bis(trichloromethyl)carbonate, an efficient activator for the one-pot conversion of aldehydes into nitriles under mild conditions

Article abstract of DOI:10.1081/SCC-120014975

A single step conversion of aldehydes into the corresponding nitriles has been achieved in high yields using stoichiometric amounts of NH₂OH·HCl, Et₃N and bis(trichloromethyl)-carbonate at room temperature.

Full text of DOI:10.1081/SCC-120014975

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BIS(TRICHLOROMETHYL)CARBONATE, AN EFFICIENT
ACTIVATOR FOR THE ONE-POT CONVERSION OF
ALDEHYDES INTO NITRILES UNDER MILD CONDITIONS*
D. Subhas Bose a & P. Ravinder Goud a
a Organic Chemistry Division-III , Fine Chemicals Laboratory , Indian Institute of Chemical
Technology , Hyderabad, 500 007, India
Published online: 16 Aug 2006.
To cite this article: D. Subhas Bose & P. Ravinder Goud (2002) BIS(TRICHLOROMETHYL)CARBONATE, AN EFFICIENT ACTIVATOR
FOR THE ONE-POT CONVERSION OF ALDEHYDES INTO NITRILES UNDER MILD CONDITIONS*, Synthetic Communications:
An International Journal for Rapid Communication of Synthetic Organic Chemistry, 32:23, 3621-3624, DOI: 10.1081/
SCC-120014975
To link to this article: http://dx.doi.org/10.1081/SCC-120014975
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SYNTHETIC COMMUNICATIONS
Vol. 32, No. 23, pp. 3621–3624, 2002
BIS(TRICHLOROMETHYL)CARBONATE,
AN EFFICIENT ACTIVATOR FOR THE
ONE-POT CONVERSION OF ALDEHYDES
INTO NITRILES UNDER MILD
CONDITIONS*
D. Subhas Bosey and P. Ravinder Goud
Organic Chemistry Division-III, Fine Chemicals
Laboratory, Indian Institute of Chemical Technology,
Hyderabad 500 007, India
ABSTRACT
A single step conversion of aldehydes into the corresponding
nitriles has been achieved in high yields using stoichiometric
amounts of NH2OHÁHCl, Et3N and bis(trichloromethyl)-
carbonate at room temperature.
Key Words: Triphosgene; Nitriles; Aldehydes; One-pot;
Activator
Nitriles are of particular interest as intermediates in organic synthesis
due to their conversion into amides, carboxylic acids, amines and ketones.[1]
They are usually prepared by nucleophilic substitution[2a] with CNÀ or by
regenerating CN group via oxidation,[2b] elimination or rearrangement.[2c]
*IICT Communication No. 4560.
yCorresponding author. E-mail: dsb@iict.ap.nic.in
3621
DOI: 10.1081/SCC-120014975
Copyright & 2002 by Marcel Dekker, Inc.
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3622
BOSE AND GOUD
Scheme 1.
As part of our ongoing program on the synthesis and development of new
methodologies for nitriles,[3] we herein wish to report a convenient chemo-
selective synthesis of nitriles from aldehydes, hydroxylamine hydrochloride,
and triphosgene under mild conditions in the presence of Et3N at room
temperature (Scheme 1).
Triphosgene is known to react with acids to produce acid chlorides or
anhydrides.[4] We have successfully utilized approximately one molar ratio
of this reagent for a one step transformation of aldehydes into nitriles.[5] The
reaction was found to be very clean and gave excellent yields of nitriles. The
general applicability of the protocol is demonstrated with various aldehydes
illustrated in Scheme 1 and several experimental results are summarized in
Table 1. Substrates containing nitro and chloro groups remain unaffected by
competitive aromatic nucleophilic substitution. However, substrates bearing
strong electron withdrawing group such as nitro require a longer reaction
time as the extent of leaving group departure decreases with the electron-
withdrawing ability of the b-aryl substituent. Excellent chemoselectivity was
observed in that methoxy, benzyloxy and methylenedioxy groups did not
experience any ether cleavage despite the known a-nucleophilicity of oxime
and the ability of ClÀ to deprotect aryl methyl ether.
In conclusion, we have developed an efficient method [NH2OHÁHCl-
Et3N-(CCl3O)2CO] which can directly convert aldehydes into the corre-
sponding nitriles in high yields.
General Procedure
NH2OHÁHCl (0.38 g, 5.5 mmol) was added slowly to a stirred ice-
cooled solution (or suspension) of the aldehyde 1 (0.87 g, 5.0 mmol) in dry
CHCl3 (15 mL) and anhyd. Et3N (1.54 mL, 11.0mmol) at such a rate that
the temperature was kept below 5ꢀC. The reacion mixture was allowed to
warm to room temperature and stirred for another 3–4 h. After the oxime
formation, bis(trichloromethyl) carbonate (1.65 g, 5.4 mmol) was added in
portions over a period of 15 min. After each addition, an exothermic reac-
tion is observed. The resulting mixture was stirred at room temperature for

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BIS(TRICHLOROMETHYL)CARBONATE
3623
Table 1. One-Pot Conversion of Aldehydes into Nitriles by
NH2OHꢀHCl/Et3N and (CCl3O)2CO in Chloroform at Room
Temperature
Entry
1
Substrate 1a
Product 2b
Yieldc (%)
95
2
92
3
4
90
87
5
85
6
7
89
93
8
9
86
65
aAll substrates were commercially available and purchased from
Aldrich; bProducts were characterized by comparison of their
1
m.p., IR and H NMR spectra with those of authentic samples;
cIsolated yields.

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3624
BOSE AND GOUD
about additional 2 h. The progress of the nitrile formation is monitored
by T.L.C. On completion of the reaction, quenched with H2O (5 mL) and
extracted with CHCl3 (2 Â 15 mL). The combined organic phases were
washed with brine, dried (Na2SO4) and the solvent was removed in vacuo
to afford the crude product which was purified by column chromatography
(EtOAc/hexane, 1 : 9 v/v) on silica gel to afford pure nitriles 2 in 80–98%
yields (Table 1).
REFERENCES
1. (a) Friedrich, K.; Wallensfels, K. In The Chemistry of Cyano Group;
Rappoport, Z., Ed.; Wiley-Interscience: New York, 1970; (b) Mowry,
D.T. Chem. Rev. 1948, 42, 250.
2. (a) Fatiadi, A.J. The Chemistry of Triple-Bonded Functional Group,
Part 2; Patai, S., Rappoport, Z., Eds.; John Wiley and sons: New York,
1983; pp. 1057; (b) Stevens, T.E. J. Org. Chem. 1961, 26, 2531; (c)
Pakusch, J.; Ruchardt, C. Chem. Ber. 1991, 124, 971.
3. (a) Bose, D.S.; Jayalakshmi, B. J. Org. Chem. 1999, 64, 1713; (b) Bose,
D.S.; Goud, P.R. Tetrahedron Lett. 1999, 40, 747; (c) Bose, D.S.; Kiran
Kumar, K. Synth. Commun. 2000, 30, 3047.
4. Cotarca, L.; Delogu, P.; Nardelli, A.; Sunjic, V. Synthesis 1996, 553.
5. Work on the similar line has been reported by Prasad Sahu, D, Ind. J.
Chem. 1993, 32B, 385 in which total completion of the reaction takes
place using half molar ratio of triphosgene to carboxamides instead of
theoretical one third molar ratio of triphosgene at 50ꢀC.
Received in the Netherlands November 22, 2001