Green synthesis and characterization of novel α-acyloxycarboxamides through three-component reaction between pyridine carbaldehydes, cyclohexyl isocyanide, and benzoic acid derivatives

Article abstract of DOI:10.1007/s00706-011-0536-0

Novel α-acyloxycarboxamides were synthesized and characterized by the Passerini three-component reaction between pyridine carbaldehydes, cyclohexyl isocyanide, and benzoic acid derivatives in water. The reactions were carried out in one pot at room temper

Full text of DOI:10.1007/s00706-011-0536-0

Monatsh Chem (2011) 142:1143–1147
DOI 10.1007/s00706-011-0536-0
ORIGINAL PAPER
Green synthesis and characterization of novel
a-acyloxycarboxamides through three-component reaction
between pyridine carbaldehydes, cyclohexyl isocyanide,
and benzoic acid derivatives
•
Esmail Vessally Ali Ramazani Elham Yaaghubi
•
Received: 25 November 2010 / Accepted: 30 May 2011 / Published online: 28 June 2011
Ó Springer-Verlag 2011
Abstract Novel a-acyloxycarboxamides were synthe-
sized and characterized by the Passerini three-component
reaction between pyridine carbaldehydes, cyclohexyl iso-
cyanide, and benzoic acid derivatives in water. The
reactions were carried out in one pot at room temperature
with a quantitative yield. The products were obtained
without any need for purification.
isocyanide, and a nucleophile. These reactions are beginning
to find utility in the drug discovery process and total syn-
theses of biologically relevant natural products [13]. As a
continuation of our recent studies on isocyanide chemistry
[14–18], we report the Passerini multicomponent reaction
between pyridine carbaldehydes 1, cyclohexyl isocyanide
(2), and benzoic acid derivatives 3.
Keywords Passerini reaction Á Isocyanide Á
Pyridine carbaldehyde Á a-Acyloxycarboxamide
Results and discussion
The pyridine carbaldehydes 1, cyclohexyl isocyanide (2),
and benzoic acid derivatives 3 were allowed to react in a
1:1:1 ratio at room temperature in water to yield a-acyl-
oxycarboxamides 4a–4o (Fig. 1; Table 1). The reaction
proceeds smoothly and cleanly under mild conditions in
water and is therefore considered to be a green chemistry
method. The products were obtained without any further
purification with a quantitative yield in one-pot reactions.
The products were crystallized from an ethanol/water
mixture. The structures of the products were deduced from
Introduction
The great potential of isocyanides for development of mul-
ticomponent reactions lies in the diversity of bond-forming
processes available, their functional group tolerance, and the
high levels of chemo-, regio-, and stereoselectivity often
observed [1–9]. In 1921, Passerini pioneered the use of
isocyanides and successfully developed a three-component
synthesis of a-acyloxycarboxamides by the reaction between
carboxylic acid, an aldehyde, and an isocyanide [10–12].
The Passerini reactions involve an oxo component, an
1
their elemental analyses and IR, H NMR, and 13C NMR
1
spectra. For example, the H NMR spectrum of 4a exhib-
ited distinct signals arising from –CH2 of cyclohexyl
(d = 0.86–2.32 ppm), –N–CH (3.76–3.79 ppm), –CH–O
(6.39 ppm), –NH (6.78–6.81 ppm), and aromatic –CH
(7.24–8.58 ppm).
The 13C NMR spectrum of 4a indicated 16 distinct reso-
nancesarisingfrom –CH2 ofcyclohexyl (d = 24.6–32.8 ppm),
–N–CH (48.4 ppm), C–O (76.0 ppm), aromatic carbons
(122.0–155.2 ppm), CO of an ester (165.2 ppm), and CO of an
amide (165.9 ppm). The IR spectrum showed a symmetric
absorption at 3,270 cm-1 attributed to the –NH, three absorp-
tions at 3,062, 2,954, and 1,726 cm-1 attributed to the C=O of
the ester, an absorption at 1,689 cm-1 attributed to the C=O of
E. Vessally (&)
Payame Noor University, Zanjan, Iran
e-mail: vessally@yahoo.com
A. Ramazani (&)
Chemistry Department, Zanjan University,
P.O. Box 45195-313, Zanjan, Iran
e-mail: aliramazani@gmail.com
E. Yaaghubi
Department of Chemistry, Tabriz Branch,
Islamic Azad University, Tabriz, Iran
123

1144
E. Vessally et al.
Fig. 1 Preparation of
a-acyloxycarboxamides 4a–4o
from pyridine carbaldehydes 1,
cyclohexyl isocyanide (2), and
benzoic acid derivatives 3 in
water
HN
O
Ar
O
NC
COOH
O
O
R
H2O
r.t.
Ar
H
R
1
2
3
4a-4o
Ar = 2-pyridinyl, 3-pyridinyl, 4-pyridinyl
R = H, Cl, CH3, NO2, OCH3
Table 1 Conditions and yield of reactions for synthesis of a-acyl-
oxycarboxamides 4a–4o
9100 apparatus. IR spectra were measured on a Perkin-Elmer
RXI FT-IR spectrometer. 1H and 13C NMR spectra (CDCl3)
were recorded on a Bruker Avance spectrometer at 250.0 and
62.9 MHz, respectively. Elemental analyses were performed
by using a Perkin-Elmer 2400(II) CHN/O analyzer. Mass
spectra were recorded on a FINNIGAN-MATT 8430 mass
spectrometer operating at an ionization potential of 20 eV.
The TLC plates were prepared from Merck silica gel powder.
Entry
Products
R
Pyridine
carbaldehyde
Reaction
time/h
Yield/
%
1
4a
4b
4c
4d
4e
4f
H
2-Pyridine
2-Pyridine
2-Pyridine
2-Pyridine
2-Pyridine
3-Pyridine
3-Pyridine
3-Pyridine
3-Pyridine
3-Pyridine
4-Pyridine
4-Pyridine
4-Pyridine
4-Pyridine
4-Pyridine
2
1
1
1
1
2
1
1
1
1
2
1
1
1
1
95
96
96
99
96
95
96
96
99
96
95
96
96
99
96
2
Cl
3
CH3
NO2
OCH3
H
4
5
General procedure for the synthesis of 4a–4o
6
7
4g
4h
4i
Cl
Isocyanide 2 (0.2 mmol) was added to a magnetically
stirred solution of pyridine carbaldehyde 1 (0.2 mmol) and
benzoic acid derivative 3 (0.2 mmol) in 5 cm3 water at
room temperature over 10 min. The mixture was stirred for
the time specified in Table 1 at room temperature after
which time single spot products were obtained by TLC.
The solvent was removed under reduced pressure and the
products were purified by plate thin-layer liquid chroma-
tography and then crystallized.
8
CH3
NO2
OCH3
H
9
10
11
12
13
14
15
4j
4k
4l
Cl
4m
4n
4o
CH3
NO2
OCH3
a-Benzoyloxy-N-cyclohexylpyridine-2-acetamide
(4a, C20H22N2O3)
the amide, and three absorptions at 1,552, 1,272, and
1,114 cm-1 attributed to the C–O.
White powder, yield 95%; m.p.: 154–155 °C; IR (KBr):
A reasonable mechanism for the formation of compounds
4a–4o is shown in Fig. 2. The acid 3 protonates pyridine
carbaldehyde 1 to form an intermediate which is then attacked
by the isocyanide 2 leading to formation of 4 [19] (Fig. 2).
ꢀ
m = 3,270 (NH), 3,062, 2,954, 1,726 (C=O of ester), 1,689
(C=O of amide), 1,552, 1,272, 1,114 (C–O) cm-1; 1H NMR
(CDCl3): d = 0.86–2.32 (m, 10H, 5 CH2 of cyclohexyl),
3.76–3.79 (m, 1H, N–CH), 6.39 (s, 1H, CH–O), 6.78–6.81 (d,
J = 7.24 Hz, 1H, NH), 7.24–8.58 (m, 9H, arom CH) ppm;
13C NMR (CDCl3): d = 24.58, 24.63, 25.47, 32.70, 32.76,
48.42, 76.03, 121.95, 123.49, 128.25, 129.34, 129.95,
133.50, 137.21, 149.11, 155.20, 165.18, 165.90 ppm.
Experimental
Starting materials and solvents were purchased from Merck
(Germany) and Fluka (Switzerland) and were used without
further purification. The reactions were monitored by TLC
and NMR techniques, which indicated that there were no side
products. Melting points were measured on an Electrothermal
a-(4-Chlorobenzoyloxy)-N-cyclohexylpyridine-2-acetamide
(4b, C20H21ClN2O3)
White powder, yield 96%; m.p.: 211–213 °C; IR (KBr):
ꢀ
m = 3,305 (NH), 3,071, 2,937, 1,735 (C=O of ester), 1,664
123

Green synthesis and characterization of novel a-acyloxycarboxamides
1145
Fig. 2 Proposed mechanism for
the formation of compounds
4a–4o
R
O
OH
O
O
H
O
C
O
HO
HC
Ar
N
H
H
C
C
C
N
Ar
Ar
R
HN
O
Ar
O
Ar
HC
HO
N
O
C
O
O
R
R
(C=O of amide), 1,547, 1,265, 1,246 (C–O), 1,117 cm-1; 1H
NMR (CDCl3): d = 0.82–2.37 (m, 10H, 5 CH2 of cyclo-
hexyl), 3.85–3.89 (m, 1H, N–CH), 6.17 (s, 1H, CH–O),
6.76–6.79 (d, J = 7.24 Hz, 1H, NH), 7.22–8.05 (m, 8H, arom
CH) ppm; 13C NMR (CDCl3): d = 24.55, 24.60, 25.47,
32.67, 32.73, 48.95, 76.05, 121.95, 122.08, 128.24, 128.65,
131.05, 136.92, 138.01, 151.18, 155.20, 165.28, 167.90 ppm.
1H, CH–O), 6.82–6.84 (d, J = 7.24 Hz, 1H, NH),
7.24–8.60 (m, 8H, arom CH) ppm; 13C NMR (CDCl3):
d = 24.50, 24.57, 25.43, 32.64, 32.72, 48.59, 76.52,
121.33, 123.65, 131.09, 134.87, 137.39, 149.18, 150.79,
154.59, 163.54, 165.14 ppm.
N-Cyclohexyl-a-(4-methoxybenzoyloxy)pyridine-2-
acetamide (4e, C21H24N2O4)
N-Cyclohexyl-a-(4-methylbenzoyloxy)pyridine-2-
acetamide (4c, C21H24N2O3)
White powder, yield 96%; m.p.: 231–232 °C; IR (KBr):
ꢀ
m = 3,280 (NH), 3,085, 2,960, 1,730 (C=O of ester), 1,665
(C=O of amide), 1,556, 1,447, 1,260, 1,122, 1,091
White powder, yield 96%; m.p.: 216–217 °C; IR (KBr):
1
m = 3,351 (NH), 3,067, 2,986, 1,724 (C=O of ester), 1,677
(C–O) cm-1; H NMR (CDCl3): d = 1.11–2.10 (m, 10H,
ꢀ
(C=O of amide), 1,557, 1,273, 1,257 (C–O) cm-1
;
1H
5 CH2 of cyclohexyl), 3.76–3.80 (m, 1H, N–CH), 3.87 (s,
3H, O–CH3), 6.31 (s, 1H, CH–O), 6.72–6.75 (d,
J = 7.24 Hz, 1H, NH), 6.93–8.58 (m, 8H, arom CH) ppm;
13C NMR (CDCl3): d = 24.58, 24.63, 25.48, 32.73, 32.78,
48.36, 55.47, 75.84, 113.78, 121. 66, 122.00, 123.07, 132.05,
137.18, 149.15, 155.43, 163.81, 164.84, 166.12 ppm.
NMR (CDCl3): d = 0.87–1.73 (m, 10H, 5 CH2 of cyclo-
hexyl), 2.17 (s, 3H, CH3), 3.95–4.09 (m, 1H, N–CH), 6.22
(s, 1H, CH–O), 6.65–6.66 (d, J = 7.24 Hz, 1H, NH),
7.25–8.38 (m, 8H, arom CH) ppm; 13C NMR (CDCl3):
d = 21.42, 24.56, 24.60, 25.37, 32.67, 32.76, 49.05, 75.85,
121.85, 122.97, 126.84, 127.95, 128.85, 137.31, 137.90,
149.99, 155.30, 165.58, 166.90 ppm.
a-Benzoyloxy-N-cyclohexylpyridine-3-acetamide
(4f, C20H22N2O3)
N-Cyclohexyl-a-(4-nitrobenzoyloxy)pyridine-2-acetamide
(4d, C20H21N3O5)
White powder, yield 95%; m.p.: 155–157 °C; IR (KBr):
ꢀ
m = 3,226 (NH), 3,044, 2,961, 1,721 (C=O of ester), 1,688
White powder, yield 99%; m.p.: 245–246 °C; IR (KBr):
ꢀm = 3,316 (NH), 3,075, 2,936, 1,736 (C=O of ester), 1,673
(C=O of amide), 1,548, 1,531, 1,347 (NO), 1,269, 1,251
(C–O) cm-1; 1H NMR (CDCl3): d = 1.13–2.16 (m, 10H, 5
CH2 of cyclohexyl), 3.75–3.77 (m, 1H, N–CH), 6.34 (s,
(C=O of amide), 1,550, 1,265, 1,112 (C–O) cm-1 1H
;
NMR (CDCl3): d = 0.86–2.32 (m, 10H, 5 CH2 of cyclo-
hexyl), 3.76–3.79 (m, 1H, N–CH), 6.39 (s, 1H, CH–O),
6.78–6.81 (d, J = 7.24 Hz, 1H, NH), 7.24–8.58 (m, 9H,
arom CH) ppm; 13C NMR (CDCl3): d = 24.58, 24.64,
123

1146
E. Vessally et al.
25.49, 32.71, 32.76, 48.42, 75.34, 121.95, 128.22, 129.04,
129.85, 133.25, 133.63, 136.59, 148.98, 155.20, 165.18,
165.90 ppm.
a-Benzoyloxy-N-cyclohexylpyridine-4-acetamide
(4k, C20H22N2O3)
White powder, yield 95%; m.p.: 155–157 °C; IR (KBr):
ꢀm = 3,287 (NH), 3,087, 2,931, 1,735 (C=O of ester), 1,658
a-(4-Chlorobenzoyloxy)-N-cyclohexylpyridine-3-acetamide
(4g, C20H21ClN2O3)
(C=O of amide), 1,559, 1,265, 1,118 (C–O) cm-1 1H
;
NMR (CDCl3): d = 0.86–2.32 (m, 10H, 5 CH2 of cyclo-
hexyl), 3.76–3.79 (m, 1H, N–CH), 6.29 (s, 1H, CH–O),
6.78–6.81 (d, J = 7.24 Hz, 1H, NH), 7.24–8.58 (m, 9H,
arom CH) ppm; 13C NMR (CDCl3): d = 24.59, 24.67,
25.49, 32.73, 32.76, 48.42, 77.56, 121.95, 128.12, 129.15,
129.90, 132.93, 149.02, 155.20, 165.18, 165.90 ppm.
White powder, yield 96%; m.p.: 213–215 °C; IR (KBr):
ꢀ
m = 3,279 (NH), 3,099, 2,963, 1,732 (C=O of ester), 1,667
(C=O of amide), 1,560, 1,447, 1,261, 1,112 (C–O), 1,103
(C–Cl) cm-1; H NMR (CDCl3): d = 1.04–2.26 (m, 10H,
1
5 CH2 of cyclohexyl), 3.26–3.30 (m, 1H, N–CH), 5.77
(s, 1H, CH–O), 6.10 (s, 1H, NH), 7.44–8.77 (m, 8H, arom
CH) ppm; 13C NMR (CDCl3): d = 24.55, 24.62, 25.43,
32.69, 32.73, 48.74, 75.35, 121.95, 128.25, 128.29, 131.14,
133.15, 134.59, 138.63, 149.38, 153.20, 165.18,
167.73 ppm.
a-(4-Chlorobenzoyloxy)-N-cyclohexylpyridine-4-acetamide
(4l, C20H21ClN2O3)
White powder, yield 96%; m.p.: 213–215 °C; IR (KBr):
ꢀ
m = 3,277 (NH), 3,095, 2,963, 2,928, 1,732 (C=O of ester),
1,660 (C=O of amide), 1,562, 1,261, 1,093 (C–O), 1,029
(C–Cl) cm-1; 1H NMR (CDCl3): d = 0.82–2.37 (m, 10H, 5
CH2 of cyclohexyl), 3.21–3.26 (m, 1H, N–CH), 5.30 (s, 1H,
CH–O), 6.75–6.78 (d, J = 7.24 Hz, 1H, NH), 7.22–8.08 (m,
8H, arom CH) ppm; 13C NMR (CDCl3): d = 24.59, 24.68,
25.65, 32.69, 32.75, 48.49, 77.69, 122.40, 128.32, 128.50,
131.44, 138.82, 149.23, 150.59, 165.50, 166.50 ppm.
N-Cyclohexyl-a-(4-methylbenzoyloxy)pyridine-3-
acetamide (4h, C21H24N2O3)
White powder, yield 96%; m.p.: 217 °C; IR (KBr):
ꢀ
m = 3,283 (NH), 3,087, 2,986, 1,736 (C=O of ester),
1,661 (C=O of amide), 1,559, 1,414, 1,262, 1,094 cm-1
;
1H NMR (CDCl3): d = 1.04–1.75 (m, 10H, 5 CH2 of
cyclohexyl), 2.07 (s, 3H, CH3), 3.35 (m, 1H, N–CH), 5.80
(s, 1H, CH–O), 6.08 (s, 1H, NH), 7.20–8.35 (m, 8H, arom
CH) ppm; 13C NMR (CDCl3): d = 21.42, 24.56, 24.66,
25.50, 32.70, 32.76, 47.85, 75.24, 123.58, 126.80, 127.75,
128.93, 133.29, 136.39, 137.84, 149.68, 155.30, 165.18,
166.91 ppm.
N-Cyclohexyl-a-(4-methylbenzoyloxy)pyridine-4-
acetamide (4m, C21H24N2O3)
White powder, yield 96%; m.p.: 216–218 °C; IR (KBr):
ꢀ
m = 3,281 (NH), 3,086, 2,962, 1,734 (C=O of ester), 1,660
(C=O of amide), 1,559, 1,260, 1,091 (C–O) cm-1 1H
;
NMR (CDCl3): d = 1.11–2.08 (m, 10H, 5 CH2 of cyclo-
hexyl), 2.39 (s, 3H, CH3), 3.30–3.35 (m, 1H, N–CH), 5.75
(s, 1H, CH–O), 6.06 (s, 1H, NH), 7.35–8.62 (m, 8H, arom
CH) ppm; 13C NMR (CDCl3): d = 20.56, 24.58, 24.64,
25.60, 32.70, 32.78, 48.49, 77.56, 121.40, 127.21, 127.80,
128.35, 141.84, 149.23, 155.15, 163.50, 164.46 ppm.
N-Cyclohexyl-a-(4-nitrobenzoyloxy)pyridine-3-acetamide
(4i, C20H21N3O5)
White powder, yield 99%; m.p.: 247–249 °C; IR (KBr):
ꢀ
m = 3,313 (NH), 3,073, 2,936, 1,733 (C=O of ester), 1,656
(C=O of amide), 1,540, 1,260 (NO2), 1,099, 1,037
(C–O) cm-1; H NMR (CDCl3): d = 1.08–2.49 (m, 10H,
1
5 CH2 of cyclohexyl), 3.24–3.36 (m, 1H, N–CH), 5.75
(s, 1H, CH–O), 6.15 (s, 1H, NH), 7.97–8.79 (m, 8H, arom
CH) ppm; 13C NMR (CDCl3): d = 24.50, 24.61, 25.42,
32.76, 32.82, 48.49, 75.52, 121.33, 122.77, 131.36, 133.55,
134.06, 136.79, 148.48, 152.09, 153.59, 163.64,
165.24 ppm.
N-Cyclohexyl-a-(4-nitrobenzoyloxy)pyridine-4-acetamide
(4n, C20H21N3O5)
White powder, yield 99%; m.p.: 242–243 °C; IR (KBr):
ꢀ
m = 3,313 (NH), 3,073, 2,936, 1,733 (C=O of ester), 1,656
(C=O of amide), 1,540, 1,260 (N=O), 1,099, 1,037
(C–O) cm-1; H NMR (CDCl3): d = 1.03–2.06 (m, 10H,
1
5 CH2 of cyclohexyl), 3.35–3.47 (m, 1H, N–CH), 5.84 (s,
1H, CH–O), 6.25 (s, 1H, NH), 7.24–8.60 (m, 8H, arom
CH) ppm; 13C NMR (CDCl3): d = 24.50, 24.58, 25.00,
32.68, 32.72, 48.59, 77.42, 120.97, 121.33, 131.00, 134.06,
149.23, 152.09, 154.20, 163.54, 165.14 ppm.
N-Cyclohexyl-a-(4-methoxybenzoyloxy)pyridine-3-
acetamide (4j, C21H24N2O4)
White powder, yield 96%; m.p.: 231–232 °C; IR (KBr):
ꢀ
m = 3,297 (NH), 3,089, 2,929, 1,734 (C=O of ester), 1,658
(C=O of amide), 1,559, 1,448, 1,265, 1,117 (C–O) cm-1
;
1H NMR (CDCl3): d = 1.11–2.10 (m, 10H, 5 CH2 of
cyclohexyl), 3.76–3.80 (m, 1H, N–CH), 3.87 (s, 3H,
O–CH3), 6.31 (s, 1H, CH–O), 6.72–6.75 (d, J = 7.24 Hz,
1H, NH), 6.93–8.50 (m, 8H, arom CH) ppm; 13C NMR
(CDCl3): d = 24.58, 24.63, 25.70, 32.70, 32.78, 48.36,
55.47, 77.41, 113.78, 121.28, 122.97, 131.98, 133.35,
136.69, 148.62, 153.19, 163.71, 164.84, 166.32 ppm.
N-Cyclohexyl-a-(4-methoxybenzoyloxy)pyridine-4-
acetamide (4o, C21H24N2O4)
White powder, yield 96%; m.p.: 236–237 °C; IR (KBr):
ꢀ
m = 3,289 (NH), 3,095, 2,963, 1,733 (C=O of ester), 1,663
(C=O of amide), 1,561, 1,447, 1,262, 1,123 (C–O) cm-1
;
1H NMR (CDCl3): d = 1.11–2.10 (m, 10H, 5 CH2 of
cyclohexyl), 3.76–3.80 (m, 1H, N–CH), 3.87 (s, 3H,
123

Green synthesis and characterization of novel a-acyloxycarboxamides
1147
¨
5. Domling A, Beck B, Herdtweck E, Antuch W, Oefner C, Yehia
N, Gracia-Marques A (2007) Arkivoc 17:99
O–CH3), 6.31 (s, 1H, CH–O), 6.72–6.75 (d, J = 7.24 Hz,
1H, NH), 6.93–8.50 (m, 8H, arom CH) ppm; 13C NMR
(CDCl3): d = 24.58, 24.63, 24.95, 32.69, 32.78, 48.36,
55.47, 77.41, 112.71, 121.33, 123.17, 132.25, 149.23,
150.43, 155.43, 163.81, 166.12 ppm.
¨
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Acknowledgments The authors are thankful to the Payame Noor
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