One-pot synthesis of nitriles from aldehydes and hydroxylamine hydrochloride over silica gel, montmorillonites K-10, and KSF catalysts in dry media under microwave irradiation

Article abstract of DOI:10.1081/SCC-120037915

A rapid and facile one-pot synthesis of nitriles has been carried out from the corresponding aldehydes and hydroxylamine hydrochloride in the presence of environmentally benign silica gel (84-95%), Mont K-10 (85-96%), and Mont KSF clay (88-98%) catalysts in dry media under microwave irradiation.

Full text of DOI:10.1081/SCC-120037915

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One‐Pot Synthesis of Nitriles from Aldehydes and
Hydroxylamine Hydrochloride over Silica Gel,
Montmorillonites K‐10, and KSF Catalysts in Dry
Media Under Microwave Irradiation
Sharwan K. Dewan a , Ravinder Singh a & Anil Kumar a
a Department of Chemistry, M.D. University, Rohtak, Haryana, 124001, India
Published online: 20 Aug 2006.
To cite this article: Sharwan K. Dewan , Ravinder Singh & Anil Kumar (2004): One‐Pot Synthesis of Nitriles from Aldehydes
and Hydroxylamine Hydrochloride over Silica Gel, Montmorillonites K‐10, and KSF Catalysts in Dry Media Under Microwave
Irradiation, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic Chemistry,
34:11, 2025-2029
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 11, pp. 2025–2029, 2004
One-Pot Synthesis of Nitriles from
Aldehydes and Hydroxylamine
Hydrochloride over Silica Gel,
Montmorillonites K-10, and KSF
Catalysts in Dry Media Under
Microwave Irradiation
*
Sharwan K. Dewan, Ravinder Singh, and Anil Kumar
Department of Chemistry, M.D. University, Rohtak, Haryana, India
ABSTRACT
A rapid and facile one-pot synthesis of nitriles has been carried out from
the corresponding aldehydes and hydroxylamine hydrochloride in the
presence of environmentally benign silica gel (84–95%), Mont K-10
(85–96%), and Mont KSF clay (88–98%) catalysts in dry media under
microwave irradiation.
Key Words: Nitriles; Aldehydes; Hydroxylamine hydrochloride; Silica
gel; Mont K-10, Mont KSF.
*
Correspondence: Sharwan K. Dewan, Department of Chemistry, M.D. University,
Rohtak, Haryana 124001, India; E-mail: sharwandewan@rediffmail.com.
2025
DOI: 10.1081/SCC-120037915
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Dewan, Singh, and Kumar
INTRODUCTION
Nitriles form an important functional group from the point of view of
organic transformations. They are widely used for conversion into amides
amines, esters, carboxylic acids, etc.[1–3] The general method for the synthesis
of nitriles is the nucleophilic substitution reaction of alkyl halides with metal
cyanides. The dehydration of aldoximes into nitriles has been achieved by
using a variety of reagents such as triethylamine/sulfurdioxide,[4] zeolites,[5]
sulfuryl chloride fluoride,[6] etc. but many of these transformations suffer from
limitations. While ketoximes are undergo Beckman rearrangement over Mont
K-10 in dry media under microwave irradiation,[7] we have recently reported
that the aldoximes are dehydrated into nitriles under microwave irradiation
using silica gel.[8] We have reported the synthesis of oximes from aldehydes
and hydroxylamine hydrochloride in high yields using silica gel, Mont K-10,
and Mont KSF catalysts under MW conditions.[9] We reasoned that one-pot
synthesis of nitriles from aldehydes and hydroxylamine hydrochloride under
microwave irradiation in presence of these catalysts (Sch. 1) should be
investigated.
3,4-Dimethoxy benzaldehyde was condensed with hydroxylamine hydro-
chloride in presence of silica gel, Mont K-10, and Mont KSF clay catalysts
under varying levels of irradiation (80, 160, 240, 320, 400, 480, 560, 640,
720, and 800 W). The yield between 95% and 98% was observed at 560 W
after 4 min of irradiation (TLC monitoring). Subsequent reactions described
herein were carried out under these reaction conditions. A variety of substi-
tuted aromatic aldehydes have been attempted. These results are indicated
in Table 1.
In conclusion, we have shown that one-pot synthesis of nitriles from
aldehydes and hydroxylamine hydrochloride can be carried out in high yields
in presence of environmentally benign silica gel (84–95%), Mont K-10
(85–96%), and Mont KSF (88–98%) clays as catalysts.
EXPERIMENTAL
Melting points were determined in open capillaries on an electrically
heated metal block and are uncorrected. PMR (CDCl3) spectra were recorded
Scheme 1.

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One-Pot Synthesis of Nitriles
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Dewan, Singh, and Kumar
on a Jeol FX90Q instrument using TMS as an internal standard. IR spectra
were recorded on a Perkin–Elmer 782 spectrophotometer. TLC was done
can silica gel G plates with benzene–ethylacetate (4 : 1) system.
Typical Procedure
3,4-Dimethoxy benzaldehyde (166 mg, 1 mmol), hydroxylamine hydro-
chloride (105 mg, 1.2 mmol) were mixed with silica gel G (1 g) or Mont
K-10 (1 g) or Mont KSF (1 g) and taken up in an Earlenmeyer flask and
irradiated at 560 W for 4 min in an unmodified domestic microwave oven
(Kenstar OM-9925E, 800 W, operating at 2450 MHz). The flask was taken
out, cooled, and ether (50 mL) was added. The catalyst was filtered off and
the resultant solution evaporated to give a residue, which was purified by chro-
matography using benzene–ethylacetate (4 : 1) as eluent to afford the desired
nitrile (Table 1).
Spectroscopic data for 3,4-dimethoxybenzonitrile (1). 1H-NMR
(CDCl3), d 3.8 (s, 3H, –OCH3), 3.9 (S, 3H, –OCH3), 6.9 (m, 1H, ArH), 7.0
;;
(m, 2H, ArH); IR (neat) 2940 (C–H str.), 2220 (C N str.), 1610, 1540,
and 1450 (C–C str.); m.p. 62.58C, reported 638C.[10]
ACKNOWLEDGMENTS
We thank Dr. R. Sharma of DayChem Inc. (Dayton) for gifts of Mont
K-10 and KSF clays and Mr. Yashwant for a gift of the microwave oven
used in this investigation and Professor A.J. Bellamy for inspiration.
REFERENCES
1. Cohen, M.A.; Sawden, J.; Turner, N.J. Tetrahedron Lett. 1990, 31, 7223.
2. Fabiani, M.E. Drug News Perspect. 1999, 12, 207.
3. Baxendale, I.R.; Ley, S.V.; Sneddon, F.H. Synlett. 2002, 5, 775 (and
references therein).
4. Olah, G.A.; Vankar, Y.D. Synthesis 1978, 702.
5. Narayana Rao, M.; Kumar, P.; Garyali, K. Org. Prep. Proceed. Int. 1989,
21, 230.
6. Olah, G.A.; Narang, S.C.; Garcia-Luma, A. Synthesis 1980, 659.
7. Bosch, A.I.; De laCruz, P.; Diez-Barra, E.; Loupy, A.; Langa, F. Synlett.
1995, 1259.
8. Dewan, S.K.; Singh, R. Synth. Commun., in press.

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One-Pot Synthesis of Nitriles
9. Dewan, S.K.; Singh, R. Orient J. Chem., in press.
2029
10. Sakamoto, T.; Ohsawa, K. J. Chem. Soc. Perkin Trans. 1999, 1, 2323.
11. The Aldrich Library, NY; 1993; Vol. 2, 1510–1523.
12. Effenberger, F.; Kremser, A.; Stelzer, U. Tetrahedron Asymm. 1996,
7, 607.
Received in India January 9, 2004

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