Microwave-promoted transformation of nitriles to amides with aqueous sodium perborate

Article abstract of DOI:10.1081/SCC-100000535

Microwave irradiation of several aromatic and aliphatic nitriles, including an α,β-bistrimethysilylnitrile, with sodium perborate tetrahydrate in a mixture of water/ethanol (2:1), smoothly produced corresponding amide in short times and with high yields. Other functional groups, such as aldehyde, are unaffected under these conditions.

Full text of DOI:10.1081/SCC-100000535

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MICROWAVE-PROMOTED TRANSFORMATION OF
NITRILES TO AMIDES WITH AQUEOUS SODIUM
PERBORATE
Ali Sharifi a , Farshid Mohsenzadeh a , Mohammad M. Mojtahedi b , Mohammad R. Saidi c
& Said Balalaie d
a Chemistry and Chemical Engineering Research of Iran , Tehran, Iran
b Department of Chemistry , Shrif University of Technology , Tehran, Iran
c Department of Chemistry , Shrif University of Technology , Tehran, Iran
d Chemistry Department , K.N. Toosi University of Technology , Tehran, Iran
Published online: 09 Nov 2006.
To cite this article: Ali Sharifi , Farshid Mohsenzadeh , Mohammad M. Mojtahedi , Mohammad R. Saidi & Said Balalaie
(2001) MICROWAVE-PROMOTED TRANSFORMATION OF NITRILES TO AMIDES WITH AQUEOUS SODIUM PERBORATE, Synthetic
Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry, 31:3, 431-434, DOI:
10.1081/SCC-100000535
To link to this article: http://dx.doi.org/10.1081/SCC-100000535
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SYNTHETIC COMMUNICATIONS, 31(3), 431–434 (2001)
MICROWAVE-PROMOTED
TRANSFORMATION OF NITRILES
TO AMIDES WITH AQUEOUS
SODIUM PERBORATE
Ali Sharifi,1 Farshid Mohsenzadeh,1 Mohammad M.
Mojtahedi,2 Mohammad R. Saidi,2,∗
and Said Balalaie3
1Chemistry and Chemical Engineering Research of Iran,
Tehran, Iran
2Department of Chemistry, Shrif University of Technology,
Tehran, Iran
3Chemistry Department, K. N. Toosi University of
Technology, Tehran, Iran
ABSTRACT
Microwave irradiation of several aromatic and aliphatic ni-
triles, including an α,β-bistrimethysilylnitrile, with sodium perbo-
rate tetrahydrate in a mixture of water/ethanol (2:1), smoothly pro-
duced corresponding amide in short times and with high yields.
Other functional groups, such as aldehyde, are unaffected under
these conditions.
During the past few years, the use of conventional microwave ovens as
a source of energy has rapidly increased in organic synthesis. The advantage of
∗Corresponding author.
431
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

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REPRINTS
432
SHARIFI ET AL.
O
CN
NH2
NaBO3, 4H2O
H2O, ethanol, MW
OHC
OHC
Scheme 1. Conversion of nitriles to amides by MW irradiation.
microwave irradiation includes reduction of the reaction time and cleaner work-up,
with generally higher yield of product (1–4). Strauss and his co-workers reported
a batchwise and continuous microwave reactor for conducting organic reaction on
a large scale (5).
Sodium perborate tetrahydrate, NaBO3, 4H2O, has the 1,4-diboratetra-
oxane structure, which is disrupted in water and ethanol (6). This is a cheap
and easily handed reagent, which was shown to be a highly effective and in
some cases selective reagent for conversion of a variety of functional groups
(7–9).
In continuation of our studies on microwave-assisted organic reactions,
we examined the oxidative hydration of several aromatic and aliphatic nitriles,
including α,β-bistrimethylsilylnitrile, with sodium perborate tetrahydrate in an
environmentally benign sovent such as water/ethanol. When 2-cyanobenzene–
carboxaldehyde (2-cyanobezaldehyde) and 4-cyanobenzenecarboxaldehyde
(Table 1, entries 7 and 8) are used as the substrate, amides A and B were obtained
in 83 and 97% yields, respectively, with unaffected aldehyde group (Scheme 1).
Microwave irradiation of several aromatic and aliphatic nitriles, including α,β-
bistrimethylsilylnitrile, with sodium perborate tetrahydrate, smoothly produced
corresponding amide C in short time and with high yields. The results of the
oxidative hydration of nitriles are shown in Table 1.
EXPERIMENTAL
IR spectra were taken on Matt Son 1000 Unicam FTIR, 1H and 13C NMR
spectra were recorded on a Bruker AC 80. Chemicals were purchased from Fluka
1
and used as received. All compounds were characterized by their IR, H and
13C NMR spectra. A domestic Moulinex microwave oven (Micro-Chefꢀ, 900 W,
2450 MHz) was used for the irradiation of the samples.
General Procedure for the Oxidative Hydration of Nitriles under
Microwave Irradiation. Sodium perborate tetrahydrate (4.0 mmol) and aro-
matic or aliphatic nitriles (1 mmol) were added to the mixture of water (10 mL)

ORDER
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NITRILES TO AMIDES
Table 1. Microwave-Promoted Oxidative Hydration of Nitriles
433
Entry
Substrate
Producta
Yieldb(%)
CN
O
NH2
1
85
CN
NH2
2
3
4
5
87
92
84
94
O
CN
NH2
O
O
CN
Cl
NH2
Cl
O
CN
NH2
O
NH2
CN
CHO
6
7
8
83
97
CHO
A
O
CN
NH2
B
OHC
OHC
Me3Si
SiMe3
CN
SiMe3
O
90c
NH2
SiMe3
C
aAll of substrates were irradiated for 2 min.
bIsolated yields.
cThe irradiation time was 4 min.
and ethanol (5 mL). The mixture was irradiated in a domestic microwave oven for
2 min (4 min for entry 4) at 900 W. The product was extracted with ether. Further
purification of the crude reaction product on silica gel column gave the pure amide.
The structure of the products was confirmed by comparison of their melting points
and spectroscopic data with those reported in the literature.
In summary, different kinds of amides are easily prepared from oxidative
hydration of nitrils with sodium perborate tetrahydrate, in about 2 min, under
microwave irradiation.

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SHARIFI ET AL.
REFERENCES
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Received in Japan February 29, 2000

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