Organic reactions in water: Transformation of aldehydes to nitriles using NBS under mild conditions

Article abstract of DOI:10.1080/00397910500522009

Aliphatic, aromatic, heterocyclic, conjugated, and polyhydroxy aldehydes gave corresponding nitriles in high yields at 0°C using NBS and ammonia in water. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910500522009

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Organic Reactions in Water: Transformation
of Aldehydes to Nitriles using NBS under Mild
Conditions
B. P. Bandgar a & S. S. Makone a
a Organic Chemistry Research Laboratory, School of Chemical Sciences,
Swami Ramanand Teerth Marathwada University, Nanded, India
Published online: 16 Aug 2006.
To cite this article: B. P. Bandgar & S. S. Makone (2006): Organic Reactions in Water: Transformation of
Aldehydes to Nitriles using NBS under Mild Conditions, Synthetic Communications: An International Journal for
Rapid Communication of Synthetic Organic Chemistry, 36:10, 1347-1352
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Synthetic Communicationsw, 36: 1347–1352, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500522009
Organic Reactions in Water:
Transformation of Aldehydes to Nitriles
using NBS under Mild Conditions
B. P. Bandgar and S. S. Makone
Organic Chemistry Research Laboratory, School of Chemical Sciences,
Swami Ramanand Teerth Marathwada University, Nanded, India
Abstract: Aliphatic, aromatic, heterocyclic, conjugated, and polyhydroxy aldehydes
gave corresponding nitriles in high yields at 08C using NBS and ammonia in water.
Keywords: Aldehydes, NBS, nitriles, organic reactions in water
Conversion of carbonyl compounds into nitriles is an important functional
group transformation in organic synthesis,[1] which is achieved in majority
of the cases via aldoxime dehydration in a two-step process. Direct con-
version of aldehydes into nitriles without isolation of nitrogen-containing
intermediates has also been explored.[2] Of the different one-pot prepara-
tive methods developed in recent years, many are mainly limited to
aromatic aldehydes, which are preferably converted to aromatic nitriles,
whereas the transformation of enolizable aliphatic aldehydes often give
unsatisfactory yields of aliphatic nitriles. The problem can be somewhat
circumvented by using less available reagents[3] and unconventional
approaches[4] for direct conversion of aldehydes into nitriles that
employ IR and microwave activation in the presence of inorganic solid
Received in India October 21, 2005
Address correspondence to B. P. Bandgar, Organic Chemistry Research Laboratory,
School of Chemical Sciences, Swami Ramanand Teerth Marathwada University,
Nanded 431 606, India. Fax: 0091-2462-29245; E-mail: bnadgar_bp@yahoo.com
1347

1348
B. P. Bandgar and S. S. Makone
supports. In one such method reported by Villemin et al.,[4a] the inter-
mediate dithiocarbonate generated by reacting the oximate with CS2 is
converted into nitrile by prolonged reaction in presence of Al2O3/KF.
Recently aliphatic and aromatic nitriles were prepared in high yields in
a direct one-pot process by heating corresponding aldehydes with hydro-
xylamine hydrochloride in N-methylpyrrolidone at a high temperature
(100–1158C) for a longer time (4 to 8 h).[5] Other methods[6] that are
applicable to both aromatic and aliphatic aldehydes often involve
expensive or hazardous reagents.
The use of ammonia combined with an appropriate oxidant is an
expedient method for the transformation of aliphatic and aromatic
aldehydes to their corresponding nitriles. Different reagents develo-
.
ped to effect this conversion are NH3/O2/CuCl2 2H2O/MeONa in
MeOH,[7a] NH3/Pb(OAc)4in dry benzene,[7b] NH3/I2/MeONa in
MeOH,[7c] NH3/S8/NaNO2,[7d] NH3/KI/MeONa in MeOH on elect-
rooxidation,[7e] NH3/H2O2/CuCl in 2-propanol,[7f] NH3/I2 in THF–
water.[7g]
The development of a method that allows the reaction under essen-
tially mild and neutral conditions should heighten the synthetic potential
of the conversion. In this communication we report preliminary results
of direct conversion of aldehydes to corresponding nitriles in excellent
yields using NBS and aq. NH3 under mild conditions (Equations 1–3
and Table 1).
RESULTS AND DISCUSSION
The aldehydes examined in this study included aliphatic aldehydes,
aromatic aldehydes, heterocyclic aromatic aldehydes, a,b-unsaturated
aldehydes, and saccharide aldehydes. It is also important to note that the
dialdehyde, terephthalaldehyde, smoothly converted into corresponding
dicyanide in excellent yield. The preparations of p-nitrobenzonitrile
(93%), furonitrile (90%), cinnamononirile (87%), and aliphatic nitriles
(88–94%) from the corresponding aldehydes in the presence of NBS–NH3
were successfully accomplished. The water-soluble 2-deoxy-D-ribose with
NBS in ammonia–water at 08C for 15 min gave (3,4,5-tri-acetoxy)pentane-
nitrile 14 (97%) after isolated acetylation (Ac2O/water). Similarly
D-glucose furnished the corresponding nitrile isolated after acetylation
to yield (2,3,4,5,6-pentaacetoxy)-D-glucononitrile 15 in 85% yield
(Equation 3).

Organic Reactions in Water
1349
Table 1. Transformation of aldehydes to nitriles using NBS in ammonia water
Reaction
time (min)
Yield
(%)
Entry
Substrate
Product
1
2
3
4
H3CCH2CHO
H3C(CH2)2CHO
H3C(CH2)4CHO
H3C(CH2)5CHO
H3CCH2CN
H3C(CH2)2CN
H3C(CH2)4CN
H3C(CH2)5CN
10
10
15
20
88
94
90
88
5
15
86
6
10
96
7
8
25
30
93
93
9
90
60
40
78
80
85
10
11
12
13
40
30
90
87

1350
B. P. Bandgar and S. S. Makone
The plausible mechanism of the reaction are shown in Equations (2)
and (3).
In conclusion, this method is general, as a variety of aldehydes (Table 1)
were successfully transformed into nitriles by treatment with NBS and
ammonia in water. This simple, economic, and environmentally benign
method is especially useful for the transformation of water-soluble
aldehydes such as carbohydrates (Equations 2 and 3).
EXPERIMENTAL
IR spectra were recorded on Bomem MB 104 FT-IR spectrometer, and
1H NMR spectra were recorded on an AC 300F NMR spectrometer
(300 MHz).
General Procedure
A suspension of an aldehyde (5 mmol) in ammonia water (10 ml of 30%)
was stirred for 2 to 3 min at room temperature, which resulted in the

Organic Reactions in Water
1351
formation of a turbid solution. To this turbid solution NBS (5 mmol) was
added slowly with constant stirring at 08C. The yellowish-brown solution
immediately becomes colorless with precipitation of the product, which
indicates completion of the reaction (TLC). Solid products are collected by
simple filtration, whereas liquid products are obtained by usual workup
after extraction with ethyl acetate.
(3,4,5-Triacetoxy)pentanenitrile (14): [a]2D5 ¼ 7.25 (c ¼ 2.6, CHCl3); IR
(neat) ¼ 22 65 cm21
;
1H NMR (300 MHz, CDCl3): d ¼ 2.1 (s, 3H,
COCH3), 2.15 (s, 3H, COCH3), 2.18 (s, 3H, COCH3), 2.6–2.7 (m, 2H,
CH2CN), 4.15 (dd, J ¼ 12.2 and 4.5 Hz, 1H), 4.35 (dd, J ¼ 12.2 and 3.3 Hz,
1H), 5.2–5.3 (m, 2H, CH2O; 13C NMR (75 MHz, CDCl3): d ¼ 17 (CH2),
21 (2 Â CH3), 22.5 (CH3), 62.3 (CH2), 65.7 (CH), 72.1 (CH), 123.2 (C),
171.4 (C), 171.8 (C), 172.1 (C). Anal. calcd. for C11H15NO6: C, 51.36; H,
5.84; N, 5.45. Found: C, 51.42; H, 5.77; N, 5.38.
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