One-pot conversion of aldoximes into nitriles via aldoxime tosylates under microwave irradiation

Article abstract of DOI:10.1080/104265090902750

Silica-gel-supported aldoximes react with tosyl chloride at room temperature to give the corresponding aldoxime tosylates. These supported aldoxime tosylates were directly converted to their corresponding nitriles in high yields under microwave irradiation. Copyright Taylor & Francis Inc.

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Phosphorus, Sulfur, and Silicon
and the Related Elements
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One-Pot Conversion of
Aldoximes Into Nitriles via
Aldoxime Tosylates Under
Microwave Irradiation
Hossein A. Oskooie a , Majid M. Heravi a , Zinab
Jaddi a & Mitra Ghassemzadeh b
a Department of Chemistry , School of Sciences,
Azzahra University , Vanak, Tehran, Iran
b Chemistry and Chemical Engineering Research
Center of Iran , Tehran, Iran
Published online: 19 Aug 2006.
To cite this article: Hossein A. Oskooie , Majid M. Heravi , Zinab Jaddi & Mitra
Ghassemzadeh (2005) One-Pot Conversion of Aldoximes Into Nitriles via Aldoxime
Tosylates Under Microwave Irradiation, Phosphorus, Sulfur, and Silicon and the Related
Elements, 180:9, 1993-1996, DOI: 10.1080/104265090902750
To link to this article: http://dx.doi.org/10.1080/104265090902750
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Phosphorus, Sulfur, and Silicon, 180:1993–1996, 2005
Copyright © Taylor & Francis Inc.
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/104265090902750
One-Pot Conversion of Aldoximes Into Nitriles via
Aldoxime Tosylates Under Microwave Irradiation
Hossein A. Oskooie
Majid M. Heravi
Zinab Jaddi
Department of Chemistry, School of Sciences, Azzahra University,
Vanak, Tehran, Iran
Mitra Ghassemzadeh
Chemistry and Chemical Engineering Research Center of Iran, Tehran,
Iran
Silica-gel-supported aldoximes react with tosyl chloride at room temperature to
give the corresponding aldoxime tosylates. These supported aldoxime tosylates were
directly converted to their corresponding nitriles in high yields under microwave
irradiation.
Keywords Aldoximes; tosylates; nitriles; microwave irradiation
INTRODUCTION
Nitriles are versatile functional groups because they can be converted
to amides via the nucleophilic addition of water and ketones via hy-
drolyzing the imine formed by the nucleophilic addition of a Grignard
reagent.1
The most widely applicable and often the most convenient methods
for the formation of a carbon–nitrogen triple bond involve an elimina-
tion process.2 The cyanation of aryl and heteroaryl iodide for the direct
introduction of cyano groups to arenes and heteroarenes are known
to be classical methods.3 Direct conversion of aldehydes to nitriles has
been also reported.4 Nitriles can be synthesized from the dehydration of
the corresponding oximes using a variety of reagents such as trimethyl
Received August 10, 2004; accepted September 16, 2004.
We are grateful to partial financial support from the Azzahra University Research
Council.
Address correspondence to Hossein A. Oskooie, Azzahra University, Department of
Chemistry, School of Sciences, Vanak, Tehran, Iran. E-mail: mmheravi@azzahra.ac.ir
1993

1994
H. A. Oskooie et al.
amine/sulfur dioxide,5 zeolite,6 sulphoryl chloride fluoride,7 and silica
gel,8 etc., each of which has its own merits and drawbacks.
Supported reagents on mineral surfaces have been widely used in
organic synthesis.9 The solventless application of a supported reagent
in combination with microwave irradiation provides an ideal reaction
condition.10
First we thought of using silica gel and zeolite as the acidic, available,
and inexpensive catalysts in combination with microwave irradiation
in a solvent-free condition.
A variety of aldoximes were mixed with silica gel and zeolite HZSM-5
and put in a microwave oven. All attempts to convert aldoximes to
nitriles failed or led to poor yields of nitriles.
After these failures, we planned to expedite o-tosylated oximes,
which can be easily synthesized by the reaction of oximes with tosyl
chloride in the presence of trimethyl amine. We used silica gel and
zeolite HZSM-5 as mineral support in this reaction. The reaction of
a silica-gel-supported oximes with tosyl chloride in the presence of
trimethyl amine in CHCl3 at room temperature proceeded smoothly to
give the corresponding o-tosylated aldoximes, which were not isolated.
The solvent was evaporated and the residue was directly subjected to
microwave irradiation to obtain the corresponding nitriles in high yields
(Table I). The isolation of nitriles was performed by adding methanol
to the residue, the evaporation of methanol, and the addition of sodium
bicarbonate solution and extraction with ether.
In conclusion, we have developed a simple and one-pot procedure for
the conversion of aldoximes to nitriles in high yields.
EXPERIMENTAL
Aldoximes were prepared by the reported route.11 All products were
known and their spectroscopic and physical data were compared with
those of authentic samples.
Conversion of Aldoximes to Their Corresponding Nitriles
(General Procedure)
An appropriate aldoxime (1 mmol) was mixed with silica gel (0.3 g)
and tosyl chloride (2 mmol) in CHCl3 (5 mL). To this mixture triethyl
amine (3 mmol) was added and stirred at room temperature for a few
seconds. The solvent was evaporated under reduced pressure. The crude
residue was directly put into an unmodified microwave oven for the
indicated time. The progress of the reaction was monitored by TLC.

One-Pot Conversion of Aldoximes
1995
TABLE I One-Pot Conversion of Aldoxime to Nitrile Under
Microwave Irradiation
mp or bp(◦C)
Time
(s)
aYield
Entry
1
Substrate
Product
Found reported (%)
10
12
12
190
19111
90
92
90
2
3
62
593
63
663
4
15
147
1483
88
5
6
7
15
15
12
92
89–9012
11012
85
82
91
111
255
25411
8
12
51
—
82
aYeilds are based on weight of oximes used.
After the reaction was completed, methanol was added to the crude
residue, filtered, and the filterate was evaporated to dryness. To the
residue a saturated solution of sodium bicarbonate was added and the
mixture extracted with ether. The ether layer was dried over Na2SO4,
filtered, and evaporated to afford the corresponding nitrile.
TsCL,silica gel
MW
Ar CH NOH
−→ Ar CH NOTs −→ Ar C N
Et3N
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