2634
H. Veisi
PAPER
mixture was stirred at 60 °C. When the reaction was complete (TLC
hexane–acetone, 6:1), it was quenched at this temperature with H2O
(10 mL) and it was then was extracted with Et2O (3 × 15 mL). The
combined organic layers were washed with brine and dried
(MgSO4) to give 5 in good yield. If necessary, the product was pu-
rified by column chromatography (silica gel, hexane–EtOAc, 4:1).
sponding naphthalene-1-carbonitrile (5k) in good yield
under the same conditions (Table 1, entry 34).
Clearly, the present reaction is a good method for the di-
rect preparation of aromatic nitriles from benzylic halides.
That means that the use of the Sandmeyer reaction (dia-
zonium with CuCN) or the dehydration of aromatic
amides with dehydrating agents is not required. We have
also examined the preparation of aliphatic nitriles under
the same reaction conditions, but we did not observe any
notable conversions.
Nitriles from Amines 1, Alcohols 2, and Aldehydes 3; General
Procedure
To a mixture of amine, alcohol or aldehyde (1 mmol) and aq NH3
(3.0 mL, 45 mmol) in a round-bottomed flask was added TCCA
(0.75 mmol) slowly and very carefully in several small portions at
r.t. The obtained mixture was stirred at 60 °C. When the reaction
was complete (TLC hexane–acetone, 6:1), it was quenched at this
temperature with H2O (10 mL), and it was then was extracted with
Et2O (3 × 15 mL). The combined organic layers were washed with
brine and dried (MgSO4) to give 5 in good yield. If necessary, the
product was purified by column chromatography (silica gel, hex-
ane–EtOAc, 4:1).
A possible reaction pathway for the conversion of benzyl-
ic halides into corresponding aromatic nitriles, with
trichloroisocyanuric acid in aqueous ammonia is shown in
Scheme 6. The initial nucleophilic reaction of ammonia
with the benzylic halide 4 occurs to generate correspond-
ing primary amine IX. N-Chlorination of amine IX with
trichloroisocyanuric acid take place to provide N-chloro
compound V, followed by b-elimination of HCl with am-
monia to provide aldimine III. Then, aldimine III reacts
with trichloroisocyanuric acid to generate N-chloro com-
pound IV, and this is followed by b-elimination of HCl
with ammonia to give the corresponding nitrile 5.
Acknowledgment
We are thankful to Payame Noor University of Songhor, Istanbul
Technical University, and the University of Sheffield for NMR,
Mass spectra and CHN.
TCCA
References
3 RCH2X
3 R CN
5
4
NH3, 60 °C
(1) North, M. Comprehensive Organic Functional Group
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NH3
– HX
– HX
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Cl
RCH NH
3
2
2
IX
3
R-C=N
H
IV
O
Cl
O
Cl
N
N
O
O
N
TCCA
HN
NH
Cl
H
3
O
O
N
H
R-CH=NH
3
NH
R
– HX
Cl
V
III
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Scheme 6
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In conclusion, a simple and convenient method has been
developed for the direct conversion of alcohols, alde-
hydes, primary amines, and alkyl halides to their corre-
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ammonia catalyzed by trichloroisocyanuric acid as the ox-
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methods are their mild reaction conditions, operational
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reactions.
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All commercially available chemicals were obtained from Merck
and Fluka companies, and used without further purification unless
otherwise stated. 1H NMR spectra were recorded on a Jeol 90 MHz
FT NMR spectrometer using TMS as internal standard. IR spectra
were measured on a Perkin Elmer GX FT-IR spectrophotometer.
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Nitriles 5 from Benzyl Halides 4; General Procedure
To a mixture of alkyl halide (1 mmol) and aq NH3 (3.0 mL, 45
mmol) in round bottomed flask was added TCCA (1 mmol) slowly
and very carefully in several small portions at r.t.. The obtained
Synthesis 2010, No. 15, 2631–2635 © Thieme Stuttgart · New York