Silica supported perchloric acid: A Convenient and environmentally friendly catalyst for the one-pot multicomponent synthesis of β-acetamido ketones

Article abstract of DOI:10.1002/cjoc.201190038

A modified Dakin-West one-pot, four-component condensation of an aryl aldehyde, aryl ketone, acetyl chloride and acetonitrile in the presence of silica supported perchloric acid as an active, inexpensive, recoverable and recyclable catalyst is reported fo

Full text of DOI:10.1002/cjoc.201190038

FULL PAPER
Silica Supported Perchloric Acid: A Convenient and
Environmentally Friendly Catalyst for the One-pot
Multicomponent Synthesis of β-Acetamido Ketones
Nasr-Esfahani, Masoud*
Montazerozohori, Morteza
Gholampour, Tahere
Department of Chemistry, Yasouj University, Yasouj 75918-74831, Iran
A modified Dakin-West one-pot, four-component condensation of an aryl aldehyde, aryl ketone, acetyl chloride
and acetonitrile in the presence of silica supported perchloric acid as an active, inexpensive, recoverable and recy-
clable catalyst is reported for the synthesis of β-acetamido ketones under mechanical stirring and ultrasonic irradia-
tion conditions. This system has advantages of short reaction times, good to excellent yields and the ability to carry
out the large scale reactions. The use of ultrasound increases the rate of reactions compared with reactions at reflux
conditions.
Keywords silica supported perchloric acid, β-acetamido ketone, Dakin-West reaction, supported catalyst, multi-
component reaction
Introduction
Multicomponent reactions (MCRs) have proved to be
remarkably successful in generating molecular com-
plexity in a single synthetic step operation.21 This proc-
ess has emerged as an efficient and powerful tool in
modern synthetic chemistry allowing the facile creation
of several new bonds in a one-pot transformation. The
organic chemists have transformed this powerful tech-
nology into one of the most efficient and economic tools
for combinatorial and parallel synthesis.22
The β-acetamido carbonyl compounds has gained
considerable attention in organic synthesis, owing to
their importance as valuable building blocks for prepa-
ration of β-amino acids,1 or 1,3-amino alcohols2 as well
as for the synthesis of various antibiotics such as nik-
komycins or neopolyoxines3 and potent molecules in
α-glucosidase inhibitory activity.4
β-Acetamido ketones were usually prepared through
Michael addition to α,β-unsaturated ketones,5 acylation
of β-aminoketones6 or photoisomerization of phthalim-
ides.7
The conventional way for the preparation of these
compounds is the Dakin-West reaction involving con-
densation of an α-amino acid with acetic anhydride in
the presence of a base via an intermediate azalactone.8
Iqbal and coworkers10 reported the best-known route for
the synthesis of β-acetamido carbonyl compounds in the
one-pot condensation of aldehyde, enolizable ketone,
acetyl chloride, and acetonitrile catalyzed by both
CoCl2,9 and Montmorillonite K-10 clay.
Synthesis of β-acetamido ketones has also been
catalyzed using Sn(II),11 Sc(III) triflates,12 InCl3,12
H2SO4/SiO2,13 zirconia,14 ZnO,15 phosphotungstic
acid,16 sulfamic acid,17a aluminium hydrogen sulfate,17b
CeCl3,18 cerium(IV) sulfate19 and Nafion-H.20 These
methods are valuable but they suffer from different
drawbacks such as hazardous reagents, high temperature,
expensive catalysts, long reaction time, tedious workup
and low yield. Hence, the development of a simple and
new protocol with more efficiency is still in demand.
In recent years, using of solid supported acids have
become more important in synthetic organic chemistry
due to some advantages such as enhanced selectivity,
reactivity and easy product isolation.23 Silica supported
perchloric acid (HClO4-SiO2) has received considerable
attention for numerous organic transformations, includ-
ing acylation of alcohols24 or aldehydes,25 the Ferrier
rearrangement,26 cleavage of benzylidene acetals,27
electrophilic substitution of indole with various alde-
hydes and ketones,28 synthesis of Hantzsch dihydro-
pyridine,29 homoallylic amines through a three-compo-
nent reaction,30 tetrasubstituted imidazoles under sol-
vent free conditions31 and 1,8-dioxo-octahydro-
xanthenes via Knoevenagel condensation.32 In view of
its inherent properties like environmental friendly,
greater selectivity, operational simplicity, non-corrosive
nature, moisture-insensitive and ease of isolation, it is
therefore, interesting to find out the behavior of the
catalytic system in the synthesis of β-acetamido ketones.
Ultrasound has been used in organic synthesis in the
last decades both in cavitations and per-cavitations re-
gimes.33 The success and advantages of sonochemical
reactions include higher yields, shorter reaction times
*
E-mail: manas@mail.yu.ac.ir
Received July 13, 2010; revised September 16, 2010; accepted September 29, 2010.
Chin. J. Chem. 2011, 29, 123— 130
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Nasr-Esfahani, Montazerozohori & Gholampour
FULL PAPER
and milder reaction conditions in comparison to classi-
cal methods.34 The mostly important effect of ultra-
sound by passing its waves through a liquid medium is
the generation of many cavities. This leads to develop-
ment of high temperatures and high pressures within the
cavities during their collapse.
were used. Table 1 shows differences in catalytic activ-
ity among catalysts having 30—60 wt% of HClO4 on
silica. Lowering the loading of the deposited perchloric
acid causes the reduction of the catalytic activity. No
improvements in the reaction rate and yield were ob-
served by increasing the amount of acid on SiO2 from
30 to 60 wt%. Since 50 wt% of perchloric acid was the
best catalyst loading, it was used to study the effect of
various parameters on yields.
Results and discussion
In this work, we wish to report a convenient and ef-
ficient procedure for the synthesis of β-acetamido ke-
tones using Silica supported perchloric acid as catalyst
(Eq. 1).
Table 1 Effect of HClO4-SiO2 weight ratios in the synthesis of
β-acetamido ketones from benzaldehyde, acetophenone, acetoni-
trile and acetyl chloride
Entry
HClO4-SiO2/wt%
Time/min
Yielda/%
1
2
3
4
30
40
50
60
50
35
20
20
68
75
85
86
a Isolated yields.
Preparation of the supported perchloric acid
Perchloric acid (2.67 g, 18.7 mmol, as a 70% aque-
ous solution) was added to the suspension of silica gel
(23.13 g, 230—400 mesh) in diethyl ether (75 mL). The
mixture was concentrated and the residue dried under
vacuum at 100 ℃ for 72 h to afford HClO4-SiO2 (0.75
Effect of catalyst concentration
The catalyst concentration was varied over a range
of 0.07—0.2 g (0.25—1 mmol of H＋) on the basis of
the total volume of the reaction mixture. Table 2 shows
the effect of catalyst concentration on the reaction of
benzaldehyde, acetophenone, acetonitrile and acetyl
chloride. The yield of the corresponding β-acetamido
ketones increased with increasing catalyst concentration
from 0.25 to 0.75 mmol of H＋. Further addition of
catalyst had no noticeable effect on the yield. This was
due to the fact that beyond a certain concentration, there
exists an excess of catalyst sites over what is actually
required by the reactant molecules, and hence, the addi-
tional catalyst does not increase the rate of the reaction.
Therefore, in all further reactions 0.75 mmol of H＋
(equal to 75 mol% of HClO4) were used for 50 wt% of
perchloric acid.
－1
mmol•g ) as a free flowing powder.
FT-IR spectra can be used as a powerful technique
for the investigation of surface interaction between per-
chloric acid and inorganic supports. Pure acid display
infrared bands at 1089, 1062 [νas(ClO4)], 962 [νs(ClO4)],
－1 35
627 [δas(ClO4)] and 467 [δs(ClO4)] cm .
However, small shifts of vibrations were registered
indicating interactions of the support with the oxygen
atoms of acid. In addi－tion, a broad, intense band cen-
1
tered around 3433 cm (νO— stretching) and a weak
H
absorption at 1630 cm−1 [δ(H2O) bending] indicate the
presence of water (Figure 1).
Table 2 Investigation of catalyst effects in the synthesis of β-
acetamido-β-phenyl propiophenone from benzaldehyde, aceto-
phenone, acetonitrile and acetyl chloridea
Entry Amount of catalyst/g H+/mmol Time/min Yieldb/%
1
2
3
4
0.05
0.1
0.25
0.5
0.75
1
55
35
20
20
60
78
85
88
0.15
0.2
a 50% HClO4-SiO2 were used as catalyst. b Isolated yields.
Figure 1 FT-IR spectra of silica supported perchloric acid (A),
perchlorate anion (B) and SiO2 (C).
Synthesis of β-acetamido ketones catalyzed by sup-
ported perchloric acid
Effect of perchloric acid loading on SiO2
The results from the reactions of aryl aldehydes, aryl
methyl ketones and acetyl chloride in the presence of
optimized HClO4-SiO2 in acetonitrile at 80 ℃ and un-
der ultrasonic irradiation are shown in Table 3. The ex-
For investigation of the effect of different amounts
of HClO4 loading on support in the synthesis of
β-acetamido ketones, various weight percents of acid
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One-pot Multicomponent Synthesis of β-Acetamido Ketones
perimental procedure for this reaction requires no inert
atmosphere. Both aromatic aldehydes and acetophe-
nones bearing either activating or deactivating groups
underwent transformation well to the corresponding
β-acetamido ketones, without the formation of any side
products, in high to excellent yields (Entries 1—25).
When the reaction mixture was exposed to ultrasonic
irradiation, the corresponding β-acetamido ketones de-
rivatives were obtained in 5—15 min. When the same
reaction was carried out in the thermal condition, the
reaction times were longer (20—65 min).
Interestingly, no acetylation of an aromatic hydroxyl
group was observed under the reaction conditions and
the corresponding β-acetamido ketone was isolated in
an excellent yield (Table 3, Entries 24 and 25). We ob-
served that aliphatic aldehydes react under these condi-
tions, but produce the corresponding product in low
yields (Table 3, Entry 26).
Table 3 Synthesis of β-acetamido ketones in the presence of HClO4-SiO2 under thermal and ultrasonic conditions
Thermal
Time/min Yieldb/%
Ultrasonic
Time/min Yield/%
Entry
1
Ar
Ar'
Producta
C6H5
C6H5
20
65
85
5
90
2
3-NO2C6H4
C6H5
80
15
84
3
4
5
6
7
8
4-NO2C6H4
2-NO2C6H4
4-ClC6H4
2-ClC6H4
4-BrC6H4
C6H5
C6H5
C6H5
55
50
30
25
30
40
78
85
85
92
87
10
10
6
80
90
87
92
90
90
C6H5
C6H5
5
C6H5
6
4-BrC6H4
80
10
9
3-NO2C6H4
4-NO2C6H4
4-BrC6H4
4-BrC6H4
45
45
80
90
10
10
85
90
10
Chin. J. Chem. 2011, 29, 123— 130
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Nasr-Esfahani, Montazerozohori & Gholampour
Continuted
FULL PAPER
Thermal
Time/min Yieldb/%
Ultrasonic
Entry
11
Ar
Ar'
Producta
Time/min Yield/%
4-ClC6H4
4-BrC6H4
30
25
35
40
92
90
90
80
6
5
94
92
90
85
12
13
14
2-ClC6H4
4-BrC6H4
4-BrC6H4
4-BrC6H4
4-BrC6H4
8
2,4-Cl2C6H3
10
15
16
17
2-Cl-6-FC6H3
4-BrC6H4
4-NO2C6H4
4-NO2C6H4
60
40
55
87
80
75
15
8
90
86
80
C6H5
3-NO2C6H4
12
18
19
20
21
22
23
4-NO2C6H4- 4-NO2C6H4-
55
35
45
45
30
55
85
90
90
70
80
70
12
8
87
90
92
78
85
74
4-ClC6H4
4-BrC6H4
4-FC6H4
4-NO2C6H4
4-NO2C6H4
4-NO2C6H4
10
10
5
4-CH3OC6H4 4-NO2C6H4
4-CH3C6H4
4-NO2C6H4
12
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One-pot Multicomponent Synthesis of β-Acetamido Ketones
Continued
Ultrasonic
Time/min Yield/%
Thermal
Time/min Yieldb/%
Entry
24
Ar
Ar'
Producta
2-OHC6H4
4-NO2C6H4
40
35
76
75
20
10
80
80
30
25
2-OHC6H4
3-NO2C6H4
8
26
CH3CH2CH2
C6H5
125
30
a All products were characterized by 1H NMR, 13C NMR and IR spectroscopy and compared with those reported in literatures.9,19,20 b Iso-
lated yields.
Effect of unsupported acid in synthesis of
To use HClO4-SiO2 in large scale synthesis espe-
cially in chemical laboratory, a typical reaction was
performed for synthesis of 1 with tenfold amounts of
reactants and catalyst with respect to one mentioned in
the experimental section. The result showed that the
yield of 80% in these conditions is comparable with one
in Table 3.
To achieve the reaction efficiency of recovered
catalyst, the reaction mixture of 1 was filtered and
washed with hot acetonitrile twice to give silica sup-
ported perchloric acid. The recovered acid was used
again for synthesis of 1 that led to the yield of 80%. It
can also be recovered and reused at least four times
without noticeable losing activity.
β-acetamido ketones
As shown in Table 4, in the presence of perchloric
acid without supporting on SiO2, the synthesis of
β-acetamido ketones were performed in longer time
with reduced yields in comparison with supported one.
For example, in presence of HClO4-SiO2, the reaction of
benzaldehyde and acetophenone (Entry 1) was com-
pleted in 20 min with 85% yield, while by using of un-
supported catalyst this reaction was carried out in 100
min with 50% yield. This results show that supporting
of perchloric acid on SiO2 accelerates catalytic strength
of this catalyst.
The plausible mechanism based on Iqbal’s sugges-
tion36 for the formation of β-acetamido ketones is shown
in Scheme 1. The presence of acetyl chloride is neces-
sary for the transformation and the desired product in its
absence was not prepared even after 3 h.
Conclusion
In conclusion, we have found an efficient, inexpen-
sive and straightforward procedure for one-pot synthesis
of β-acetamido ketones using HClO4-SiO2 as catalyst.
The catalyst can be easily prepared and can be handled
safely. Moreover, nonhygroscopic and inexpensive for
this transformation are other advantages of this proce-
dure.
Scheme 1
Experimental
Chemicals were purchased from Merck, Fluka and
Aldrich chemical companies. All of the products were
identified by comparison of their physical and spectral
data with those of authentic samples. IR spectra were
1
recorded on a JASCO IR-680 spectrophotometer. H
NMR spectra were obtained with a Bruker-Arance AQS
300 MHz or a Bruker 400 Ultrasheild (400 MHz) spec-
trometers. The ultrasonic device used was an UP 400 S
instrument.
Preparation of the supported catalyst
The silica gel supported HClO4 was prepared by
Chin. J. Chem. 2011, 29, 123— 130
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Nasr-Esfahani, Montazerozohori & Gholampour
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Table 4 Synthesis of some imidazolines in the presence of HClO4
HClO4
Time/min
HClO4/ SiO2
Time/min
Entry
1
Product
Yielda/%
50
Yield/%
100
150
20
30
85
2
3
60
45
35
92
80
76
180
120
65
40
4
a Isolated yield.
mixing silica gel (6 g, Merck grade 40, 0.063—0.2 mm)
with 70% aqueous acid solution (0.70 g) in diethyl ether
(20 mL). The resulting mixture was stirred for 30 min.
After removal of water and ether in a rotary evaporator,
the solid powder was dried at 80 ℃ for 4 h followed
by 4 h calcinations at 120 ℃.
5.6, 17.5 Hz, 1H), 3.74 (dd, J＝5.2, 17.4 Hz, 1H),
5.56—5.64 (m, 1H), 6.93 (d, J＝7.5 Hz, 1H), 7.42—
7.47 (m, 3H), 7.54 (t, J＝7.5, 1H), 7.68 (d, J＝7.4 Hz,
1H), 7.86 (d, J＝6.9 Hz, 2H), 8.05 (d, J＝6.9 Hz, 1H),
8.17 (s, 1H); R (KBr) ν: 3292, 3067, 1687, 1643, 1523,
－ 1
1350, 1290, 750, 685, 632 cm . Anal. calcd for
C17H16N2O4: C 65.38, H 5.16, N 8.97; found C 65.3, H
5.2, N 8.8.
General procedure for the preparation of
β-acetamido ketones
N-[1-(4-Chlorophenyl)-3-phenyl-3-oxopropyl]ace-
tamide (5) m.p. 147—149 ℃ (Lit.37 146 ℃); Rf＝
A mixture of the aryl aldehyde (1 mmol), aryl ketone
(1 mmol), acetyl chloride (0.3 mL) and acetonitrile (2
mL) in the presence of HClO4-SiO2 (0.15 g, equal to
0.75 mmol H＋) was heated at 80 ℃, with stirring for 20
—65 min. The progress of the reaction was monitored
by TLC. After completion of the reaction, the mixture
was filtered and the filtrate poured into 50 mL ice-water.
The solid product was filtered, washed with ice-water
and recrystallized from ethyl acetate/n-heptane to give
the pure products in 70%—92% yields based on the
starting aldehyde (Table 3).
1
0.50 (n-hexane/ethyl acetate, V∶V＝1∶4); H NMR
(CDCl3, 400 MHz) δ: 1.98 (s, 3H), 3.36 (dd, J＝6.2,
17.0 Hz, 1H), 3.71 (dd, J＝5.0, 17.2 Hz, 1H), 5.50—
5.56 (m, 1H), 6.76 (d, J＝7.5 Hz, 1H), 7.17—7.23 (m,
4H), 7.46 (t, J＝7.2, 2H), 7.54 (t, J＝7.5 Hz, 1H), 7.84
(d, J＝7.7 Hz, 2H); IR (KBr) ν: 3280,－3085, 1680, 1640,
1
1545, 1260, 1110, 890, 825, 687 cm . Anal. calcd for
C17H16ClNO2: C 67.66, H 5.34, N 4.64; found C 67.7, H
5.5, N 3.4.
N-[3-(4-Bromophenyl)-1-(4-chlorophenyl)-3-oxo-
propyl]acetamide (11) m.p. 141—143 ℃ (Lit.38
140—142 ℃); Rf＝0.42 (n-hexane/ethyl acetate, V∶
N-(1,3-Diphenyl-3-oxopropyl)acetamide (1) m.p.
101 —103 ℃ (Lit.19 102 —104 ℃); Rf ＝0.48
(n-hexane/ethyl acetate, V ∶V ＝1 ∶4); 1H NMR
(CDCl3, 400 MHz) δ: 1.85 (s, 3H), 3.45 (dd, J＝6.5,
16.8 Hz, 1H), 3.75 (dd, J＝5.5, 16.8 Hz, 1H), 5.50—
5.54 (m, 1H), 6.68 (d, J＝7.5 Hz, 1H), 7.20—7.28 (m,
5H), 7.49—7.52 (m, 3H), 7.90 (d, J＝7.7 Hz, 1H), 8.28
(d, J＝7.5 Hz, 1H); IR (KBr) ν: 3290, 3093, 16－90, 1640,
1
V＝1∶4); H NMR (CDCl3, 400 MHz) δ: 2.07 (s, 3H),
3.32 (dd, J＝7.9, 16.8 Hz, 1H), 3.80 (dd, J＝7.8, 16.3
Hz, 1H), 5.59—5.64 (m, 1H), 7.34 (d, J＝7.6 Hz, 1H),
7.62 (dd, J＝8.2 Hz, 2H), 7.83 (dd, J＝8.3 Hz, 2H),
7.92 (d, J＝8.5 Hz, 2H), 8.33 (d, J＝8.4 Hz, 2H); IR
(KBr) ν: 3263, 3053, 1680, 1632, 1585, 1293, 1085, 887,
1
－1
1543, 1440, 1347, 1295, 1197, 990, 740 cm . Anal.
827 cm . Anal. calcd for C17H15BrClNO2: C 53.64, H
calcd for C17H17NO2: C 76.38, H 6.41, N 5.24; found C
76.4, H 6.5, N 5.3.
3.97, N 3.68; found C 53.7, H 4.0, N 3.8.
N-[3-(4-Bromophenyl)-1-(2,4-dichlorophenyl)-3-
oxopropyl]acetamide (14) m.p. 192—195 ℃; Rf＝
N-[1-(3-Nitrophenyl)-3-phenyl-3-oxopropyl]ace-
tamide(2) m.p. 112—114 ℃ (Lit.19 110—112 ℃);
1
0.53 (n-hexane/ethyl acetate, V∶V＝1∶4); H NMR
1
Rf＝0.49 (n-hexane/ethyl acetate, V∶V＝1∶4); H
(CDCl3, 400 MHz) δ: 1.72 (s, 3H), 3.36 (dd, J＝10.8,
NMR (CDCl3, 400 MHz) δ: 2.02 (s, 3H), 3.47 (dd, J＝
16.8 Hz, 1H), 3.1 (dd, J＝9.8, 16.8 Hz, 1H), 5.50—5.54
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One-pot Multicomponent Synthesis of β-Acetamido Ketones
(m, 1H), 6.98 (d, J＝2.1 Hz, 1H), 7.11 (d, J＝2.0 Hz,
1H), 7.25 (s, 1H), 7.37 (d, J＝6.7 Hz, 2H), 7.58 (d, J＝
6.8 Hz, 2H); 13C NMR (CDCl3) δ: 23.24, 42.80, 47.29,
127.53, 128.77, 129.39, 129.60, 129.96, 132.22, 133.47,
135.50, 138.31, 169.89, 196.38; IR (KBr) ν: 3288, 3087,
1687, 1656, 1585, 1549, 1474, 1290, 998, 810, 750
propyl]acetamide (25) m.p. 131—132 ℃ (Lit.19
128—130 ℃); Rf＝0.44 (n-hexane/ethyl acetate, V∶
1
V＝1∶4); H NMR (CDCl3, 400 MHz) δ: 1.97 (s, 3H),
3.42 (dd, J＝6.9, 17.5 Hz, 1H), 3.64 (dd, J＝7.6, 17.3
Hz, 1H), 5.44—5.50 (m, 1H), 6.89—6.95 (m, 2H), 7.53
(t, J＝7.8 Hz, 1H), 7.60—7.68 (m, 1H), 7.76—7.83 (m,
2H), 8.13 (d, J＝6.8 Hz, 1H), 8.26 (s, 1H), 8.62 (d, J＝
7.2 Hz, 1H), 10.96 (s, 1H); IR (KBr) ν: 3267, 3054,
－1
cm . Anal. calcd for C17H14BrCl2NO2: C 49.19, H 3.40,
N 3.37; found C 49.1, H 3.3, N 3.4.
－1
N-[3-(4-Bromophenyl)-1-(2-chloro-6-flourophen-
yl)-3-oxopropyl]acetamide (15) m.p. 135—138 ℃;
Rf ＝0.6 (n-hexane/ethyl acetate, V∶V＝1∶4); 1H
NMR (CDCl3, 400 MHz) δ: 1.96 (s, 3H), 3.48 (dd, J＝
8.4, 15.51 Hz, 1H), 3.57 (dd, J＝8.1, 15.5 Hz, 1H), 6.17
—6.20 (m, 1H), 6.35 (d, J＝8.4 Hz, 1H), 6.97—6.99 (m,
1H), 7.18 (d, J＝2.4 Hz, 2H), 7.58 (d, J＝6.9 Hz, 2H),
7.80 (d, J＝7.0 Hz, 2H); 13C NMR (CDCl3) δ: 23.63,
43.15, 45.47, 115.28, 126.56, 126.58, 129.150, 129.94,
130.03, 130.20, 132.47, 134.65, 134.70, 135.43, 169.62,
196.29; IR (KBr) ν: 3291, 3079, 1681, 1650, 1580, 1545,
1652, 1533, 1348, 1093, 765 cm . Anal. calcd for
C17H16N2O5: C 62.19, H 4.91, N 8.53; found C 62.1, H
5.0, N 8.6.
Acknowledgement
We are thankful to Yasouj University for partial
support of this work.
References
1
Mukhopadhyay, M.; Bhatia, B.; Iqbal, J. Tetrahedron Lett.
1997, 38, 1083.
－1
1425, 1289, 1240, 997, 908, 788, 598 cm . Anal. calcd
for C17H14BrClFNO2: C 51.22, H 3.54, N 3.51; found C
51.1, H 3.6, N 3.5.
2
(a) Barluenga, J.; Viado, A. L.; Aguilar, E.; Fustero, S.;
Olano, B. J. Org. Chem. 1993, 58, 5972.
N-[3-(4-Nitrophenyl)-1-(3-nitrophenyl)-3-oxopro-
pyl]acetamide (17) m.p. 155—157 ℃ (Lit.39 154—
157 ℃); Rf＝0.45 (n-hexane/ethyl acetate, V∶V＝1∶
(b) Enders, D.; Moser, M.; Geibel, G.; Laufer, M. C.
Synthesis 2004, 2040.
3
(a) Kobinata, K.; Uramoto, M.; Nishii, M.; Kusakabe, H.;
Nakamura, G.; Isono, K. Agric. Biol. Chem. 1980, 44, 1709.
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Wolf, G.; Zaehner, H. Arch. Microbiol. 1976, 107, 249.
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1
4); H NMR (CDCl3, 400 MHz) δ: 2.03 (s, 3H), 3.45
(dd, J＝7.5, 16.3 Hz, 1H), 3.68 (dd, J＝7.9, 16.0 Hz,
1H), 5.82 (s, 1H), 6.85 (d, J＝7.1 Hz, 1H), 7.21 (dd, J＝
7.5 Hz, 2H), 7.32 (dd, J＝7.7 Hz, 2H), 7.65—7.83 (m,
4H); IR (KBr) ν: 3279,－3075, 1691, 1645, 1512, 1350,
4
5
6
7
1
1535, 997, 851, 740 cm . Anal. calcd for C17H15N3O6:
C 57.14, H 4.23, N 11.76; found C 57.2, H 4.3, N 12.8.
N-[3-(4-Nitrophenyl)-1-(4-nitrophenyl)-3-oxopro-
pyl]acetamide (18) m.p. 151—153 ℃ (Lit.4 150 ℃);
1
Rf＝0.43 (n-hexane/ethyl acetate, V∶V＝1∶4); H
NMR (CDCl3, 400 MHz) δ: 2.05 (s, 3H), 3.52 (dd, J＝
8.5, 17.2 Hz, 1H), 3.80 (dd, J＝8.9, 17.0 Hz, 1H), 5.60
—5.64 (m, 1H), 6.67 (d, J＝8.0 Hz, 1H), 7.53 (dd, J＝
8.5 Hz, 2H), 7.74 (dd, J＝8.7 Hz, 2H), 8.12 (d, J＝8.9
Hz, 2H), 8.28 (d, J＝9.0 Hz, 2H); IR (KBr) ν: 3271,
3078, 1697, 1663, 1512, 1348, 1111, 999, 855, 740
8
9
Dakin, H. D.; West, R. J. Biol. Chem. 1928, 78, 745.
Rao, I. N.; Prabhakaran, E. N.; Das, S. K.; Iqbal, J. J. Org.
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10 Bahulayan, D.; Das, S. K.; Iqbal, J. J. Org. Chem. 2003, 68,
5735.
11 Nagarapu, L.; Bantu, R.; Puttireddy, R. Appl. Catal. A: Gen.
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－1
cm . Anal. calcd for C17H15N3O6: C 57.14, H 4.23, N
11.76; found C 57.2, H 4.3, N 12.8.
N-[3-(4-Nitrophenyl)-1-(4-bromophenyl)-3-oxo-
propyl]acetamide (20) m.p. 141—143 ℃; Rf＝0.36
(n-hexane/ethyl acetate, V ∶V ＝1 ∶4); 1H NMR
(CDCl3, 400 MHz) δ: 2.02 (s, 3H), 3.46 (dd, J＝10.5,
17.0 Hz, 1H), 3.80 (dd, J＝10.9, 16.9 Hz, 1H), 5.47—
5.51 (m, 1H), 6.47 (d, J＝7.8 Hz, 1H), 7.21 (dd, J＝8.4
Hz, 2H), 7.44 (dd, J＝8.5 Hz, 2H), 8.05 (d, J＝9.1 Hz,
2H), 8.28 (d, J＝9.2 Hz, 2H); 13C NMR (CDCl3) δ:
23.82, 44.15, 49.93, 122.18, 124.41, 128.77, 129.60,
132.37, 139.78, 141.13, 150.99, 170.02, 197.01; IR
(KBr) ν: 3286, 3082, 1680, 16－45, 1590, 1510, 1497,
12 Pandey, G.; Singh, R. P.; Garg, A.; Singh, V. K. Tetrahe-
dron Lett. 2005, 46, 2137.
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1328, 998, 842, 740
cm 1. Anal. calcd for
C17H15BrN2O4: C 52.19, H 3.86, N 7.16; found C 52.1,
H 3.8, N 7.1.
N-[1-(2-Hydroxyphenyl)-3-(3-nitrophenyl)-3-oxo-
18 Khan, A. T.; Choudhury, L. H.; Parvin, T.; Ali, M. A. Tet-
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