See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/225426870

Hydroxylamine on Clay: a Direct Synthesis of Nitriles from Aromatic

Aldehydes Using Microwaves Under Solvent-Free Conditions

Article  in  Molecules Online · March 1998

DOI: 10.1007/s007830050061

CITATIONS READS

18 65

2 authors:

Rajender S Varma Kannan P. Naicker

United States Environmental Protection Agency 26 PUBLICATIONS   698 CITATIONS   
818 PUBLICATIONS   30,921 CITATIONS   
SEE PROFILE
SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Microwave-Assisted Reactions View project

Advanced Nanomaterials - synthesis and applications in Catalysis View project

All content following this page was uploaded by Rajender S Varma on 14 April 2016.

The user has requested enhancement of the downloaded file.

Molecules Online 1998, 2, 94-96

N OTE  Springer-Verlag 1998

Hydroxylamine on Clay: a Direct Synthesis of Nitriles from Aromatic

Aldehydes Using Microwaves Under Solvent-Free Conditions
Rajender S. Varma1, 2 and Kannan P. Naicker1

1 Department of Chemistry, Sam Houston State University, Huntsville, TX 77341–2117, USA.

Fax: +1-409–294–1585; E-mail: chm_rsv@shsu.edu

2Texas Research Institute for Environmental Studies (TRIES), Sam Houston State University, Huntsville, TX 77341-2117,
USA

Received: January 26 1998/Accepted: 23 February 1998/Published: March 11 1998

Abstract In a solvent-free system, hydroxylamine hydrochloride impregnated montmorillonite K 10

clay expeditiously converts arylaldehydes to the corresponding nitriles under microwave irradiation
conditions. This rapid one-pot method produces pure products in high yields (89–95%) within 1 to 1.5
min.

Keywords Arylaldehydes, Nitriles, Hydroxylamine hydrochloride, Montmorillonite K 10 clay,

Microwave irradiation

Introduction
The conversion of aldehydes to the corresponding nitriles is
an important chemical transformation [1]. In the majority of
cases, the aldoxime is prepared first and then dehydrated
using a wide variety of reagents such as chloramine/base
[2a], O,N-bis-(trifluoroacetyl)-hydroxylamine or trifluoro-
acetohydroximic acid [2b], triethylamine/dialkyl hydrogen
phosphinates [2c], p-chlorophenyl chlorothionoformate/py-
ridine [2d], nitromethane/pyridine hydrochloride [2e],
TiCl4/pyridine [2f], triethylamine/phosphonitrilic chloride
[2g], 1,1’-dicarbonylbiimidazole [2h], Envirocat EPZG
(100 °C, 16–23 h) [2i], and (H2SO4/SiO2) [2j]. In most of
these conventional methods, the dehydration of aldoxime
generally proceeds at a much slower rate, requiring long re-
action times: e.g. montmorillonite KSF (110 °C, 13–19 h)
[3] or elevated temperatures: e.g. zeolite (350 °C) [4].
The use of inorganic supports as reaction media in or-
ganic synthesis is becoming increasingly popular due to im-
proved efficiency of many surface bound reagents [5]. Fur-
thermore, with the advent of microwave dielectric heating,
the rate of several organic reactions can be accelerated to
afford faster and cleaner chemical conversions [6]. The ap-
plication of microwave heating techniques under solvent-
free reaction conditions has gained acceptance and notewor-
thy among them are the reactions on inorganic solid sup-
ports that are accelerated by exposure to microwaves. Thus,
by choice of suitable mineral supports like clay, silica, alu-
mina, a variety of organic reactions can be carried out suc-
cessfully in solventless systems using ordinary domestic
microwave ovens [7, 8]. In view of the limitations of the ex-
isting processes which require longer reaction times, te-
dious procedure and special equipment such as sealed
Teflon vessel etc., and in continuation of our ongoing pro-
gram to develop environmentally benign solvent-free meth-
ods [8], we explored the direct solventless transformation of
arylaldehydes to nitriles. These solvent-free reactions are
especially appealing as they provide an attractive option to
execute microwave manipulations in open vessels, thus
avoiding the risk of high pressure development and with a
possibility of upscaling the reactions to preparative scales.
Herein, we wish to report a facile conversion of alde-
hydes to nitriles using montmorillonite K 10 clay supported
hydroxylamine hydrochloride coupled with microwave acti-
vation.

Correspondence to: R. S. Varma

Molecules Online 1998, 2 95

Results and Discussion Experimental Section

In these reactions, arylaldehydes bearing both electron-re- General

leasing and electron-withdrawing substituents, are rapidly
converted into nitriles in good yields (89–95%) with clay
supported hydroxylamine hydrochloride coupled with MW
irradiation in the absence of solvent. We examined various
mineral supports such as clay, alumina, and silica and found
that all are equally effective in terms of formation of pure
products. The procedure in its entirety involves admixing
aldehydes with clay supported hydroxylamine hydrochlo-
ride and subjecting the solid reaction mixture to microwave
irradiation in an unmodified household MW oven at its full
power (900 Watts) for 1–1.5 min. A variety of aldehydes
undergo facile conversion in the presence of hydroxylamine
hydrochloride ’doped’ montmorillonite K 10 clay to afford
high yield of nitriles within a short time of irradiation. In
the case of aliphatic aldehydes, however, only poor yields
of nitriles (10–15%) are obtained with complex byproduct
formation.
In conclusion, the present solid state reaction of alde-
hydes to nitriles with montmorillonite K 10 clay supported
hydroxylamine hydrochloride is a very facile and practical
method. The operational simplicity, use of inexpensive cata-
lyst, and high yields in a significantly very rapid reaction
makes this an ideal procedure and a useful and attractive al-
ternative to the currently available methods.
Montmorillonite K 10 clay was obtained from the Aldrich
Chemical Co., and hydroxylamine hydrochloride from Lan-
caster Synthesis Inc. A Sears Kenmore microwave oven op-
erating at 2450 MHz (power 900 Watts) was used for all the
experiments. Products were identified by comparison of
their m.p., IR, and NMR spectra with those of the authentic
samples.
General Procedure for the Conversion of Aromatic Alde-
hydes to Nitriles
The reagent, prepared by thoroughly mixing montmorillo-
nite K 10 clay (1.5 g) and hydroxylamine hydrochloride
(0.5 g, 7.7 mmol) using a pestle and mortar, is admixed
with benzaldehyde (0.7 g, 6.6 mmol) in a glass test tube.
The reaction mixture was placed in an alumina bath (neutral
alumina: 125 g, mesh ~150, Aldrich; bath: 5.7 cm diameter)
inside an unmodified household microwave oven and irradi-
ated for 1–1.5 min at its full power of 900 Watts. On com-
pletion of the reaction, followed by TLC examination (hex-
ane:EtOAc, 8:2), the product was extracted into methylene
chloride (3 × 15 ml). The solvent was removed under re-

Table 1 Solvent-free microwave-assisted conversion of arylaldehydes to nitriles by clay-hydroxylamine

O
K 10 clay/
R1 C R1 C N
H NH2OH · HCl
MW (1–1.5 min),
R2 (89–95 %) R2

Where R1 = H, R2 = H, OMe, NO2, OH, Br, Me

R1 = R2 = OMe

Entry Product Time Yielda m.p. or b.p. (ºC)/torr

(min) (%) found reported [9]

1 C6H5CN 1.5 92 190/760 191/760

2 4-MeOC6H4CN 1.0 95 56–58 57–59
3 4-NO2C6H4CN 1.5 92 146–147 146–149
4 4-BrC6H4CN 1.5 91 110–112 112–114
5 4-MeC6H4CN 1.5 89 216–217/760 103–106/20 mm
6 4-HOC6H4CN 1.5 91 110–112 110–113
7 3,4(MeO)2C6H3CN 1.0 93 68–69 68–70
8 Cinnamonitrile 1.5 91 254/760 254–255/760
a Yields of isolated products that are characterized by IR and 1H-NMR spectra
96
duced pressure to afford nitriles in more than 90% yield.
The crude product was further purified by a simple filtra-
tion through a silica gel column using hexane:EtOAc (8:2)
mixture as an eluent.
Acknowledgments We are grateful to the Texas Advanced
Research Program (ARP) in Chemistry (Grant #
003606–023) and the Texas Research Institute for Environ-
mental Studies (TRIES) for financial support.
References
1. (a) Fizet C, Streith J (1974) Tetrahedron Lett 3187; (b)
Miller M, Loudon G (1975) J Org Chem 40:126; (c)
Sosnovsky G, Krogh JA, Umhoefer SG (1979) Synthe-
sis 722; (d) Olah GA, Keuni T (1979) Synthesis 112; (e)
Friedrich K, Wallensfels K (1970) In: Rappoport Z (ed)
The chemistry of cyano groups. Wiley-Interscience,
New York
2. (a) Mowry DT (1948) Chem Rev 42:250; (b) Pomeroy
JH, Craig CA (1959) J Am Chem Soc 81:6340; (c)
Foley PJ (1969) J Org Chem 34:2805; (d) Clive DL
(1970) J Chem Soc Chem Commun 1014; (e) Dauzonne
D, Demerseman P, Royer R (1981) Synthesis 739; (f)
Karmarkar SN, Kelkar SL (1985) Wadia Synthesis 510;
(g) Villemin D, Lalaoui M, Ben Album D (1991) Chem
and Ind 176; (h) Delgado F, Cano AC, Garcia O,
Alvarado J, Velasco L, Alvarez C, Rudler H (1992)
Synth Commun 22:2125; (f) Lehnert W (1971) Tetrahe-
dron Lett 6:559; (g) Rosini G, Baccolini G, Cacchi S
(1973) J Org Chem 38:1060; (h) Foley HG, Dalton DR
(1973) J Chem Soc Chem Commun 628; (i) Bandgar
BP, Jagtap SR, Ghodeshwar SB, Wadgaonkar PP (1995)
Synth Commun 25:2993; (j) Sampath Kumar HM,
Mohanty PK, Suresh Kumar M, Yadav JS (1997) Synth
Commun 27:1327
3. Meshram HM (1992) Synthesis 943
4. Narayan Rao M, Kumar P, Garyaki K (1989) Org Prep
Proceed Int 21:230
5. (a) McKillop A, Young DW (1979) Synthesis 401, 481;
(b) Laszlo P (1987) Preparative chemistry using sup-
ported reagents. Academic Press, San Diego; (c) Clark
JH (1994) Catalysis of organic reactions by supported
inorganic reagents. VCH, New York
6. For recent reviews on microwave-assisted chemical re-
actions see: (a) Abramovich RA (1991) Org Prep Proced
View publication stats
Molecules Online 1998, 2
Int 23:683; (b) Whittaker AG, Mingos DMP (1994) J
Microwave Power Electromagn Energy 29:195; (c)
Majetich G, Hicks R (1995) J Microwave Power
Electromagn Energy 30:27; (d) Caddick S (1995) Tetra-
hedron 51:10,403; (e) Bose AK, Banik BK, Lavlinskaia
N, Jayaraman M, Manhas MS (1997) Chemtech 27:18;
(f) Varma R S (1997) Microwave-assisted reactions un-
der solvent-free dry conditions. In: Clark DE, Sutton
WH, Lewis DA (eds) Microwaves: theory and applica-
tion in material processing IV. American Ceramic Soci-
ety, Ceramic Transactions, pp 375–365
7. (a) Oussaid A, Thach LN, Loupy A (1997) Tetrahedron
Lett 38:2451; (b) Villemin D, Benalloum A (1991)
Synth Commun 21:1, 63; (c) Lerestif JM, Toupet L,
Sinbandhit S, Tonnard F, Bazureau JP, Hamelin J (1997)
Tetrahedron 53:6351
8. For cleavage-deprotection reactions see: (a) Varma RS,
Chatterjee AK, Varma M (1993) Tetrahedron Lett
34:3207; (b) Varma RS, Chatterjee AK, Varma M (1993)
Tetrahedron Lett 34:4603; (c) Varma RS, Varma M,
Chatterjee AK (1993) J Chem Soc Perkin Trans 1 999;
(d) Varma RS, Lamture JB, Varma M (1993) Tetrahe-
dron Lett 34:3029; (e) Varma RS, Saini RK (1997) Tet-
rahedron Lett 38:2623; (f) Varma RS, Meshram HM
(1997) Tetrahedron Lett 38:5427; (g) Varma RS,
Meshram HM (1997) Tetrahedron Lett 38:7973; (h)
Varma RS, Dahiya R, Saini RK (1997) Tetrahedron Lett
38:8819
For condensation-cyclization reactions see: (i) Varma
RS, Dahiya R, Kumar S (1997) Tetrahedron Lett
38:2039; (j) Varma RS, Dahiya R (1997) Synlett 1245;
(k) Varma RS, Dahiya R, Kumar S (1997) Tetrahedron
Lett 38:5131; (l) Varma RS, Saini RK (1997) Synlett
857
For oxidation reactions see: (m) Varma RS, Dahiya R
(1997) Tetrahedron Lett 38:2043; (n) Varma RS, Saini
RK, Meshram HM (1997) Tetrahedron Lett 38:6525; (o)
Varma RS, Dahiya R, Saini RK (1997) Tetrahedron Lett
38:7029; (p) Varma RS, Dahiya R, Saini RK (1997) Tet-
rahedron Lett 38:7823; (q) Varma RS, Dahiya R (1998)
Tetrahedron Lett 39:1307; (r) Varma RS, Saini RK
(1998) Tetrahedron Lett 39:1481
For reductions see: (s) Varma RS, Saini RK (1997) Tet-
rahedron Lett 38:4337
9. (a) CRC hand book of data on organic compounds
(1998). CRC Press, Boca Raton, Florida; (b) Hand book
of tables for organic compounds identification, 3rd edn
(1978). Chemical Rubber Company, Cleveland, Ohio
Molecules Online (electronic publication) – ISSN 1433-1373