 3358, 2263 cmꢀ1; H NMR (CDCl3, 500 MHz) δ
4.23 (d, J=8.34 Hz, 1H), 5.42 (d, J=8.44 Hz, 1H), 6.87 (d,
J=7.75 Hz, 2H), 7.06 (t, J=7.42 Hz, 1H), 7.49 (m, 2H), 7.66 (m,
3H), 7.78 (m, 2H).
2ꢀAnilinoꢀ2ꢀ(4ꢀbromo phenyl) acetonitrile (Table 2,
entry22):
IR (KBr): 3305, 2309 cmꢀ1; 1H NMR (CDCl3, 300 MHz) δ 4.07
(d, 1H, J= 8.9 Hz), 5.32 (d, 1H, J= 8.9 Hz), 6.88 (d, 2H, J= 8.6
Hz), 6.96 (t, 1H, J= 7.4 Hz), 7.29 (t, 2H, J= 8.4 Hz), 7.60 (d,
2H, J= 8.9 Hz), 7.69–7.72 (m, 2H).
2ꢀAnilinoꢀ2ꢀ(furfuryl) acetonitrile (Table 2, entry20):
IR (KBr): 3358, 3093 cmꢀ1; 1H NMR (CDCl3, 500 MHz) δ 4.62
(br s, 1H), 5.72 (s, 1H), 6.44 (d,J=4.9 Hz, 1H), 6.61 (t, J=4.9
Hz,1H), 6.91 (d, J=7.8 Hz, 2H), 6.96 (t, J=7.8 Hz, 1H), 7.47
(t,J=7.8 Hz,2H), 7.81 (d,J=4.9 Hz, 1H).
(4ꢀchloroꢀbenzylidene)ꢀPhenylꢀamine (Table 4, entry 1):
1
IR (KBr): 3055, 1623 cmꢀ1; H NMR (CDCl3, 300 MHz) δ
2ꢀAnilinoꢀ2ꢀ(2ꢀchloro phenyl) acetonitrile (Table 2,
1
entry23): IR (KBr): 3367, 2253 cmꢀ1; H NMR (CDCl3, 500
7.27ꢀ7.37 (m, 3H), 7.43−7.58 (m, 4H), 7.92 (d, J =
8.7Hz, 2H), 8.93(s, 1H).
MHz) δ 3.92 (d, 1H, J = 7.5 Hz), 5.73 (d, 1H, J = 8.0 Hz), 6.74
(d, 2H, J = 8.0 Hz), 6.82 (t, 1H, J = 7.5 Hz), 7.29 (t, 2H, J = 8.0
Hz), 7.30ꢀ7.32 (m, 2H), 7.39ꢀ7.41 (m, 1H), 7.66ꢀ7.69 (m, 1H).
6 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C4RA11957F
23.
S. M. Baghbanian, M. Farhang and R. Baharfar, Chinese
Chemical Letters, 2011, 22, 555ꢀ558.
Acknowledgments
We are grateful to the Research Council of to the
Department of Chemistry Iran University of Science.
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