Facile synthesis of nitriles from aromatic aldehydes using DMSO-I2

Article abstract of DOI:10.1080/00397910601033500

Nitriles have been prepared from different aromatic aldehydes by a one-pot process using hydroxylamine hydrocloride and molecular iodine in the presence of dimethylsulphoxide. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910601033500

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Facile Synthesis of Nitriles from Aromatic
Aldehydes Using DMSO‐I2
Digambar D. Gaikwad a , Sameer V. Renukdas a , Babasaheb V. Kendre a
,
Suresh U. Shisodia b , Ravikumar M. Borade b , Praveen S. Shinde b , Sunil S.
Chaudhary b & Rajendra P. Pawar b
a Department of Chemistry, Vaidyanath College, Parli‐Vaijnath, India
b Department of Chemistry, Dnyanopasak College, Parbhani, 431 401,
Maharashtra, India
Published online: 25 Jul 2007.
To cite this article: Digambar D. Gaikwad , Sameer V. Renukdas , Babasaheb V. Kendre , Suresh U. Shisodia ,
Ravikumar M. Borade , Praveen S. Shinde , Sunil S. Chaudhary & Rajendra P. Pawar (2007) Facile Synthesis
of Nitriles from Aromatic Aldehydes Using DMSO‐I2 , Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 37:2, 257-259, DOI: 10.1080/00397910601033500
To link to this article: http://dx.doi.org/10.1080/00397910601033500
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Synthetic Communicationsw, 37: 257–259, 2007
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910601033500
Facile Synthesis of Nitriles from Aromatic
Aldehydes Using DMSO-I2
Digambar D. Gaikwad, Sameer V. Renukdas, and
Babasaheb V. Kendre
Department of Chemistry, Vaidyanath College, Parli-Vaijnath, India
Suresh U. Shisodia, Ravikumar M. Borade, Praveen S. Shinde,
Sunil S. Chaudhary, and Rajendra P. Pawar
Department of Chemistry, Dnyanopasak College, Parbhani,
Maharashtra, India
Abstract: Nitriles have been prepared from different aromatic aldehydes by a one-pot
process using hydroxylamine hydrocloride and molecular iodine in the presence of
dimethylsulphoxide.
Keywords: acetonitrile, aromatic aldehydes, dimethylsulphoxide, hydroxylamine-
hydrochloride, molecular iodine
INTRODUCTION
The efficient and mild transformations of aldehydes to nitriles were exten-
sively studied, and many methods were reported. For example, aldehydes
were transformed into nitriles by using Zn/I2 in acetonitrile,[1] ammonia
water and iodine in ionic liquid,[2] acetonitrile,[3] NH4OAc under
[5]
microwave irradiation,[4] NH2OH HCl under microwave irradiation, I2/
.
[7]
NH3/THF[6] catalyst, NaN3/AlCl3 catalyst, HY-zeolite catalyst under
microwave irradiation[8] and H2O2/NH2OH/Cu[9] (Scheme 1).
In the present work benzaldehyde (1) was stirred at room temperature
with hydroxylamine hydrochloride (2) and molecular iodine in the presence
of dimethylsulphoxide. After an aqueous workup, benzonitrile (3) was
isolated. Other aromatic nitriles have been similarly synthesized and are
Received June 16, 2006
Address correspondence to Rajendra P. Pawar, Department of Chemistry, Dnyano-
pasak College, Parbhani, 431 401, Maharashtra, India. E-mail: rppawar@yahoo.com
257

258
D. D. Gaikwad et al.
Scheme 1.
Table 1. Conversion of aromatic aldehydes to nitriles using two different solvents
Yield Yield
(%)
Mp/bp (%)
Entry
1
Starting material (1)
Products (3)
(8C) DMSO CH3CN
193
98
90
85
87
40
45
45
2
3
113
4
5
252
225
85
89
34
45
6
7
45
98
80
85
43
47
8
9
58
83
84
43
48
135
(continued)

Nitriles from Aromatic Aldehydes
259
Table 1. Continued
Yield Yield
Mp/bp (%) (%)
(8C) DMSO CH3CN
Entry
10
Starting material (1)
Products (3)
265
89
38
Note: All products are known compounds and identified by comparing their melting
points with standards described in the literature.
listed in Table 1. The structures of nitriles prepared were confirmed on the basis
of IR and 1H NMR spectral data. Although other organic solvents were tried, the
best results were obtained with dimethylsulphoxide (DMSO) as a solvent.
EXPERIMENTAL
A solution of benzaldehyde (1.06 g) in DMSO (5 ml), hydroxylamine hydro-
chloride (0.69 g), and iodine (10 mg) was stirred at room temperature for 4 h.
The progress of the reaction was checked on thin-layer chromatography (TLC)
(hexane/ethylacetate, 8 : 2). After the completion of reaction, the reaction
mixture was poured over crushed ice and extracted with ether. The ether
layer was washed with brine, dried over anhydrous sodium sulphate, and
evaporated to give benzonitrile (0.93 g, 90%).
ACKNOWLEDGMENTS
The authors are thankful to the principal, Vaidyanath College, Parli Vaijnath,
for providing laboratory facilities. The authors are also thankful to
A. W. Vadal for help during the work and to the Department of Chemistry,
Pune University, for providing spectral data.
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