Tetrabutylammonim peroxydisulfate in organic synthesis X.1 An efficient nickel-catalyzed one-pot synthesis of nitriles from aldehydes by oxidation with tetrabutylammonium peroxydisulfate

Article abstract of DOI:10.1055/s-2000-7595

Various aliphatic, aromatic and heterocyclic aldehydes were efficiently transformed to the corresponding nitriles in a one-pot procedure by nickel-catalyzed oxidation with tetrabutylammonium peroxydisulfate in the presence of ammonium hydrogen carbonate under basic aqueous conditions. The process affords excellent yields of pure nitriles.

Full text of DOI:10.1055/s-2000-7595

SHORT PAPER
1519
Tetrabutylammonim Peroxydisulfate in Organic Synthesis X.1 An Efficient
Nickel-Catalyzed One-Pot Synthesis of Nitriles from Aldehydes by Oxidation
with Tetrabutylammonium Peroxydisulfate
Fen-Er Chen,* Han Fu, Ge Meng, Yu Cheng, Yin-Xiang Lü
Department of Chemistry, Fudan University, Shanghai 200433, People’s Republic of China
Fax +86(21)65652021; E-mail: rfchen@fudan.edu.cn
Received 7 March 2000; revised 11 May 2000
treatment of ammonium hydrogen carbonate as the nitro-
Abstract: Various aliphatic, aromatic and heterocyclic aldehydes
gen source, (Bu4N)2S2O8 as an oxidant, and nickel copper
formate as a catalyst in the presence of aqueous potassium
hydroxide in acetonitrile at room temperature (Table).
were efficiently transformed to the corresponding nitriles in a one-
pot procedure by nickel-catalyzed oxidation with tetrabutylammo-
nium peroxydisulfate in the presence of ammonium hydrogen car-
bonate under basic aqueous conditions. The process affords Among the various solvents studied, acetonitrile appears
excellent yields of pure nitriles.
to be the best choice. When these reactions were carried
out in dichloroethane or dichloromethane the conversions
were only marginal (35-46%) even after comparatively
longer reaction times (8-12 h). No desirable nitriles were
obtained in hydrocarbon solvent such as toluene or xylene
even at the reflux temperature. Moreover, by virture of the
mild reaction conditions, a variety of functional groups
like C,C double bonds, ether etc. in the substrate were tol-
erated under these reaction conditions.
Key words: tetrabutylammonium peroxydisulfate, aldehydes, ni-
triles, oxidations
Among the plethora of available methods to prepare ni-
triles,2 the most simple and straightforward routes seem to
be those based on the oxidation of the aldimines, formed
in situ by condensation of aldehydes and ammonia, with
several kinds of oxidants such as iodine,3 lead tetraace-
tate,4 nickel peroxide,5 oxygen-copper(II) chloride,6 etc.
However, in spite of their inherent simplicity, these
methods are not generally applicable to alkyl, aryl, as well
as heterocyclic aldehydes and often give unsatisfactory
yields. As a result, there is still a need for new, convenient
and universally applicable methods for one-pot synthesis
of nitriles from the corresponding aldehydes.
The effect of nickel copper formate was also evaluated in
this reaction. We tried the reaction of 1e with
(Bu4N)2S2O8 without using nickel copper formate. The re-
action was unsuccessful and 1e remained unchanged after
2 hours and also the reaction did not go to completion
when reduced amounts of nickel copper formate catalyst
was used.
In conclusion, we have presented here a simple, efficient
method for direct conversion of aldehydes into the corre-
sponding nitriles which is superior to previously reported
methods in terms of selectivities, high yields, and conve-
nient workup.
Recently, we have reported that in the presence of nickel
copper formate as a catalyst, various primary amines are
conveniently oxidized with tetrabutylammonium peroxy-
disulfate [(Bu4N)2S2O8]under basic aqueous conditions to
the corresponding nitriles in excellent yields.7 Further in-
vestigations along this line have revealed that
(Bu4N)2S2O8 can be applied to the selective oxidation of
aldimines, formed in situ from aldehydes and ammomium
hydrogen carbonate, to the corresponding nitriles in the
presence of nickel copper formate under basic aqueous
conditions as shown in the Scheme.
All melting points were measured with a WRS-1 digital melting
point apparatus and are uncorrected. IR spectra were recorded on a
Nicolet FI-IR 360 spectrometer. 1H NMR spectra were taken on a
JEOL-90Q spectrometer. The substrates and nickel copper formate
(anhydrous) used in this study are commercially available.
(Bu4N)2S2O8 was synthesized according to the known procedure.10
The structures of the products 2a-p were identified by comparsion
of their IR and 1H NMR spectra with those in the literature.
4-Methoxybenzonitrile (2e); Typical Procedure
To a solution of nickel copper formate (0.9 g, 3 mmol) in H2O
(5 mL) was added a mixture of 4-methoxybenzaldehyde (13.6 g,
100 mmol) in MeCN (60 mL), (Bu4N)2S2O8 (67.8 g, 100 mmol) in
MeCN (245 mL), NH4HCO3 (8.4 g, 110 mmol) in H2O (45 mL) and
KOH (5.6 g, 100 mmol) in H2O (240 mL). The reaction mixture was
stirred vigorously at r.t. for 1.5 h, and the insoluble compounds were
removed by filtration and the filtrate was extracted with CH2Cl2
(4 × 75 mL). The combined CH2Cl2 layers were washed with brine
(2 × 55 mL), dried (Na2SO4) and the solvent was evaporated to dry-
ness under reduced pressure. The crude product was recrystallized
Scheme
Various aliphatic, aromatic and heterocyclic aldehydes 1
bearing different functionalities were cleanly converted
into the corresponding nitriles 2 in excellent yields upon
Synthesis 2000, No. 11, 1519–1520 ISSN 0039-7881 © Thieme Stuttgart · New York

1520
F.-E. Chen et al.
SHORT PAPER
Table Conversion of Aldehydes 1 to Nitriles 2
Entry
R
Producta
Reaction Time (h)
Yieldb (%)
mp (°C) or bp (°C)/Torr
found
reported
1
2
3
C4H9
C6H13
Ph
2a
2b
2c
1.5
1.5
2
89
90
91
139−140/760
70−71/10
189−191/760
138/7602d
69/102d
190−191/
7607
4
4-MeC6H4
2d
2
91
217−218/760
216−218/
7607
5
6
7
8
9
10
11
12
4-MeOC6H4
3-MeOC6H4
4-NO2C6H4
3,4,5-(MeO)3C6H2
2-naphthyl
3,4-(MeO)2C6H3
4-Me2N C6H4
(E)-PhCH=CH
2ec
2f
2g
2h
2i
2j
2k
2l
2
92
90
90
93
94
91
94
90
61−63
86−87
148−150
93−95
63−65
65−67
60−627
80−872p
149−1508
92−957
64−667
65−677
749
1.5
2.5
1
1
1.5
1
74−76
254−255/760
2
254−256/
7602q
13
2-ClC6H4
2md
2
90
228−230/760
238/760/
7602d
14
15
16
2-furyl
2-pyridyl
piperonyl
2n
2o
2p
1.5
1.5
2
92
90
91
147−148
57−53
69−70
146−1487
50−527
68−702p
a Solids were purified by crystallization from EtOH unless otherwise noted and liquids by distillation.
b Yield of isolated pure products.
c From Et2O.
d From Et2O/hexane.
from Et2O to afford the pure 2e (12.2 g, 92%) as a white solid; mp
61-63 ∞C (Lit.2o,7 mp 60-62 ∞C).
(n) Olah, G. A.; Narang S. C.; Garcia-Luna, A. Synthesis
1980, 659.
(o) Sampath Kumar, H. M.; Mohanty, P. K.; Suresh Kumar
M.; Yasav, J. S. Synth. Commun. 1997, 27, 1327.
(p) Sampath Kumar, H. M.; Subba Reddy, B. V.; Tirupathi
Reddy, P.; Yadav, J. S. Synthesis 1999, 586.
(q) Subhas Bose, D.; Jayalakshmi, B. Synthesis 1999, 64.
(3) Misono, A.; Oda T.; Koga, S. Bull. Chem. Soc. Jpn. 1966, 39,
854.
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Article Identifier:
1437-210X,E;2000,0,11,1519,1520,ftx,en;F01300SS.pdf
Synthesis 2000, No. 11, 1519–1520 ISSN 0039-7881 © Thieme Stuttgart · New York